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Publication numberCN1859894 B
Publication typeGrant
Application numberCN 200480028042
PCT numberPCT/US2004/024489
Publication date26 Jan 2011
Filing date28 Jul 2004
Priority date26 Sep 2003
Also published asCA2540201A1, CN1859894A, DE602004016353D1, EP1663115A1, EP1663115B1, US7250452, US7465758, US20050070627, US20080014560, WO2005034884A1
Publication number200480028042.0, CN 1859894 B, CN 1859894B, CN 200480028042, CN-B-1859894, CN1859894 B, CN1859894B, CN200480028042, CN200480028042.0, PCT/2004/24489, PCT/US/2004/024489, PCT/US/2004/24489, PCT/US/4/024489, PCT/US/4/24489, PCT/US2004/024489, PCT/US2004/24489, PCT/US2004024489, PCT/US200424489, PCT/US4/024489, PCT/US4/24489, PCT/US4024489, PCT/US424489
Inventors乔尔D奥克斯曼, 拉杰迪普卡尔古特卡尔, 阿弗申法尔萨菲
Applicant3M创新有限公司
Export CitationBiBTeX, EndNote, RefMan
External Links: SIPO, Espacenet
Dental compositions with arylsulfinate salts and hardening method and uses
CN 1859894 B
Abstract
Polymerizable compositions and methods are provided that include an ethylenically unsaturated compound and an arylsulfinate salt. The polymerizable compositions are useful as hardenable dental compositions.
Claims(37)  translated from Chinese
  1. 一种可聚合的组合物,其包括:烯键式不饱和化合物;和引发剂体系,其包括芳基亚磺酸盐,该芳基亚磺酸盐包括阴离子和阳离子,该阴离子为下式ⅠAr1‑SO2‑ Ⅰ该阳离子选自:1)式Ⅲ的含磷阳离子:其中每个R2独立地是未取代的烷基,羟基取代的烷基,未取代的芳基,由烷基、羟基、或其组合取代的芳基,2)含氮的阳离子,其包括含有带正电荷的氮原子的4~12元杂环的环结构,所述杂环是饱和或不饱和的,并含有选自氮、氧、硫、或其组合的高达3个杂原子,其中所述环结构是未取代的或被选自烷基、芳基、酰基、烷氧基、芳氧基、卤素、巯基、氨基、羟基、偶氮、氰基、羧基、烷氧基羰基、芳氧基羰基、卤代羰基、或其组合的取代基取代,或者3)式Ⅱ的阳离子:其中R1和各R4独立地是含3‑10个碳原子的烷基;其中该芳基亚磺酸盐在N,N‑二甲基甲酰胺中相对于银/硝酸银参考电极的氧化电势为0.0~+0.4伏,及其中Ar1是未取代的或用吸电子基或吸电子基与供电子基的组合所取代的C6‑30芳基或C3‑30杂芳基,和,其中所述可聚合的组合物是适用于口腔环境中的牙科材料。 A polymerizable composition comprising: an ethylenically unsaturated compound; and an initiator system comprising arylalkylene sulfonates, aryl-sulphonates include the anion and cation, the anion of the formula ⅠAr1 -SO2- Ⅰ The cation is selected from: 1) a phosphorus-containing cation of Formula Ⅲ: wherein each R2 is independently an unsubstituted alkyl group, a hydroxyl-substituted alkyl group, an unsubstituted aryl group, the alkyl group, a hydroxyl group, or combinations substituted aryl group, 2) a nitrogen-containing cation, which comprises containing a positively charged nitrogen atom of the 4 to 12 membered heterocyclic ring structure, the heterocyclic ring is a saturated or unsaturated, selected from nitrogen and containing , oxygen, sulfur, or combinations thereof of up to three heteroatoms, wherein said ring structure is unsubstituted or is selected from alkyl, aryl, acyl, alkoxy, aryloxy, halogen, mercapto, amino, hydroxy, azo, cyano, carboxy, an alkoxycarbonyl group, an aryloxycarbonyl group, a halogenated carbonyl group, substituents, or combinations thereof, or 3) a cationic Ⅱ formula: wherein R1 and R4 each independently containing 3 alkyl group to 10 carbon atoms; and wherein the aryl phosphite salt in N, N- dimethylformamide with respect to a silver / silver nitrate reference electrode oxidation potential of 0.0 to + 0.4 volts, and wherein Ar1 is unsubstituted or substituted with a combination of an electron withdrawing group or an electron withdrawing group and electron donating group substituted with C6-30 aryl or C3-30 heteroaryl, and wherein the polymerizable composition is suitable for oral environment dental materials. FSB00000152351600011.tif,FSB00000152351600012.tif FSB00000152351600011.tif, FSB00000152351600012.tif
  2. 2.如权利要求1所述的可聚合的组合物,还包括牙科添加剂。 2. The polymerizable composition according to claim 1, further comprising a dental additive.
  3. 3.如权利要求2所述的可聚合的组合物,其中所述牙科添加剂是药物。 As claimed in claim 2 polymerizable composition, wherein the dental additive is a drug.
  4. 4.如权利要求2所述的可聚合的组合物,其中所述牙科添加剂选自氟化物、增白剂、抗龋齿剂、再矿化剂、酶、呼吸清凉剂、麻醉剂、凝块剂、酸中和剂、化学治疗剂、免疫反应调节剂、指示剂、染料、颜料、润湿剂、表面活性剂、缓冲剂、粘度改性剂、触变胶、填料、多元醇、抗菌剂、稳定剂、处理口腔干燥的试剂、脱敏剂和其组合。 The polymerizable composition according to claim 2, wherein the dental additive is selected from fluoride, brighteners, anti-caries agents, remineralizing agents, enzymes, breath fresheners, anesthetics, clot agent, acid neutralizers, chemotherapeutic agents, immune response modifiers, indicators, dyes, pigments, wetting agents, surfactants, buffering agents, viscosity modifiers, thixotropes, fillers, polyols, antimicrobial agents, stabilizing agent, reagent xerostomia, desensitizers, and combinations thereof.
  5. 5.如权利要求2所述的可聚合的组合物,其中所述牙科添加剂是抗真菌剂。 5. The composition according to claim 2 polymerizable composition, wherein the dental additive is an anti-fungal agent.
  6. 6.如权利要求2所述的可聚合的组合物,其中所述牙科添加剂是木糖醇。 As claimed in claim 2 polymerizable composition, wherein the dental additive is xylitol.
  7. 7.如权利要求2所述的可聚合的组合物,其中所述牙科添加剂是磷酸钙化合物。 7. The composition according to claim 2 polymerizable composition, wherein the dental additive is a calcium compound.
  8. 8.如权利要求2-4中任一项所述的可聚合的组合物,其中所述牙科添加剂是可光漂白的染料。 As claimed in any one of claims 2-4 wherein the polymerizable composition, wherein the dental additive is a dye photo-bleaching.
  9. 9.如权利要求1所述的可聚合的组合物,其中所述组合物是选自分散体、悬浮液、乳液、溶液和其组合的形式。 9. The polymerizable composition as claimed in claim 1, wherein said composition is selected from dispersion, suspensions, emulsions, solutions and any combination thereof.
  10. 10.如权利要求1所述的可聚合的组合物,其中所述组合物是底物、涂层、密封剂、修复材料或其组合。 10. The polymerizable composition as claimed in claim 1, wherein said composition is a substrate, coatings, sealants, restorative materials, or combinations thereof.
  11. 11.如权利要求10所述的可聚合的组合物,其中所述组合物是牙科粘合剂。 11. The composition of claim 10, wherein the polymerizable composition, wherein said composition is a dental adhesive.
  12. 12.如权利要求11所述的可聚合的组合物,其中所述的牙科粘合剂是正牙粘合剂。 12. The composition of claim 11, wherein the polymerizable composition, wherein the binder is a dental orthodontic adhesives.
  13. 13.如权利要求11所述的可聚合的组合物,其中所述的牙科粘合剂是胶合剂。 13. The composition of claim 11, wherein the polymerizable composition, wherein the dental adhesive is glue.
  14. 14.如权利要求1所述的可聚合的组合物,其中所述引发剂体系还包括能够吸收波长为250〜1000纳米的光化射线的敏化剂。 14. The polymerizable composition as claimed in claim 1, wherein the initiator system further comprises a wavelength capable of absorbing actinic radiation 250~1000 nm sensitizer.
  15. 15.如权利要求14所述的可聚合的组合物,其中所述敏化剂选自樟脑酮、苯偶酰、糠偶酰、3,3,6,6_四甲基环己二酮、菲醌,1-苯基-1,2-丙烷二酮和其组合。 15. The composition of claim 14 wherein the polymerizable composition, wherein the sensitizer is selected from camphor ketone, benzil, benzil bran, 3,3,6,6_ tetramethyl-cyclohexanedione, phenanthrenequinone, 1-phenyl-1,2-propane dione and combinations thereof.
  16. 16.如权利要求1所述的可聚合的组合物,其中所述引发剂体系还包括在N,N-二甲基甲酰胺中相对于银/硝酸银参考电极的还原电势为+0. 4〜-1. 0伏的电子受体。 16. The claim 1 polymerizable composition, wherein the initiator system further comprises N, N- dimethylformamide with respect to the reduction potential of the silver / silver nitrate reference electrode is +0. 4 ~ -1 electron acceptor. zero volts.
  17. 17.如权利要求16所述的可聚合的组合物,其中所述电子受体是碘鐺盐、六芳基二咪唑、过硫酸盐、过氧化物、氧化态的金属离子或其组合。 17. The composition of claim 16, wherein the polymerizable composition, wherein the electron acceptor is iodine pan salt, an aromatic six-diimidazole, persulfates, peroxides, oxidation state metal ion or a combination thereof.
  18. 18.如权利要求1所述的可聚合的组合物,其中所述引发剂体系还包括不同于芳基亚磺酸盐的还原剂。 18. The polymerizable composition as claimed in claim 1, wherein the initiator system further comprises a reducing agent different from arylalkylene sulfonates.
  19. 19.如权利要求1所述的可聚合的组合物,其中所述组合物是自蚀性的、可聚合的牙科组合物,和所述烯键式不饱和化合物包括带有酸官能团的烯键式不饱和化合物和不带酸官能团的烯键式不饱和化合物。 19. The polymerizable composition as claimed in claim 1, wherein said composition is from Erodibility, polymerizable dental composition, and compound the ethylenically unsaturated include ethylenically with acid functional groups unsaturated compounds and ethylenically without acid functional group unsaturated compounds.
  20. 20.如权利要求19所述的可聚合的组合物,其中所述酸官能团包括羧酸官能团、磷酸官能团、磺酸官能团或其组合。 20. The composition of claim 19 polymerizable, wherein said acid functional group include carboxylic acid functionality, phosphoric acid functionality, sulfonic acid functionality, or combinations thereof.
  21. 21.如权利要求1所述的可聚合的组合物,其中所述组合物是非水性的。 21. The polymerizable composition according to claim 1, wherein said composition is non-aqueous.
  22. 22.如权利要求1所述的可聚合的组合物,其中所述组合物还包括填料。 22. The polymerizable composition according to claim 1, wherein said composition further comprises a filler.
  23. 23.如权利要求22所述的可聚合的组合物,其中所述填料是纳米填料。 23. The composition of claim 22 polymerisable, wherein the filler is a nanofiller.
  24. 24.如权利要求19或20的可聚合的组合物,还包括:表面活性剂;和水;和其中所述自蚀性的、可聚合的牙科组合物是乳液。 19 or 24. The composition of claim 20 polymerizable, further comprising: a surfactant; and water; and wherein the self-corrosion resistance, polymerizable dental composition is an emulsion.
  25. 25.如权利要求24所述的可聚合的组合物,其中所述乳液是油包水乳液。 25. The composition of claim 24 wherein the polymerizable composition, wherein the emulsion is a water in oil emulsion.
  26. 26.如权利要求24所述的可聚合的组合物,其中所述乳液是物理稳定的。 26. The composition of claim 24 wherein the polymerizable composition, wherein the emulsion is physically stable.
  27. 27.如权利要求24所述的可聚合的组合物,其中所述组合物包括小于30wt-%的水。 27. Claim 24 wherein the polymerizable composition, wherein said composition comprises less than 30wt-% of water.
  28. 28.如权利要求24所述的可聚合的组合物,其中所述组合物是油包水微乳液。 28. The composition of claim 24 wherein the polymerizable composition, wherein said composition is a water in oil microemulsion.
  29. 29.如权利要求24所述的可聚合的组合物,还包括:40-90wt-%的填料,其中所述可聚合的组合物是自粘合的组合物。 29. The polymerizable composition according to claim 24, further comprising: 40-90wt-% of a filler, wherein the polymerizable composition is a self-adhesive composition.
  30. 30. 一种硬化如权利要求14或15所述的可聚合的组合物的方法,其包括照射该可聚合的组合物。 A composition polymerizable 30. A hardened as claimed in claim 14 or 15, which comprises irradiating the polymerizable composition.
  31. 31. 一种硬化如权利要求16或17所述的可聚合的组合物的方法,其包括:混合各成分以形成可硬化的组合物;和使该牙科组合物硬化。 A composition polymerizable 31. A hardened as claimed in claim 16 or claim 17, comprising: mixing the ingredients to form a hardenable composition; and so that the hardened dental compositions.
  32. 32.如权利要求31所述的方法,其中所述成分还包括能够吸收波长为250〜1000纳米的光化射线的敏化剂。 32. The method according to claim 31, wherein said composition further comprises a wavelength capable of absorbing actinic radiation sensitizers 250~1000 nm.
  33. 33.如权利要求32所述的方法,其中所述方法还包括照射所述组合物。 33. The method according to claim 32, wherein the method further comprises irradiating the composition.
  34. 34.如权利要求14或15的可聚合的组合物在制备用于处理需要处理的牙齿结构表面的粘合剂中的用途,其中该用途包括将所述可聚合的组合物施加到所述牙齿结构表面上和照射所述组合物。 14 or 34. The composition of claim 15 polymerizable binder in the preparation of the tooth structure to be treated for the surface treatment of use, wherein the use comprises the polymerizable composition is applied to the tooth irradiating the surface of the structure and composition.
  35. 35.如权利要求14或15的可聚合的组合物在制备用于处理需要处理的牙齿结构表面的牙科材料中的用途,其中该用途包括将所述可聚合的组合物施加到所述牙齿结构表面上和照射所述组合物。 14 or 35. The composition of claim 15 polymerizable dental material was prepared in the tooth structure to be treated for the surface treatment of use, wherein the use comprises the polymerizable composition is applied to the tooth structure and irradiating the surface of the composition.
  36. 36.如权利要求29的可聚合的组合物在制备用于处理需要处理的牙科结构表面的粘合剂中的用途。 36. The composition of claim 29 for the preparation of polymerizable binder for treating a dental structure surface to be treated in use.
  37. 37.如权利要求29的可聚合的组合物在制备用于处理需要处理的牙科结构表面的牙科材料中的用途。 37. The composition of claim 29 in polymerizable dental material preparation process requires handling of a dental structure surface for use.
Description  translated from Chinese

含有芳基亚磺酸盐的牙科组合物及其硬化方法和制备用途 Dental compositions and hardening method comprising aryl-sulfonate and preparation purposes

[0001] 背景 [0001] BACKGROUND

[0002] 可聚合的组合物可用于各种牙齿和正牙应用中,包括例如,底物,牙科粘合剂,正牙粘合剂,涂层,密封剂,胶合剂,复合聚合物,修复材料和其组合。 [0002] The polymerizable composition can be used for various dental and orthodontic applications, including, for example, substrates, dental adhesives, orthodontic adhesives, coatings, sealants, adhesives, polymer composite, restorative materials and combinations thereof. 例如,可聚合的牙科粘合剂通常用于将牙科材料(例如,修复材料,如固化或未固化的复合体,如玻璃离聚物胶合剂,改性的玻璃离聚物胶合剂等;填料;密封剂;镶嵌物;裱贴物;牙冠;牙桥等)粘合到相关牙科结构。 For example, dental adhesive polymerizable dental material typically used (e.g., repair materials, such as cured or uncured composite, such as glass ionomer cement, modified glass ionomer bonding agent; filler ; sealant; inlays; onlays; crowns; Dental bridges) adhered to the relevant dental structure. 相似地,正牙粘合剂用于将正牙用具(例如,牙环,颊管,牙带,牙夹板,牙扣, 舌固定器,和咬合器)粘合到牙科结构。 Similarly, orthodontic adhesive for orthodontic appliances (eg, tooth ring, buccal tubes, dental tape, dental splints, dental deduction, tongue holder, and an occluder) adhered to the dental structure.

[0003] 牙科和正牙应用中用的可聚合的组合物通常包括可聚合的成分和引发剂体系。 [0003] The dental and orthodontic applications using polymerizable composition typically comprises a polymeric component and an initiator system. 通常,引发剂体系包括烯键式不饱和可聚合成分的自由基聚合,从而硬化组合物。 Typically, the initiator system comprises an ethylenically unsaturated polymerizable radical polymerizable component, thereby hardening the composition. 在一些可聚合的组合物中,聚合包括照射组合物。 In some of the polymerizable composition, including polymerizable composition is irradiated. 在其他可聚合的组合物中,聚合包括混合引发剂体系的各成分。 Other polymerizable composition, the polymerization initiator system comprises mixing the ingredients.

[0004] 需要牙科和正牙应用中用的可聚合的组合物在聚合之前具有足够的稳定性(例如,物理或化学稳定性),但是经聚合引发后容易硬化。 [0004] The composition may require aggregation of dental and orthodontic applications used before polymerization has sufficient stability (for example, physical or chemical stability), but easily cured by polymerization initiators. 尽管引发剂体系的性质通常会影响各种性能平衡,但是也需要牙科组合物可用于各种引发剂体系中(例如,单组分组合物,二组分组合物,酸性组合物等)。 Although the nature of the initiator system typically affect the balance of various properties, but also require a dental composition may be used in a variety of initiator systems (e.g., one-component compositions, two component composition, acidic composition, etc.). 此外,也需要在聚合过程中或聚合之后,弓I发剂体系不会发生不需要的颜色变化。 In addition, it needs to or during polymerization after polymerization initiator system will not bow I unwanted color changes. 本发明的优选实施方案满足了这些要求中的一些。 A preferred embodiment of the present invention satisfies these requirements in some of them.

[0005] 发明概述 [0005] Summary of the Invention

[0006] 本发明提供适用于在口腔环境中用作牙科材料的可聚合的组合物,和使用这种组合物的方法。 [0006] The present invention provides a dental material suitable for use in the oral environment polymerizable composition, and methods of use of such compositions. 可聚合的组合物包括烯键式不饱和化合物和引发剂体系。 Polymerizable composition comprising an ethylenically unsaturated compound and an initiator system. 在一些实施方案中,可聚合的组合物包括牙科添加剂(例如,可光漂白的染料)。 In some embodiments, the polymerizable composition includes a dental additive (e.g., photo-bleaching of the dye). 可聚合的组合物可以是分散体,悬浮液,乳液,溶液,或其组合的形式。 The polymerizable composition may be a dispersion, suspensions, emulsions, solutions, or a combination thereof. 优选地,可聚合的组合物是化学稳定的。 Preferably, the polymeric composition is chemically stable. 可聚合的组合物可以是,例如,底物,牙科粘合剂,正牙粘合剂,涂层,密封剂,胶合剂,修复材料, 或其组合。 The polymerizable composition may be, for example, substrates, dental adhesives, orthodontic adhesives, coatings, sealants, adhesives, repair materials, or combinations thereof.

[0007] 引发剂体系包括芳基亚磺酸盐,该芳基亚磺酸盐包括阴离子和阳离子,该阴离子为下式I [0007] The initiator system comprises arylalkylene sulfonates, aryl-sulphonates include the anion and cation, the anion of formula I

[0008] Ar1-SO2- I [0008] Ar1-SO2- I

[0009] 该阳离子包括带正电荷的氮原子或者带正电荷的磷原子,其中该芳基亚磺酸盐在N,N- 二甲基甲酰胺中相对于银/硝酸银参考电极的氧化电势为0. 0〜+0. 4伏,及其中Ar1 是未取代的或用吸电子基或吸电子基与供电子基的组合所取代的C6,芳基和C3,杂芳基。 [0009] The cation comprising a positively charged nitrogen atom or a positively charged phosphorus atom, wherein the aryl phosphite salt in N, N- dimethylformamide with respect to the oxidation potential of the silver / silver nitrate reference electrode 0. 0~ + 0.4 volts, and wherein Ar1 is an unsubstituted or a combination of an electron withdrawing group or an electron withdrawing group and electron donating group substituted C6, aryl, and C3, heteroaryl. 优选地,芳基亚磺酸盐与可聚合组合物中的烯键式不饱和化合物互溶。 Preferably, the aryl-sulfonate polymerizable composition of ethylenically unsaturated compound solubility.

[0010] 在一些实施方案中,引发剂体系还包括敏化剂,电子受体,和/或不同于芳基亚磺酸盐的还原剂。 [0010] In some embodiments, the initiator system further includes a sensitizer, an electron acceptor, and / or different from aryl-sulfonate reducing agent. 优选地,敏化剂能够吸收波长为250〜1000纳米的光化射线。 Preferably, the sensitizer is capable of absorbing actinic radiation having a wavelength of 250~1000 nm. 优选地,该电子受体在在N,N-二甲基甲酰胺中相对于银/硝酸银参考电极的还原电势为+0. 4〜-1. 0 伏。 Preferably, in the electron acceptor in N, N- dimethylformamide with respect to a silver / silver nitrate reduction potential of the reference electrode is +0. 4 ~-1 0 volts.

[0011] 本发明还提供硬化所述可聚合组合物的方法。 [0011] The present invention also provides a method of hardening the polymerizable composition. 所述方法通过将可硬化的牙科组合物涂覆到牙科结构表面,和硬化组合物,可用于处理牙科结构表面。 The method of the hardenable dental composition to a dental structure surface, and hardening the composition, may be used to handle dental structure surface.

5[0012] 在一个实施方案中,本发明提供一种硬化可聚合的组合物的方法,其中上述引发剂体系还包括能够吸收波长为250〜1000纳米的光化射线的敏化剂。 5 [0012] In one embodiment, the present invention provides a method of hardening a composition polymerizable, wherein said initiator system further comprises a wavelength capable of absorbing actinic radiation 250~1000 nm sensitizer. 该方法包括照射可聚合的组合物。 The method comprises irradiating the polymerizable composition. 可选择地,引发剂体系还包括在N,N- 二甲基甲酰胺中相对于银/硝酸银参考电极的还原电势为+0. 4〜-1. 0伏的电子受体。 Alternatively, the initiator system further comprises N, N- dimethylformamide with respect to the reduction potential of the silver / silver nitrate reference electrode as electron acceptor +0. 4 ~-1 zero volts.

[0013] 在另一个实施方案中,本发明提供一种硬化可聚合的组合物的方法,其中上述引发剂体系还包括在N,N-二甲基甲酰胺中相对于银/硝酸银参考电极的还原电势为+0. 4〜-1. 0伏的电子受体。 [0013] In another embodiment, the present invention provides a method of hardening a composition polymerizable, wherein said initiator system further comprises N, N- dimethylformamide with respect to a silver / silver nitrate reference electrode The reduction potential of the electron acceptor +0. April to-1 zero volts. 该方法包括:混合可聚合的组合物的各成分,形成可硬化的牙科组合物,和使该牙科组合物硬化。 The method comprising: mixing the ingredients of the polymerizable composition to form hardenable dental composition, and so that the hardened dental compositions. 可选择地,引发剂体系还包括能够吸收波长为250〜 1000纳米的光化射线的敏化剂。 Alternatively, the initiator system further comprises capable of absorbing actinic radiation having a wavelength of 1000 nm 250~ sensitizer. 可选择地,该方法还包括照射可硬化的牙科组合物。 Alternatively, the method further comprises irradiating the hardenable dental composition.

[0014] 在另一个方面中,本发明提供自蚀的可聚合牙科组合物和/或自粘合的可聚合牙科组合物。 [0014] In another aspect, the present invention provides a self-etching polymerizable dental composition and / or polymerizable dental composition self adhesive. 可选择地,组合物是非水性的。 Alternatively, the composition is non-aqueous. 可选择地,组合物可以包括填料,可以是纳米填料。 Alternatively, the composition may include fillers, may be nanofiller. 在一些实施方案中,组合物可以包括水和表面活性剂(例如,非离子表面活性剂和/或可聚合的表面活性剂),和组合物可以是乳液(例如,油包水乳液和/或微乳液)。 In some embodiments, the composition may include water and surfactants (eg, nonionic surfactants and / or polymeric surfactant), and the composition may be an emulsion (for example, water in oil emulsion and / or microemulsion). 在一些实施方案中,乳液包括小于30wt-%的水。 In some embodiments, the emulsion comprises less than 30wt-% of water. 优选地,组合物是物理和/或化学稳定的。 Preferably, the composition is a physical and / or chemical stability. 可选择地,组合物包括牙科添加剂(例如,可光漂白的染料)。 Alternatively, the composition includes a dental additive (e.g., photo-bleaching of the dye).

[0015] 在一个实施方案中,本发明提供一种自蚀的可聚合的牙科组合物,其包括:带有酸官能团的烯键式不饱和化合物;不带酸官能团的烯键式不饱和化合物;和上述引发剂体系。 [0015] In one embodiment, the present invention provides a self-etching dental polymerizable composition comprising: ethylenic acid functional groups with unsaturated compounds; ethylenically without acid functional group unsaturated compound ; and said initiator system. 酸官能团可以包括羧酸官能团,磷酸官能团,磺酸官能团,或其组合。 Acid functional groups may include carboxylic acid functionality, phosphoric acid functionality, sulfonic acid functionality, or combinations thereof.

[0016] 在另一个实施方案中,本发明提供一种自粘合可聚合的牙科组合物,其包括:带有酸官能团的烯键式不饱和化合物;不带酸官能团的烯键式不饱和化合物;上述引发剂体系,和至少40wt_%的填料。 [0016] In another embodiment, the present invention provides a self-adhesive polymerizable dental composition comprising: ethylenic acid functional groups with unsaturated compounds; ethylenically without unsaturated acid functional groups said initiator system, and at least 40wt_% filler; compound. 可选择地,组合物是自蚀的。 Alternatively, the composition is from erosion.

[0017] 定义 [0017] defines

光化射线"指能够产生光化学活性的电磁射线。 酰基"指式-(CO)Ra的一价基团,其中Ra是烷基或芳基。 Actinic radiation. "Refers to the ability to produce electromagnetic radiation photochemical activity group" refers to the formula - (CO) Ra is a monovalent group in which Ra is an alkyl or aryl group. 链烯基"指链烯的一价基团(即,链烯是具有至少一个碳-碳双键 Alkenyl "refers to alkenyl monovalent group (ie, olefin having at least one carbon - carbon double bond

[0018] 本文中,术语 [0018] As used herein, the term

[0019] 本文中,术语 [0019] As used herein, the term

[0020] 本文中,术语 [0020] As used herein, the term

的脂肪族化合物)。 Aliphatic compounds).

[0021] 本文中,术语 [0021] As used herein, the term

基,丙氧基,丁氧基等。 Group, propoxy, butoxy.

[0022] 本文中,术语 [0022] As used herein, the term

氧基羰基。 Butoxycarbonyl.

[0023] 本文中,术语 [0023] As used herein, the term

[0024] 本文中,术语 [0024] As used herein, the term

族化合物)。 Compounds).

[0025] 本文中,术语"烷基"指烷烃的一价基团。 [0025] As used herein, the term "alkyl" refers to a monovalent alkane group. 烷基可以是直链、支链、环状或其组合, 并通常含有1〜30个碳原子。 The alkyl group may be linear, branched, cyclic, or combinations thereof, and generally contain 1~30 carbon atoms. 在一些实施方案中,烷基含有1〜20,1〜14,1〜10,4〜 10,4〜8,1〜6,或1〜4个碳原子。 In some embodiments, the alkyl group contains 1~20,1~14,1~10,4~ 10,4~8,1~6, or 1 ~ 4 carbon atoms. 烷基的例子包括但不限于甲基,乙基,正丙基,异丙基, 正丁基,叔丁基,异丁基,正戊基,正己基,环己基,正辛基,正庚基,和乙基己基。 Examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, isobutyl, n-pentyl, n-hexyl, cyclohexyl, n-octyl, n-heptyl group, and ethyl hexyl.

[0026] 本文中,术语"烷基磺酰基"指式-SO2R的一价基团,其中R是烷基。 [0026] As used herein, the term "alkylsulfonyl" refers to a monovalent group of formula -SO2R wherein R is alkyl.

[0027] 本文中,术语"氨基"指式-NRb2的一价基团,其中每个Rb独立地是氢,烷基,或芳 [0027] As used herein, the term "amino" refers to the type -NRb2 monovalent group, wherein each Rb is independently hydrogen, alkyl, or aryl

烷氧基"指式-OR的基团,其中R是烷基。例子包括甲氧基,乙氧 Alkoxy "refers to a group of the formula -OR, wherein R is an alkyl group. Examples include methoxy, ethoxy

烷氧基羰基"指式-(CO)OR的一价基团,其中R是烷基。例子是乙 Alkoxycarbonyl group "refers to the formula - (CO) OR a monovalent group, wherein R is an alkyl group B is an example.

烷氧基磺酰基"指式-SO3R的一价基团,其中R是烷基。 炔基"指炔的一价基团(即,炔是具有至少一个碳_碳三键的脂肪 Alkoxy sulfonyl group "refers to a monovalent group of the formula -SO3R, wherein R is alkyl. Alkynyl" refers to a monovalent alkynyl group (i.e., an alkynyl having at least one carbon-carbon triple bond fat _

6基。 6 group. 在伯氨基中,每个Rb是氢。 In primary amino, each Rb is hydrogen. 在仲氨基中,一个Rb是氢,另一个Rb是烷基或芳基。 In a secondary amino group, one Rb is hydrogen and the other Rb is alkyl or aryl. 在叔氨基中,两个Rb都是烷基或芳基。 In the tertiary amino groups, two Rb are alkyl or aryl.

[0028] 本文中,术语"氨基羰基"指式-(CO)NRb2的一价基团,其中每个Rb独立地是氢, 烷基,或芳基。 [0028] As used herein, the term "aminocarbonyl" refers to the formula - (CO) NRb2 a monovalent group, wherein each Rb is independently hydrogen, alkyl, or aryl.

[0029] 本文中,术语"芳香"指碳环芳香化合物或基团和杂芳香化合物或基团。 [0029] As used herein, the term "aromatic" refers to carbocyclic aromatic compounds or groups and heteroaromatic compounds or groups. 碳环芳香化合物是仅在芳环结构中含有碳原子的化合物。 Carbon ring aromatic compound is a compound containing only carbon atoms in the aromatic ring structure. 杂芳香化合物是在芳环结构中含有至少一个选自S,0,N,或其组合的杂原子的化合物。 Heteroaromatic compound containing S, 0, N, or a combination of compounds, at least one hetero atom selected from an aromatic ring structure.

[0030] 本文中,术语"芳基"指一价芳香碳环基团。 [0030] As used herein, the term "aryl" refers to a monovalent aromatic carbocyclic group. 芳基可以具有一个芳环,或可以包括与芳环连接或稠合的5个碳环结构。 An aryl group which may have one aromatic ring, or may comprise connected or fused aromatic ring 5 carbocyclic ring structure. 其他环结构可以是芳香、非芳香,或其组合。 Other ring structures can be aromatic, non-aromatic, or combinations thereof. 芳基的例子包括但不限于苯基,联苯基,三联苯基,蒽基,萘基,苊基,蒽醌基,菲基,蒽基,芘基,二萘嵌苯基,和芴基。 Examples of aryl groups include, but are not limited to, phenyl, biphenyl, terphenyl, anthryl, naphthyl, acenaphthyl, anthraquinone group, phenanthryl, anthryl, pyrenyl, perylene phenyl, and fluorenyl .

[0031] 本文中,术语"芳氧基"指式-OAr的一价基团,其中Ar是芳基。 [0031] As used herein, the term "aryloxy" refers to the type -OAr monovalent group, wherein Ar is an aryl group.

[0032] 本文中,术语"芳氧基羰基"指式-(CO)OAr的一价基团,其中Ar是芳基。 [0032] As used herein, the term "aryloxycarbonyl group" refers to the formula - (CO) OAr a monovalent group, wherein Ar is an aryl group.

[0033] 本文中,术语"芳氧基磺酰基"指式-SO3Ar的一价基团,其中Ar是芳基。 [0033] As used herein, the term "aryloxy sulfonyl" refers to a monovalent formula -SO3Ar group wherein Ar is aryl.

[0034] 本文中,术语〃偶氮〃指式-N = N-的二价基团。 [0034] As used herein, the term refers to the type 〃 〃 azo -N = N- divalent group.

[0035] 本文中,术语"羰基"指式-(CO)-的二价基团,其中碳原子通过双键与氧原子连接。 [0035] As used herein, the term "carbonyl" refers to the formula - (CO) - a divalent group in which the carbon atoms connected by a double bond to an oxygen atom.

[0036] 本文中,术语〃羧基〃指式-(CO)OH的一价基团。 [0036] As used herein, the term refers 〃 〃 carboxyl formula - (CO) OH monovalent group.

[0037] 本文中,术语"共轭的"指具有至少两个碳-碳双键或三键的不饱和化合物,其中碳_碳单键与碳_碳双键或三键交替。 [0037] As used herein, the term "conjugated" means having at least two carbon - carbon double bond or unsaturated triple bond, wherein the carbon-carbon single bond _ _ carbon-carbon double bond or triple bond alternately.

[0038] 本文中,术语〃氰基〃指式-CN的基团。 [0038] As used herein, the term refers to the formula -CN 〃 〃 cyano group.

[0039] 本文中,术语"二烷基膦酸酯基"指式-(PO) (OR)2的基团,其中R是烷基。 [0039] As used herein, the term "dialkyl phosphonate group" refers to the formula - (PO) (OR) 2 group, wherein R is an alkyl group. 本文中,式"(PO)“指磷原子通过双键与氧原子键合。 Herein, the formula "(PO)" refers to a phosphorus atom through a double bond with an oxygen atom is bonded.

[0040] 本文中,术语"二芳基膦酸酯基"指式-(PO) (OArb)2的基团,其中Arb是杂芳基。 [0040] As used herein, the term "diaryl phosphonate group" refers to the formula - (PO) (OArb) groups 2, wherein Arb is heteroaryl.

[0041] 本文中,术语"供电子"指能够供给电子的取代基。 [0041] As used herein, the term "electron donating" refers to substituents capable of supplying electrons. 适合的例子包括但不限于伯 Suitable examples include, but are not limited to, primary

氨基,仲氨基,叔氨基,羟基,烷氧基,芳氧基,烷基,或其组合。 An amino group, a secondary amino group, tertiary amino group, a hydroxyl group, an alkoxy group, an aryloxy group, an alkyl group, or a combination thereof.

[0042] 本文中,术语"吸电子"指能够吸引电子的取代基。 [0042] As used herein, the term "electron-withdrawing" refers to the ability to attract electrons substituent. 适合的例子包括但不限于卤素,氰基,氟代烷基,全氟烷基,羧基,氨基羰基,烷氧基羰基,芳氧基羰基,商代羰基,甲酰基,羰基,磺酸基,烷氧基磺酰基,芳氧基磺酰基,全氟烷基磺酰基,烷基磺酰基,偶氮,链烯基,炔基,二烷基膦酸酯基,二芳基膦酸酯基,或其组合。 Suitable examples include, but are not limited to, halogen, cyano, fluoroalkyl, perfluoroalkyl, carboxy, aminocarbonyl, alkoxycarbonyl, aryloxycarbonyl, Shang carbonyl, formyl, a carbonyl group, a sulfonic acid group, alkoxy sulfonyl group, aryloxy sulfonyl group, perfluoroalkyl sulfonyl, alkylsulfonyl, azo, alkenyl, alkynyl, dialkyl phosphonate, diaryl phosphonate group, or combinations thereof.

[0043] 本文中,术语"氟代烷基"指至少一个氢原子被氟原子取代的烷基。 [0043] As used herein, the term "fluoroalkyl" refers to at least one hydrogen atom is replaced by fluorine atoms.

[0044] 本文中,术语"甲酰基"指式-(CO)H的一价基团,其中碳通过双键与氧原子相连。 [0044] As used herein, the term "formyl" refers to the formula - (CO) H to a monovalent group, wherein the carbon is connected by a double bond to an oxygen atom.

[0045] 本文中,术语"卤代"指卤素基团(8卩斤,(:1,81~,或1)。在一些实施方案中,卤代基是F或Cl。 [0045] As used herein, the term "halo" refers to a halogen group (8 Jie pounds (: 1,81 ~, or 1) In some embodiments, halo is F or Cl..

[0046] 本文中,术语"卤代羰基"指式-(CO)X的一价基团,其中X是卤素基团(S卩,F, Cl,Br,或I)。 [0046] As used herein, the term "halo carbonyl" refers to the formula - (CO) X is a monovalent group in which X is a halogen group (S Jie, F, Cl, Br, or I).

[0047] 本文中,术语"杂芳基"指具有5〜7元芳环的一价基团,在芳环中包括一个或多个独立地选自S,0,N,或其组合的杂原子。 [0047] As used herein, the term "heteroaryl" refers to a 5 ~ 7-membered aromatic ring of a monovalent group, in an aromatic ring includes one or more groups independently selected from S, 0, N, or a combination of miscellaneous atoms. 这种杂芳基可以与芳香、脂肪或其组合的五元环 Such heteroaryl may ring with an aromatic, aliphatic or a combination of five dollars

7结构连接或稠合。 7 structural connections or fused. 杂芳基的例子包括但不限于喹啉基,异喹啉基,喹唑啉基,喹喔啉基,噌啉基,苯并呋喃基,苯并巯基苯基,苯并噁唑基,苯并噻唑基,苯并咪唑基,吲哚基,二氮杂萘基,苯并噻二唑基,苯并三嗪基,吩嗪基,菲啶基,吖啶基,和吲唑基等。 Examples of heteroaryl groups include, but are not limited to, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, cinnolinyl, benzofuranyl, benzo thiol group, a benzoxazolyl, benzene and thiazolyl, benzimidazolyl, indolyl, quinazolinyl, benzo thiadiazolyl, benzo triazinyl, phenazine group, phenanthridinyl, acridinyl, indazolyl, and the like. 杂芳基是杂环的子集。 Heteroaryl is a subset of heterocycle.

[0048] 本文中,术语"杂环"指具有饱和或不饱和的环结构并且在环中包括一个或多个独立地选自S, 0,N,或其组合的杂原子的一价基团。 [0048] As used herein, the term "heterocyclic" refers to a saturated or unsaturated ring structure and in the ring includes one or more groups independently selected from S, 0, N, or combinations thereof hetero atom monovalent group . 杂环可以是单环,双环,或者可以与另一个环或双环稠合。 Heterocyclic ring may be monocyclic, bicyclic, or with another ring or bicyclic ring. 稠合环或双环可以是饱和或不饱和的,并可以是碳环或含有杂原子。 Fused bicyclic ring or may be saturated or unsaturated, and may be carbocyclic or contains hetero atoms.

[0049] 本文中,术语 [0049] As used herein, the term

[0050] 本文中,术语 [0050] As used herein, the term

[0051] 本文中,术语氟代烷基的子集。 [0051] As used herein, the term & subset fluoroalkyl group.

[0052] 本文中,术语 [0052] As used herein, the term

[0053] 本文中,术语 [0053] As used herein, the term

羟基"指式-OH的基团。 巯基"指式-SH的基团。 Hydroxy "refers to a group of formula -OH. Thiol group" means a group of the formula -SH.

全氟烷基"指所有氢原子都被氟原子所取代的烷基。全氟烷基是 Perfluoroalkyl group "refers to all of the hydrogen atoms are substituted by fluorine atoms alkyl perfluoroalkyl group is

全氟烷基磺酰基"指式-SO2Rf的一价基团,其中Rf是全氟烷基。 磺酸基"指式-SO3HW基团。 Perfluoroalkylsulfonyl group "refers to a monovalent formula -SO2Rf group wherein Rf is a perfluoroalkyl group. Sulfonic acid group" means a group of formula -SO3HW.

[0054] 本文中,“粘合剂"或"牙科粘合剂"指牙齿结构(例如,牙齿)预处理所用的组合物,从而将"牙科材料"(例如,"修复材料",正牙用具(例如,牙环),或"正牙粘合剂")连接到牙齿结构上。 [0054] As used herein, "binder" or "dental adhesive" means tooth structure (for example, dental) pretreatment with a composition, which will "dental material" (eg, "repair material", orthodontic appliances (e.g., teeth ring), or "orthodontic adhesive") is connected to the tooth structure. “正牙粘合剂"指一种高度(通常大于40wt-% )填充的组合物(与"牙科粘合剂"相比,更相似于"修复材料"),用于使正牙用具与牙齿结构(例如,牙齿)的表面连接。 "Orthodontic adhesive" refers to a highly (generally greater than 40wt-%) (compared to the "dental adhesive", more similar to "repair material") filler composition for making orthodontic appliances with teeth Surface structure (e.g., tooth) connection. 通常,牙齿结构表面被预处理,例如,通过浸蚀,涂底物,和/或涂覆粘合剂以增强"正牙粘合剂"与牙齿结构表面的粘合。 Typically, the structure of the tooth surface is pretreated, e.g., by etching, priming, and / or coated with an adhesive to enhance bonding "orthodontic adhesive" structure of the surface of the tooth.

[0055] 本文中,“非水性"组合物(例如,粘合剂)指其中水不作为成分的组合物。 [0055] As used herein, "non-aqueous" composition (e.g., an adhesive) refers to a composition wherein the water component. 然而,在组合物其他成分中可以有外来的水,但是水总量对非水性组合物的稳定性(例如,贮存期)没有不利的影响。 However, the other components in the composition can have external water, but the total amount of water has no adverse effect on the stability of non-aqueous composition (e.g., storage period). 按非水性组合物的总重计,非水性组合物优选包括小于lwt-%,更优选小于0. 5wt-%,最优选小于0. Iwt-%的水。 Non-aqueous composition according to the total weight of the non-aqueous composition preferably comprises less than lwt-%, more preferably less than 0. 5wt-%, most preferably less than 0. Iwt-% of water.

[0056] 本文中,“自蚀"组合物(或自蚀粘合组合物)指在没有用浸蚀剂预处理牙齿结构表面的情况下,可以与牙齿结构表面粘接的组合物。 [0056] As used herein, the term "self-etching" composition (or self-etch adhesive composition) means in the absence of pretreatment by etching the surface of the tooth structure agent, composition and surface bonded to the tooth structure. 优选地,自蚀组合物也可以用作没有使用单独的浸蚀剂或底物的自底物。 Preferably, the self-etching composition can also be used without the use of separate etchant or the substrate from the substrate.

[0057] 本文中,“自粘合剂"组合物(或自粘合剂复合体)指在没有用底物或粘接剂预处理牙齿结构表面的情况下,能够与牙齿结构表面粘接的组合物。 [0057] As used herein, the term "self-adhesive" compositions (or self-adhesive composite) refers to the absence of pretreatment of the surface of the tooth structure with a substrate or an adhesive, capable of bonding with tooth structure surface composition. 优选地,自粘合组合物也是一种没有使用单独的浸蚀剂的自蚀组合物。 Preferably, the self-adhesive composition is used without a separate self-etching composition of the etchant.

[0058] 本文中,“硬化"或"固化"组合物可以交换使用,指聚合和/或交联反应,包括例如涉及到组合物中所含的一种或多种材料的光聚合反应和化学聚合技术(例如,离子反应)。 [0058] As used herein, the term "hardening" or "curing" compositions can be used interchangeably, refers to polymerization and / or cross-linking reaction, including, for example relates to photopolymerizable compositions containing one or more materials and chemical reactions polymerization techniques (e.g., ion reaction).

[0059] 本文中,“牙齿结构表面"指牙齿结构(例如,牙釉质和牙本质)和骨。 [0059] As used herein, "dental structure surface" means tooth structure (such as enamel and dentin) and bone.

[0060] 本文中,“混溶〃指至少部分溶解。 [0060] As used herein, "means at least partially miscible 〃 dissolved.

[0061] 本文中,“水包油"乳液指其中水形成连续相和油是不连续液滴的水包油混合物。 [0061] As used herein, "oil in water" emulsion refers to an oil in water wherein the water to form a mixture of a continuous phase and the discontinuous oil droplets.

[0062] 本文中,“油包水"乳液指其中油形成连续相和水是不连续液滴的油包水混合物。 [0062] As used herein, "water in oil" refers to emulsions in which the oil forms the continuous phase and water droplets are discontinuous water in oil mixture. 可以根据2003年8月12日提交的美国临时申请60/494,603所述的方法使用电乳液测试仪区分油包水乳液和水包油乳液。 You can apply for the provisional 60 / 494,603 according to the United States August 12, 2003 to submit a method to distinguish between the use of electrical emulsion tester oil-in-water emulsions and water-in-oil emulsion. 水包油乳液的电阻相对较低,可以导电,因为水形成 Resistance-water emulsion is relatively low, it can be electrically conductive, since water is formed

8外部或连续相,而油包水乳液不导电,或导电极差。 8 external or continuous phase and water in oil emulsion the non-conductive or poor conductive.

[0063] 本文中,油包水乳液中的"油相"指制剂中的所有成分,其中各成分在水相中超过其溶解度极限;这些通常是在蒸馏水中溶解度小于的材料,然而,水相成分如盐可以降低某些油的溶解度,从而分配进油相中。 [0063] As used herein, water in oil emulsion of the "oil phase" refers to all components of the formulation, wherein the components in the aqueous phase exceeds its solubility limit; these are usually in distilled water solubility of less than the material, however, the aqueous phase components such as salts may decrease the solubility of certain oils, thereby dispensed into the oil phase.

[0064] 本文中,油包水乳液中的"水相"指存在的水和水可溶解的任何成分,即,在水中没有超过其溶解度限制的成分。 [0064] As used herein, water in oil emulsion of the "water phase" refers to the presence of any component of water and water-soluble, i.e., not exceed its solubility in water composition limits.

[0065] 本文中,“物理稳定的"乳液指根据2003年8月12日提交的美国临时申请60/494,603所述的乳液稳定性测试方案,在一次(优选二次,更优选三次)的冷冻/解冻/ 离心循环后,乳液中没有观察到水分离。 [0065] As used herein, "physically stable" means the emulsion U.S. August 12, 2003 filed provisional application programs emulsion stability test 60 / 494,603, wherein the at once (preferably twice, more preferably three times) The freeze / thaw / centrifuge cycles, the emulsion water separation was not observed.

[0066] 本文中,"化学稳定的"或"保存稳定的"化合物或组合物指在室温下贮存期至少1年,优选至少2年的化合物或组合物。 [0066] As used herein, the term "chemically stable" or "Save stable" refers to a compound or composition of storage at room temperature for at least 1 year, preferably at least 2 years of a compound or composition. 自粘合组合物的贮存期通常通过测定当老化的组合物与牙齿结构表面粘接时,老化的组合物是否能够提供可接受的粘接强度来测量。 Self-adhesive composition during storage of the composition typically by tooth bonding surface of the structure when the measured aging, aging composition is capable of providing an acceptable bond strength was measured.

[0067] 本文中,“表面活性剂"指可以改变表面性能(例如,降低表面张力)的表面活性试剂,包括通常称为"润湿剂"的表面活性试剂。 [0067] As used herein, "surfactant" refers to surface properties may change (e.g., lower the surface tension) surface active agents include surface active agents are generally referred to as "wetting agents" a.

[0068] 本文中,除非另有所指,''一个(a)''或〃 一个(an)''指〃至少一个〃或〃 一个或多个〃。 [0068] As used herein, unless otherwise indicated, '' a (a) '' or 〃 a (an) '' refers to at least one 〃 〃 〃 or one or more 〃.

[0069] 优选实施方案详细说明 [0069] Detailed description of preferred embodiments

[0070] 本发明的牙科组合物包括烯键式不饱和化合物和芳基亚磺酸盐。 [0070] The dental composition of the present invention include ethylenically unsaturated compounds and arylsulfinate sulfonate. 优选地,芳基亚磺酸盐在烯键式不饱和化合物中是可混溶的,更优选以所用水平溶解。 Preferably, the aryl-sulfonate ethylenically unsaturated compound is miscible, more preferably in the horizontal dissolved. 在一些实施方案中, 优选的是,芳基亚磺酸盐在烯键式不饱和化合物中溶解至少lwt-%,更优选至少5wt_%, 最优选至少lOwt-%。 In some embodiments, it is preferable that at least arylsulfinate lwt-% salt dissolved in an ethylenically unsaturated compound, more preferably at least 5wt_%, most preferably at least lOwt-%. 相比而言,芳基亚磺酸金属盐通常在牙科组合物所用的烯键式不饱和化合物中不溶解。 In contrast, an aryl sulfinic acid metal salt is usually insoluble in ethylenically unsaturated compounds dental composition used in.

[0071] 通常,芳基亚磺酸盐是引发剂体系的一部分,该引发剂体系除了芳基亚磺酸盐之外还可以包括或不包括各种成分。 [0071] Typically, arylalkylene sulfonate initiator system is part of the initiator system arylalkylene addition salt may also include or not include the various ingredients. 这种成分包括,例如,敏化剂,电子受体,不同于芳基亚磺酸盐的还原剂(例如,次级还原剂),和其组合。 Such ingredients include, for example, a sensitizer, an electron acceptor, a reducing agent is different from the arylalkylene sulfonates (e.g., secondary reducing agents), and combinations thereof. 引发剂体系可以是热引发剂体系,光引发剂体系,或其组合。 Initiator systems a thermal initiator system may, photoinitiator system, or a combination thereof.

[0072] 在本发明的一些实施方案中,牙科组合物还包括牙科添加剂。 [0072] In some embodiments of the present invention, the dental composition further comprising a dental additive. 本发明的一些实施方案包括牙科添加剂,如填料,表面活性剂,乳化剂,和可光漂白的染料。 Some embodiments of the present invention comprises a dental additives such as fillers, surfactants, emulsifiers, dyes and photo-bleaching.

[0073] 本发明的牙科组合物可以是分散体,悬浮液,乳液,溶液,和其组合形式。 [0073] The dental composition of the present invention can be dispersions, suspensions, emulsions, solutions, and their combinations. 在本发明的一些实施方案中中,牙科组合物可以是油包水乳液。 In some embodiments of the present invention, the dental composition may be a water in oil emulsion. 牙科组合物可以是,例如,树脂改性的玻璃离聚物胶合剂,常规甲基丙烯酸酯复合体,复合聚合物,和其组合。 Dental composition may be, for example, resin-modified glass ionomer cement, the conventional methacrylate composites, polymer composites, and combinations thereof.

[0074] 本发明的牙科组合物可以用作底物(包括自蚀底物),粘合剂(包括自蚀粘合剂),正牙粘合剂,涂层,密封剂,胶合剂,和修复材料(包括填料,复合体,流动物,和修补物如牙冠,牙桥,胶合板,镶嵌物,裱贴物,等)。 [0074] The dental compositions of the present invention can be used as a substrate (including a substrate from corrosion), the binder (including self-etching adhesive), orthodontic adhesives, coatings, sealants, adhesives, and repair materials (including packing, composite, flow animals, and prostheses such as crowns, bridges, veneer, inlays, onlays, etc.). 牙科修补物通常充填有在与牙齿相连之前成形或聚合的填料复合体。 Usually filled with dental prosthesis prior to tooth forming connected or polymerized composite filler. 牙医或其他使用者可以将这种预成形物品研磨成或以其他方式形成常用形状。 Dentist or other user may be pre-formed object such milled or otherwise formed into a common shape. 当用作底物,粘合剂,或胶合剂时,牙科组合物可用于使修复材料(固化或未固化的)与牙科结构表面粘合。 When used as a substrate, an adhesive, or adhesives, dental compositions may be used to repair material (cured or uncured) adhesive dental structure surface. 当用作正牙粘合剂时,牙科组合物可用于使正牙用具(例如,牙环,颊管,牙带,牙夹板,牙扣,舌固定器,或咬合器)与牙科结构表面粘合。 When used as an orthodontic adhesive, the dental composition can be used to make orthodontic appliance (e.g., the ring teeth, buccal tubes, dental tape, dental splint, teeth buckle, the tongue anchor or occluder) a dental structure surface with adhesive co.

[0075] 引发剂体系 [0075] initiator system

9[0076] 芳基亚磺酸盐 9 [0076] aryl-sulfonate

[0077] 已知有多种材料可在聚合反应用的引发剂体系中用作电子供体。 [0077] There are a variety of materials known polymerization initiator may be used in the reaction system as an electron donor. 然而,这些材料中的一些在光引发剂体系中不足够稳定。 However, some of these materials in the photoinitiator system is not sufficiently stable. 即,在活化引发剂体系之前,这些材料中的一些不能与电子受体和/或敏化剂长期混合(例如,超过一天)。 That is, prior to activating the initiator system, some of these materials can not be receptors and electronic / or long mixing sensitizer (e.g., more than one day). 此外,这些材料中的一些基于其氧化电势和稳定性而在光引发剂体系中用作电子供体,但在烯键式不饱和化合物中的溶解度有限。 In addition, some of these materials based on their oxidation potential and stability in the photoinitiator system is used as the electron donor, but the solubility in ethylenically unsaturated compounds is limited.

[0078] 本发明的一个方面是提供一种组合物,其包括电子供体,电子受体,和可选择地敏化剂。 [0078] An aspect of the present invention is to provide a composition comprising an electron donor, an electron acceptor, and optionally a sensitizer. 本发明的另一个方面是提供一种组合物,其包括电子供体和敏化剂。 Another aspect of the present invention is to provide a composition comprising an electron donor and a sensitizer. 更具体而言,电子供体包括芳基亚磺酸盐。 More specifically, the electron donor comprises arylalkylene sulfonates. 组合物可以用作自由基聚合反应的引发剂体系。 The composition can be used as the radical polymerization initiator system. 引发剂体系可以用在光聚合方法,热聚合方法,或其组合中。 Initiator systems can be used in photo-polymerization method, thermal polymerization method, or a combination thereof. 热聚合方法包括通常的氧化还原方法,即,使用电子供体(通常还原剂)和电子受体(通常氧化剂)的方法;和通常在还原剂和氧化剂彼此接触之后,在室温下聚合。 Thermal polymerization methods include conventional redox method, i.e., using the electron donor (usually a reducing agent) and an electron acceptor (oxidant typically) method; and a reducing agent and oxidizing agent is usually in contact with each other after the polymerization at room temperature.

[0079] 该电子供体在N,N- 二甲基甲酰胺中相对于银/硝酸银参考电极的氧化电势为0. 0〜+0. 4伏,是芳基亚磺酸盐,该芳基亚磺酸盐包括阴离子和阳离子,该阴离子为下式I [0079] The electron donor in N, N- dimethylformamide with respect to a silver / silver nitrate oxidation potential of the reference electrode is 0. 0~ + 0.4 volts, is sulfonate arylalkylene, the aryl Nokia include anionic and cationic salt, the anion of the formula I

[0080] Ar1-SO2- I [0080] Ar1-SO2- I

[0081] 该阳离子包括带正电荷的氮原子或者带正电荷的磷原子。 [0081] The cation comprising a positively charged nitrogen atom or a positively charged phosphorus atom. 优选地,该阳离子具有至少一个碳原子。 Preferably, the cation having at least one carbon atom. 式I中的Ar1基团是未取代的或用吸电子基或吸电子基与供电子基的组合所取代的C6,芳基和C3,杂芳基。 Formula I Ar1 groups are unsubstituted or electron withdrawing group or an electron withdrawing group and electron donating group substituted with a combination of C6, aryl, and C3, heteroaryl. 该电子受体在在N,N- 二甲基甲酰胺中相对于银/硝酸银参考电极的还原电势为+0.4〜-1.0伏。 The electron acceptor in the N, N- dimethylformamide with respect to the reduction potential of silver silver / nitrate reference electrode is + 0.4~-1.0 volts.

[0082] 选择具有预定范围的氧化电势的电子供体和具有预定范围的还原电势的电子受体。 [0082] selective oxidation potential electron donor having a predetermined range having a predetermined range of reduction potential of the electron acceptor. 可以使用循环伏安法测定氧化和还原电势。 Determination of oxidation and reduction potential can be used cyclic voltammetry. 如与本申请同一天提交的受让人的共同未决的美国申请10/672,762 (代理机构卷号58634US002)所述,通过将相关化合物溶解在含有支持电解质(即,0.1摩尔/升四丁基六氟磷酸铵)的非水性溶剂(即,N,N-二甲基甲酰胺)中,从而测量氧化和还原电势。 As the assignee of the present application and filed on the same day of the co-pending U.S. Application No. 10 / 672,762 (Attorney Docket No. 58634US002) said, by the related compounds are dissolved in an electrolyte containing a support (i.e., 0.1 mol / liter four- butyl ammonium hexafluorophosphate) in a non-aqueous solvent (i.e., N, N- dimethylformamide), thereby measuring the oxidation and reduction potentials. 用惰性气体如氩气冲洗得到的溶液。 An inert gas such as argon flushed solution was obtained. 使用三电极结构, 包括工作电极(即,玻璃碳电极),参考电极(即,溶解在乙腈中的0. 01摩尔/升硝酸银中的银线),和反电极(即,钼线)。 Using a three-electrode structure, comprising a working electrode (i.e., glassy carbon electrode), reference electrode (i.e., dissolved in acetonitrile in 0.01 mol / liter of silver nitrate in the silver wire), and the counter electrode (i.e., a molybdenum wire). 氧化或还原电势是氧化或还原反应最大电流时的电压。 Oxidation or reduction potential is the maximum oxidation or reduction reactions voltage current.

[0083] 在本发明中,该电子供体是芳基亚磺酸盐,该芳基亚磺酸盐包括阴离子和阳离子, 该阴离子为下式I [0083] In the present invention, the electron donor is aryl-sulfonate, the aryl-sulfonate include anionic and cationic, the anion of the formula I

[0084] Ar1-SO2- I [0084] Ar1-SO2- I

[0085] 该阳离子包括带正电荷的氮原子或者带正电荷的磷原子。 [0085] The cation comprising a positively charged nitrogen atom or a positively charged phosphorus atom. 优选地,该阳离子具有至少一个碳原子。 Preferably, the cation having at least one carbon atom. 式I中的Ar1基团可以是未取代的或用吸电子基或吸电子基与供电子基的组合所取代的C6,芳基和C3,杂芳基。 Formula I Ar1 radicals may be unsubstituted or substituted with a combination of an electron withdrawing group or an electron withdrawing group and electron donating group substituted C6, aryl, and C3, heteroaryl. 芳基亚磺酸盐通常溶解在能够发生自由基聚合反应的烯键式不饱和化合物和各种非极性和极性溶剂中。 Aryl-sulfonate is usually dissolved in the radical polymerization can occur ethylenically unsaturated compound and a variety of non-polar and polar solvents. 本文中,术语"溶解"指在给定物质如溶剂或烯键式不饱和化合物中能够溶解的量至少等于0. 1摩尔/升的化合物。 Herein, the term "dissolution" means the amount of a given substance such as a solvent or ethylenically unsaturated compound capable of dissolving at least equal to 0.1 mol / liter of compound.

[0086] 在一些芳基亚磺酸盐中,Ar1基团是具有碳环芳环的芳基。 [0086] In some arylalkylene sulfonate, Ar1 is a group having an aromatic ring carbocyclic aryl groups. 芳基可以具有一个碳环芳环,或可以具有与碳环芳环稠合或连接的额外碳环。 Aryl group may have a carbon aromatic ring, or may have a carbon aromatic ring fused or connected to additional carbon ring. 任何连接或稠合的都可以是饱和或不饱和的。 Any connection or fused can be saturated or unsaturated. 芳基经常含有5个环,4个环,3个环,2个环,或1个环。 Aryl often contains five rings, four rings, three rings, two rings, or a ring. 芳基通常具有高达30个碳原子,高达24个碳原子,高达18个碳原子,高达12个碳原子,或高达6个碳原子。 Aryl group typically having up to 30 carbon atoms, up to 24 carbon atoms, up to 18 carbon atoms, up to 12 carbon atoms, or up to 6 carbon atoms. 具有一个环或多个稠合环的芳基例子包括但不限于苯基,蒽基,萘基,苊基,菲基,菲基,二 Examples of the aryl group having one ring or more fused rings include, but are not limited to, phenyl, anthryl, naphthyl, acenaphthyl, phenanthryl, phenanthryl, two

10萘嵌苯基,和蒽基。 10 Perylene, and anthryl. 单键,亚甲基(即,-CH2-),羰基(即,-(CO)-),或其组合可以连接多个环。 A single bond, methylene (i.e., -CH2-), carbonyl group (i.e., - (CO) -), or a combination thereof can be connected to a plurality of rings. 具有多个连接不的芳基例子包括但不限于蒽醌基,蒽基,联苯基,三联苯基,9,10- 二氢蒽基,禾口莉基。 Examples of the aryl group having a plurality of connections include, but are not limited to, anthraquinone, anthryl, biphenyl, terphenyl, 9,10-dihydro-anthryl, Wo mouth 莉基.

[0087] 在其他芳基亚磺酸盐中,式I中的Ar1基团可以是具有5〜7元芳环的杂芳基,在芳环中包括一个或多个独立地选自S,0,N,或其组合的杂原子。 [0087] Other aryl-sulfonate in Formula I in the Ar1 group may be a 5 ~ 7-membered aromatic ring of a heteroaryl group, in an aromatic ring includes one or more groups independently selected from S, 0 , N, heteroatoms, or combinations thereof. 杂芳基可以具有一个环,或可以具有连接或稠合到一起的多个环。 Heteroaryl group may have one ring, or may have fused together or connected to a plurality of rings. 任何额外连接或稠合的环都可以是碳环或含有杂原子,且可以是饱和或不饱和的。 Any additional connection or fused rings can be carbocyclic or contains hetero atoms, and may be saturated or unsaturated. 杂芳基经常具有5个环,4个环,3个环,2个环,或1个环。 Heteroaryl often have five rings, four rings, three rings, two rings, or a ring. 杂芳基通常含有高达30个碳原子。 Heteroaryl groups typically contain up to 30 carbon atoms. 在一些实施方案,杂芳基含有高达20个碳原子,高达10 个碳原子,或高达5个碳原子。 In some embodiments, the heteroaryl group containing up to 20 carbon atoms, up to 10 carbon atoms, or up to 5 carbon atoms. 杂芳基的例子包括但不限于喹啉基,异喹啉基,喹唑啉基, 喹喔啉基,噌啉基,苯并呋喃基,苯并巯基苯基,苯并噁唑基,苯并噻唑基,苯并咪唑基,吲哚基,二氮杂萘基,苯并噻二唑基,苯并三嗪基,吩嗪基,菲啶基,吖啶基,氮杂菲基,和吲唑基。 Examples of heteroaryl groups include, but are not limited to, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, cinnolinyl, benzofuranyl, benzo thiol group, a benzoxazolyl, benzene and thiazolyl, benzimidazolyl, indolyl, quinazolinyl, benzo thiadiazolyl, benzo triazinyl, phenazine group, phenanthridinyl, acridinyl, aza phenanthryl, and indazolyl.

[0088] 式I中的Ar1基团可以是未取代的或被吸电子基或吸电子基及供电子基的组合所取代,只要芳基亚磺酸盐在N,N- 二甲基甲酰胺中相对于银/硝酸银参考电极的氧化电势为0. 0〜+0. 4伏。 [0088] Formula I Ar1 group may be unsubstituted or substituted with an electron withdrawing group or an electron withdrawing group and electron donating group substituted with a combination of, as long as the arylalkylene salt in N, N- dimethylformamide with respect to a silver / silver nitrate oxidation potential of the reference electrode is 0. 0~ + 0.4 volts. 供电子基例如可以选自伯氨基,仲氨基,叔氨基,羟基,烷氧基,芳氧基,烷基,或其组合。 E.g., electron donating groups may be selected from a primary amino group, secondary amino group, tertiary amino group, a hydroxyl group, an alkoxy group, an aryloxy group, an alkyl group, or a combination thereof. 吸电子基例如可以选自卤素,氰基,氟代烷基,全氟烷基,羧基,烷氧基羰基, 芳氧基羰基,商代羰基,甲酰基,羰基,磺酸基,烷氧基磺酰基,芳氧基磺酰基,全氟烷基磺酰基,烷基磺酰基,偶氮,链烯基,炔基,二烷基膦酸酯基,二芳基膦酸酯基,或其组合。 For example, electron-withdrawing groups selected from halogen, cyano, fluoroalkyl, perfluoroalkyl group, a carboxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbonyl group Shang, formyl, a carbonyl group, a sulfonic acid group, an alkoxy group sulfonyl group, aryloxy sulfonyl group, perfluoroalkyl sulfonyl, alkylsulfonyl, azo, alkenyl, alkynyl, dialkyl phosphonate, diaryl phosphonate group, or a combination thereof .

[0089] 在一些实施方案中,Ar1基团包括与亚磺酸盐基团共轭的吸电子基。 [0089] In some embodiments, Ar1 groups include sulfonate groups and sub-conjugated electron withdrawing group. 例如,Ar1基团可以是被吸电子基所取代的苯基,该吸电子基选自卤素,氰基,氟代烷基,全氟烷基,羧基, 氨基羰基,烷氧基羰基,芳氧基羰基,商代羰基,甲酰基,羰基,磺酸基,烷氧基磺酰基,芳氧基磺酰基,全氟烷基磺酰基,烷基磺酰基,或其组合。 For example, Ar1 group may be substituted with an electron withdrawing group phenyl, which electron withdrawing group selected from halo, cyano, fluoroalkyl, perfluoroalkyl, carboxy, aminocarbonyl, alkoxycarbonyl, aryloxy carbonyl, Shang carbonyl, formyl, carbonyl, sulfonic acid group, alkoxy sulfonyl group, aryloxy sulfonyl group, a perfluoroalkyl sulfonyl group, an alkylsulfonyl group, or a combination thereof.

[0090] 式I的芳基亚磺酸盐阴离子的具体实例包括但不限于4-氯苯亚磺酸盐,4-氰基苯亚磺酸盐,4-乙氧基羰基苯亚磺酸盐,4-三氟甲基苯亚磺酸盐,3-三氟甲基苯亚磺酸盐, 1-萘亚磺酸盐,2-萘亚磺酸盐,和1-蒽醌亚磺酸盐。 Specific examples of [0090] Formula I arylalkylene sulfonate anions include, but are not limited to 4-chlorophenyl sulfinate, benzene sulfinate 4-cyano, 4-ethoxycarbonyl phenyl sulfinate , 4-trifluoromethyl benzene sulfinate, benzene sulfinate 3-trifluoromethylphenyl, 1-naphthyl sulfinate, sulfinate 2-naphthyl, and 1-anthraquinone sulfinate .

[0091] 芳基亚磺酸盐的阳离子包括带正电荷的氮原子或者带正电荷的磷原子。 [0091] aryl-sulfonates cations include a positively charged nitrogen atom or a positively charged phosphorus atom. 优选地, 该阳离子具有至少一个碳原子。 Preferably, the cation having at least one carbon atom. 在一个实施方案中,芳基亚磺酸盐的阳离子是式II In one embodiment, the arylalkylene sulfonate cation is of formula II

[0092] [0092]

? 1 1

R4-N+-R4 ^ R4-N + -R4 ^

Π Π

[0093] 其中R1是烷基或芳基,每个R4独立地是氢,烷基,或芳基。 [0093] wherein R1 is an alkyl or aryl group, each R4 is independently hydrogen, alkyl, or aryl. R1和R4可以是未取代的或取代的。 R1 and R4 may be unsubstituted or substituted. 烷基可以用羟基所取代。 The alkyl group may be substituted with a hydroxyl group. 芳基可以用烷基,羟基,或其组合所取代。 Substituted aryl may be combined with an alkyl, hydroxy, or.

[0094] 在式II的一些例子中,R1和每个R4独立地是未取代的或用羟基取代的C2,烷基。 [0094] In some examples of formula II, R1 and R4 each independently is unsubstituted or substituted with hydroxy C2, alkyl. 例如,R1和每个R4独立地可以是具有高达20,高达10,高达8,高达6,或高达4个碳原子的烷基。 For example, R1 and R4 each independently having up to 20 may be up to 10, up to 8, up to 6, or an alkyl group of up to 4 carbon atoms. 烷基通常具有至少2,至少3,至少4,至少6,或至少8个碳原子。 Alkyl group typically has at least 2, at least 3, at least 4, at least 6, or at least 8 carbon atoms. 在一些化合物中烷基可以具有4〜30,8〜30,3〜10,4〜10,4〜8,或4〜6个碳原子。 In some compounds may have 4~30,8~30,3~10,4~10,4~8 alkyl, or 4 ~ 6 carbon atoms. 在具体例子中,芳基亚磺酸盐的阳离子是四丁基铵离子。 In a specific example, arylalkylene sulfonate cation is tetrabutylammonium ion.

[0095] 在式II的其他例子中,R1和两个R4每一个独立地是未取代的或用羟基取代的C2, [0095] In another example of the formula II, R1 and R4 are each independently two unsubstituted or hydroxyl-substituted C2,

11烷基。 11 group. 其余R4是氢。 Remaining R4 is hydrogen. 在其他例子中,R1和一个R4每一个独立地是未取代的或用羟基取代的(;,烷基;和两个其余的R4是氢。在其他例子中,R1是未取代的或用羟基取代的C8,烷基;和R4是氢。 In other examples, R1 and R4 are each independently an unsubstituted or substituted by hydroxy (; alkyl;., And the remaining two in the other examples R4 are hydrogen, R1 is unsubstituted or substituted with hydroxy substituted C8, alkyl group; and R4 is hydrogen.

[0096] 式II中的R1和每个R4可以独立地是未取代的或用烷基,羟基,或其组合取代的芳基。 [0096] Formula II, R1 and R4 may each independently be unsubstituted or substituted with an alkyl group, a hydroxyl group, a substituted aryl group, or combinations thereof. 示例性阳离子是四苯基铵离子。 Exemplary cations are tetraphenyl ammonium ion. 在另一个例子中,R1和一个R4独立地是未取代的或用烷基,羟基,或其组合取代的芳基;和其余两个R4是氢。 In another example, R1 and R4 are independently an unsubstituted or alkyl group, a hydroxyl group, a substituted aryl group, or combinations thereof; R4 is hydrogen, and the other two. 示例性阳离子是二苯基铵离子。 Exemplary cations are diphenyl ammonium ion.

[0097] 在其他实施方案中,芳基亚磺酸盐的阳离子是包括含有带正电荷的氮原子的4〜 12元杂环的环结构。 [0097] In other embodiments, the aryl-sulfonate cation include those containing nitrogen atom is a positively charged of April to 12 yuan heterocyclic ring structure. 杂环可以是饱和或不饱和的,并可含有选自氮,氧,硫,或其组合的3个杂原子(即,一个带正电荷的氮原子和两个选自氮,氧,硫,或其组的其他杂原子合)。 Heterocyclic ring may be saturated or unsaturated, and may contain selected from nitrogen, oxygen, sulfur, or combinations thereof 3 hetero atoms (i.e., a positively charged nitrogen atom and two selected from nitrogen, oxygen, sulfur, other hetero atoms or groups combined). 环结构可以是未取代的或具有选自烷基,芳基,酰基,烷氧基,芳氧基,卤素,巯基,氨基,羟基,偶氮,氰基,羧基,烷氧基羰基,芳氧基羰基,商代羰基,或其组合的取代基。 Ring structure can be unsubstituted or substituted selected from alkyl, aryl, acyl, alkoxy, aryloxy, halogen, mercapto, amino, hydroxy, azo, cyano, carboxy, alkoxycarbonyl, aryloxycarbonyl carbonyl, Shang carbonyl, or combinations of substituents.

[0098] 阳离子环结构中的杂环可以是单环,双环,或可以稠合成另一个环或双环。 [0098] cationic heterocyclic ring structure may be monocyclic, bicyclic, or may be fused to another ring or bicyclic ring. 稠合环或双环可以是饱和或不饱和的,并可以具有0〜3个杂原子。 Fused bicyclic ring or may be saturated or unsaturated, and may have 0~3 heteroatoms. 环结构可包括高达30个碳原子,高达24个碳原子,高达18个碳原子,高达12个碳原子,高达6个碳原子,或高达4个碳原子和高达6个杂原子,高达4个杂原子,高达2个杂原子,或1个杂原子。 Ring structure may comprise up to 30 carbon atoms, up to 24 carbon atoms, up to 18 carbon atoms, up to 12 carbon atoms, up to 6 carbon atoms, or up to 4 carbon atoms and up to 6 heteroatoms, up to 4 hetero atoms, up to 2 heteroatoms, or a heteroatom. 在一些实施方案中,环结构是与具有0〜3个杂原子的芳环稠合的4〜12元杂环。 In some embodiments, the ring structure is fused with an aromatic ring having 0~3 heteroatoms bound 4~12 membered heterocyclic ring.

[0099] 含有带正电荷的氮原子的适合五元杂环的例子包括但不限于吡咯鐺离子,吡唑鐺离子,吡咯鐺离子,咪唑鐺离子,三唑鐺离子,异噁唑鐺离子,噁唑鐺离子,噻唑鐺离子,异噻唑鐺离子,噁二唑鐺离子,噁三唑鐺离子,二噁唑鐺离子,和噁噻唑鐺离子。 Examples [0099] contains a positively charged nitrogen atoms suitable five-membered heterocyclic rings include but are not limited to pyrrole clang ion, pyrazole clang ion, pyrrole clang ion, imidazole clang ion, triazole clang ion, isoxazole pan ion, oxazole clang ion, thiazole clang ion, isothiazole clang ion, oxadiazole clang ions, ion oxatriazole clang, clang dioxazole ion, and oxathiazole pan ions. 这些离子可以是未取代的,或用烧基,芳基,酰基,烧氧基,芳氧基,商素,巯基,氨基,轻基,偶氮,氰基,羧基, 烷氧基羰基,芳氧基羰基,卤代羰基,或其组合所取代。 These ions can be unsubstituted or burn group, an aryl group, an acyl group, burning, aryloxy, commercial factors, a mercapto group, an amino group, light group, azo, cyano, carboxy, alkoxycarbonyl, aryl butoxycarbonyl, halo carbonyl, or combinations thereof. 在一些应用中,阳离子是未取代的或取代的咪唑鐺离子或噁唑鐺离子。 In some applications, the cation is unsubstituted or substituted imidazole or oxazole clang clang ion ion.

[0100] 五元杂环可以与另一个环稠合。 [0100] V. membered heterocyclic ring may be fused with another ring. 在一些示例性环结构中,五元杂环与芳基稠合。 In some exemplary ring structure, the five-membered heterocyclic ring fused with aryl. 示例性环结构包括但不限于吲哚离子,吲唑离子,苯并吡咯鐺离子,苯并咪唑鐺离子,苯并三唑鐺离子,苯并异噁唑鐺离子,苯并噁唑鐺离子,苯并噻唑鐺离子,苯并异噻唑鐺离子,苯并噁二唑鐺离子,苯并噁三唑鐺离子,苯并二噁唑鐺离子,苯并噁噻唑鐺离子,咔唑离子,和嘌呤鐺离子。 Exemplary ring structures include, but are not limited to, ion indole, indazole ion, ion phthalimidine pan, pan ion-benzimidazole, benzotriazole pan ion, ion pan benzisoxazole, benzoxazole pan ions, benzothiazole clang ion, benzisothiazole clang ion, benzoxadiazolyl clang ion, benzo oxatriazole clang ions, ion benzobisoxazole clang, clang benzo oxathiazole ion, carbazole ions, and purine pan ions. 这些离子可以是未取代的,或用烷基,芳基,酰基,烷氧基,芳氧基,卤素,巯基, 氨基,羟基,偶氮,氰基,羧基,烷氧基羰基,芳氧基羰基,商代羰基,或其组合所取代。 These ions can be unsubstituted, or an alkyl, aryl, acyl, alkoxy, aryloxy, halogen, mercapto, amino, hydroxy, azo, cyano, carboxy, alkoxycarbonyl, aryloxy carbonyl, Shang carbonyl, or combinations thereof. 在一些应中,阳离子是未取代的或取代的苯并噁唑鐺离子或苯并噻唑鐺离子。 In some applications, the cation is unsubstituted or substituted benzoxazole or benzothiazole clang clang ion ion.

[0101] 含有带正电荷的氮原子的适合六元杂环的例子包括但不限于吡啶鐺离子,哒嗪鐺离子,嘧啶鐺离子,吡嗪鐺离子,哌嗪鐺离子,三嗪鐺离子,噁嗪鐺离子,哌啶鐺离子,噁噻嗪鐺离子,噁二嗪鐺离子,和吗啉鐺离子。 Suitable examples of six-membered heterocyclic ring [0101] contains a positively charged nitrogen atom include, but are not limited to pyridine pan ion, ion pan pyridazine, pyrimidine ion pan, pan ion pyrazine, piperazine ion pan, pan ion triazine, oxazine clang ion, piperidine pan ions, ion oxathiazine clang, clang oxadiazines ion, and morpholino pan ions. 这些离子可以是未取代的,或用烷基,芳基,酰基,烷氧基,芳氧基,商素,巯基,氨基,羟基,偶氮,氰基,或羧基,烷氧基羰基,芳氧基羰基,商代羰基,或其组合所取代。 These ions can be unsubstituted, or an alkyl group, an aryl group, an acyl group, an alkoxy group, an aryloxy group, business factors, mercapto, amino, hydroxy, azo, cyano group, or a carboxyl group, an alkoxycarbonyl group, an aryl butoxycarbonyl, Shang carbonyl, or combinations thereof. 在一些应用中,阳离子是未取代的或取代的吡啶鐺离子或吗啉鐺离子。 In some applications, the cation is unsubstituted or substituted pyridyl or morpholino clang clang ion ion.

[0102] 六元杂环可以与另一个环稠合。 [0102] Hexaheterocyclic can be fused with another ring. 在一些示例性环结构中,六元杂环与芳基稠合。 In some exemplary ring structure or six-membered heterocyclic aromatic group fused. 示例性环结构包括但不限于异喹啉鐺离子,喹啉鐺离子,二萘嵌苯鐺离子,喹唑啉鐺离子,苯并吡嗪鐺离子,苯并哌嗪鐺离子,苯并三嗪鐺离子,苯并噁嗪鐺离子,苯并哌啶鐺离子,苯并噁噻嗪鐺离子,苯并噁二嗪鐺离子,苯并吗啉鐺离子,萘啶鐺离子,和吖啶鐺离子。 Exemplary ring structures include, but are not limited to, isoquinoline clang ion, quinoline clang ion, perylene clang ion, quinazoline clang ion, benzo pyrazine clang ion, benzo piperazine clang ion, benzotriazine clang ions, ion benzoxazine clang, clang benzo -piperidine-ion, ion-benzo oxathiazine clang, clang benzo oxadiazines ion, benzo morpholine clang ions, ion nalidixic clang, clang ion and acridine . 这些离子 These ions

12可以是未取代的或用烷基,芳基,酰基,烷氧基,芳氧基,卤素,巯基,氨基,羟基,偶氮,氰基, 或羧基,烷氧基羰基,芳氧基羰基,商代羰基,或其组合所取代。 12 can be unsubstituted or substituted with an alkyl, aryl, acyl, alkoxy, aryloxy, halogen, mercapto, amino, hydroxy, azo, cyano group, or a carboxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group Shang carbonyl, or combinations thereof.

[0103] 含有带正电荷的氮原子的适合七元杂环的例子包括例如氮杂草鐺离子和二氮杂草鐺离子。 [0103] contains a positively charged nitrogen atom seven-membered heterocyclic ring suitable examples include, for example, ion diazepin pan and pan diazepin ions. 这些离子可以是未取代的,或用烷基,芳基,酰基,烷氧基,芳氧基,卤素,巯基, 氨基,羟基,偶氮,氰基,羧基,烷氧基羰基,芳氧基羰基,商代羰基,或其组合所取代。 These ions can be unsubstituted, or an alkyl, aryl, acyl, alkoxy, aryloxy, halogen, mercapto, amino, hydroxy, azo, cyano, carboxy, alkoxycarbonyl, aryloxy carbonyl, Shang carbonyl, or combinations thereof.

[0104] 双环的杂环例子包括但不限于N-烷基化或N-质子化的1,4_二氮杂双环[2. 2. 2] 辛烷和N-烷基化或N-质子化的1-氮杂双环[2. 2. 2]辛烷,它们可以是未取代的,或用烷基? [0104] Examples of bicyclic heterocycle include, but are not limited to, N- N- alkylated or protonated 1,4_ diazabicyclo [2.2.2] octane and N- alkylated or protonated N- of 1-azabicyclo [2.2.2] octane, which may be unsubstituted or alkyl? 方基? 酰基,烷氧基,芳氧基,商素,巯基,氨基,羟基,偶氮,氰基,羧基,烷氧基羰基,芳氧基羰基,商代羰基,或其组合所取代。 Side group? Acyl group, an alkoxy group, an aryloxy group, business factors, mercapto, amino, hydroxy, azo, cyano, carboxy, alkoxycarbonyl, aryloxycarbonyl, Shang carbonyl, or combinations thereof.

[0105] 在其他实施方案中,芳基亚磺酸盐的阳离子含有式III的带正电荷的磷原子 [0105] In other embodiments, arylalkylene sulfonate cation containing positively charged phosphorus atom of Formula III

[0106] [0106]

? 2 2

R2-P+-R2 R2-P + -R2

12 R2 12 R2

ΙΠ ΙΠ

[0107] 其中每个R2独立地是未取代的或取代的烷基或芳基。 [0107] wherein each R2 is independently an unsubstituted or substituted alkyl or aryl group. 烷基可以用羟基所取代。 The alkyl group may be substituted with a hydroxyl group. 芳基可以用烷基,羟基,或其组合所取代。 Substituted aryl may be combined with an alkyl, hydroxy, or.

[0108] 在式III的一些例子中,所有的R2是芳基。 [0108] In some instances formula III, all of R2 is aryl. 例如,阳离子可以是四苯基鳞离子。 For example, the cation may be a tetraphenyl scales ions. 在其他例子中,一个、两个或三个R2是芳基,其余R2是C2,烷基。 In other examples, one, two or three R2 is an aryl group, the remaining R2 is C2, alkyl group.

[0109] 一些芳基亚磺酸盐具有式IV的阴离子和含有带正电荷的氮原子的阳离子 [0109] Some cationic salt anion arylsulfinate formula IV and nitrogen atoms with a positive charge

[0110] [0110]

IV IV

[0111] 优选地,该阳离子具有至少一个碳原子。 [0111] Preferably, the cation having at least one carbon atom. 在式IV中,R3可以在苯环的邻、对或间位, 并且是吸电子基,该吸电子基选自卤素,氰基,氟代烷基,全氟烷基,羧基,烷氧基羰基,芳氧基羰基,商代羰基,甲酰基,羰基,磺酸基,烷氧基磺酰基,芳氧基磺酰基,全氟烷基磺酰基, 烷基磺酰基,偶氮,链烯基,炔基,二烷基膦酸酯基,或二芳基膦酸酯基。 In formula IV, R3 in the phenyl ring can be ortho, meta or against, and is an electron withdrawing group, the electron withdrawing group selected from halo, cyano, fluoroalkyl, perfluoroalkyl, carboxy, alkoxycarbonyl a carbonyl group, an aryloxycarbonyl group, a carbonyl group Shang, formyl, carbonyl, a sulfonic acid group, alkoxy sulfonyl group, aryloxy sulfonyl group, perfluoroalkyl sulfonyl, alkylsulfonyl, azo, alkenyl , an alkynyl group, a dialkyl phosphonate group, or a diaryl phosphonate group. 在一些化合物,R3 选自氰基,羧基,烷氧基羰基,芳氧基羰基,商代羰基,甲酰基,羰基,磺酸基,烷氧基磺酰基, 芳氧基磺酰基,全氟烷基磺酰基,或烷基磺酰基。 In some compounds, R3 is selected from a cyano group, a carboxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbonyl group Shang, formyl, a carbonyl group, a sulfonic acid group, alkoxy sulfonyl group, aryloxy sulfonyl group, a perfluoroalkyl arylsulfonyl group, or an alkylsulfonyl group. 在其他化合物中,R3是商素,氰基,或烷氧基幾基。 In other compounds, R3 is a commercial, cyano, alkoxy, or a few groups.

[0112] 式IV中R3在苯环对位的具体实例包括4-氰基苯亚磺酸盐,4-氯苯亚磺酸盐, 4_乙氧基羰基苯亚磺酸盐,和4-三氟甲基苯亚磺酸盐。 [0112] In formula IV the benzene ring in the para position R3 Specific examples thereof include 4-cyano-benzene sulfinate, 4-chlorobenzene sulfinate, benzene sulfinate 4_ ethoxycarbonyl, and 4- trifluoromethyl benzene sulfinate. R3在苯环间位的具体例子包括3-三氟甲基苯亚磺酸盐。 Specific examples of R3 in position between the benzene ring include 3-trifluoromethyl-benzene sulfinate.

[0113] 对于一些应用而言,芳基亚磺酸盐包括式IV的阴离子和为四烷基铵离子的阳离子。 [0113] For some applications, arylalkylene sulphonates include anions of formula IV and a tetraalkylammonium ion. 四烷基铵离子的各烷基可以相同或不同,通常含有2〜30个碳原子。 Tetraalkyl ammonium ions each alkyl may be the same or different and typically contain 2~30 carbon atoms. 例如,烷基可以含有4〜30个碳原子,8〜30个碳原子,3〜10个碳原子,4〜10个碳原子,或4〜8个碳原子。 For example, the alkyl group may contain 4~30 carbon atoms, 8~30 carbon atoms, 3~10 carbon atoms, 4~10 carbon atoms, or 4 to 8 carbon atoms. 具体的芳基亚磺酸盐包括但不限于四丁基铵4-氯苯亚磺酸盐,四丁基铵4-氰基苯亚磺酸盐,四丁基铵4-乙氧基羰基苯亚磺酸盐,四丁基铵4-三氟甲基苯亚磺酸盐,和四丁 Specific arylalkylene sulfonates include, but are not limited to, tetrabutylammonium 4-chlorophenyl sulfinate, tetrabutylammonium 4-Cyano-phenyl sulfinate, tetrabutylammonium 4-ethoxycarbonyl phenyl sulfinate, tetrabutylammonium 4-trifluoromethyl-benzene sulfinate, and tetrabutylammonium

13基铵3-三氟甲基苯亚磺酸盐。 13-yl 3-trifluoromethyl-benzylidene ammonium salt.

[0114] 电子供体的其他具体实例包括但不限于四丁基铵1-萘亚磺酸盐,四丁基铵2-萘亚磺酸盐,和四丁基铵1-蒽醌亚磺酸盐,1-乙基-3-甲基咪唑鐺4-氰基苯亚磺酸盐,4-甲基苯亚磺酸盐,N,N- 二甲基吗啉鐺4-氰基苯亚磺酸盐,3-乙基-2-甲基苯并噁唑啉鐺4-氰基苯亚磺酸盐,1-甲基-4-氮杂-1-氮阳离子双环[2. 2. 2]辛烷4-氰基苯亚磺酸盐,和N-十六烷基吡啶鐺4-氰基苯亚磺酸盐。 [0114] Other specific examples of electron donors include, but are not limited to, tetrabutylammonium sulfinate 1-naphthyl, 2-naphthyl tetrabutyl ammonium sulfinate, and tetrabutylammonium 1- anthraquinone sulfinate salt, 1-ethyl-3-methyl-imidazol-4-cyano-benzene sulfinate pan, 4-methyl benzene sulfinate, N, N- dimethyl-morpholin-4-cyano-benzylidene sulfonic pan acid, 3-ethyl-2-methyl-4-cyano-benzo oxazoline pan benzene sulfinate, 1-methyl-4-aza-1-azoniabicyclo [2. 2.2] 4-cyano-octane benzene sulfinate, and N- cetylpyridinium clang 4-cyano-benzene sulfinate.

[0115] 可以按与本申请同一天提交的受让人的共同未决的美国申请10/672,762(代理机构卷号58634US002)所述的方法来制备芳基亚磺酸盐。 [0115] and the assignee of the present application can be filed on the same day the co-pending U.S. Application 10 / 672,762 (Attorney Docket No. 58634US002) the method for preparing aryl-sulfonate.

[0116] 优选地,按可硬化的组合物成分的总重(包括水)计,电子供体(即,亚磺酸盐) 的存在量至少为0. 01wt-%,更优选至少0. lwt-%。 [0116] Preferably, the composition according to the hardening of the total weight of components (including water) meter, electron donor (ie, sub-salt) is present in an amount of at least 0. 01wt-%, more preferably at least 0. lwt -%. 优选地,按可硬化的组合物成分的总重(包括水)计,亚磺酸盐的存在量不大于IOwt-%,更优选不大于5wt-%。 Preferably, the hardenable compositions according to the total weight of components (including water) meter, sulfinate present in an amount of not more than IOwt-%, more preferably not more than 5wt-%.

[0117] 次级还原剂 [0117] secondary reductant

[0118] 在本发明的一些实施方案中,电子供体(即芳基亚磺酸盐)可以用作氧化还原引发剂体系中的主要还原剂,可选择地,还包括次级还原剂。 [0118] In some embodiments of the present invention, the electron donor (i.e., aryl-sulfonate) can be used as a redox initiator system main reducing agent, optionally, further comprising a secondary reducing agent. 次级还原剂可以是可聚合的或不可聚合的。 Secondary reducing agent may be a polymeric or non-polymeric. 常用的次级还原剂包括包括美国专利5,501,727 (Wang等人)中所述的抗坏血酸,抗坏血酸衍生物和金属配合的抗坏血酸化合物;胺,特别是叔胺,如乙基4_(N,N-二甲基氨基)苯甲酸酯和4-叔丁基二甲基苯胺;芳香亚磺酸盐,如ρ-甲苯亚磺酸盐和苯亚磺酸盐;硫脲,如1-乙基-2-硫脲,四乙基硫脲,四甲基硫脲,1,1- 二丁基硫脲,和1,3- 二丁基硫脲;和其混合物。 Commonly used reducing agents include include secondary U.S. Patent 5,501,727 (Wang et al.) Ascorbic acid, ascorbic acid, ascorbic acid derivatives, and metal complexes of compounds; amines, especially tertiary amines, such as ethyl 4_ (N, N- dimethylamino) benzoate and 4-tert-butyl dimethylaniline; aromatic alkylene sulfonates, e.g. ρ- toluene sulfinate and benzene sulfinate; thioureas, such as 1-ethyl yl-2-thiourea, tetraethyl thiourea, tetramethyl thiourea, 1,1-dibutyl thiourea, and 1,3-dibutyl thiourea; and mixtures thereof. 其他次级还原剂可以包括氯化钴(II),氯化亚铁,硫酸亚铁,胼,羟基胺(取决于氧化剂的选择),草酸,连二亚硫酸盐或亚硫酸盐阴离子的盐,和其混合物。 Other secondary reducing agents may include cobalt chloride (II), ferrous chloride, ferrous sulfate, corpus, hydroxylamine (depending on the choice of oxidizing agent), oxalic acid, dithionite or sulfite anion, and mixtures thereof. 可以用作次级还原剂的其他化合物包括如美国专利5,545,676 (Palazzotto)中所述的电子供体。 Other compounds may be used as secondary reducing agents include, for example, U.S. Patent 5,545,676 (Palazzotto) in the electron donor. 优选地,次级还原剂是胺,更优选叔胺。 Preferably, the reducing agent is a secondary amine, preferably a tertiary amine.

[0119] 优选地,按可硬化的组合物成分的总重(包括水)计,可选择的次级还原剂存在量为至少0. Olwt-%,更优选至少0. 05wt_%。 [0119] Preferably, the total weight of the hardenable composition ingredients (including water) meter, optional secondary reducing agent present in an amount of at least 0. Olwt-%, more preferably at least 0. 05wt_%. 优选地,按可硬化的组合物成分的总重(包括水)计,可选择的次级还原剂存在量不大于IOwt-%,更优选不大于5wt_%, Preferably, the composition according to the hardening of the total weight of components (including water) meter, optional secondary reducing agent present in an amount of not more than IOwt-%, more preferably not more than 5wt_%,

[0120] 电子受体 [0120] electron acceptor

[0121] 在本发明的某些实施方案中,引发剂体系的成分是电子受体(例如,包括氧化剂),该电子受体在N,N- 二甲基甲酰胺中相对于银/硝酸银参考电极的还原电势最多为+0. 4伏,优选最多+0. 1伏,更优选最多0. 0伏,再更优选最多-0. 1伏,最优选最多-0. 5伏。 [0121] In certain embodiments of the present invention, the initiator component initiator system is an electron acceptor (e.g., including an oxidant), the electron acceptor in N, N- dimethylformamide with respect to a silver / silver nitrate The reduction potential of the reference electrode up to +0. 4 volts, preferably at most +0. 1 volt, more preferably at most 0.0 volts, still more preferably at most -0. 1 volt, and most preferably at most -0. 5 volts. 在一些实施方案中,该电子受体在N,N-二甲基甲酰胺中相对于银/硝酸银参考电极的还原电势至少为-1.0伏。 In some embodiments, the electron acceptor in N, N- dimethylformamide with respect to the reduction potential of the silver / silver nitrate reference electrode is at least -1.0 volts.

[0122] 选择的电子受体通常可以溶解在能够发生自由基聚合反应的烯键式不饱和化合物中。 [0122] selected electron acceptor is usually dissolved in the radical polymerization can occur ethylenically unsaturated compounds. 适合的电子受体包括例如氧化态的金属离子、过硫酸和其盐、过氧化物和氢过氧化物、过硼酸和其盐、高锰酸和其盐、过磷酸和其盐、碘鐺盐或其组合。 Suitable electron acceptor includes, for example metal ion oxidation state, over sulfuric acid and its salts, hydrogen peroxide and peroxide, boric acid and its salts, high manganese acid and its salts, excessive phosphoric acid and its salts, iodine salt pan or combinations thereof.

[0123] 如果电子受体是氧化态的金属离子,过氧化物,过硫酸盐,或其组合,那么在引发剂体系中,在使用之前电子受体通常不与电子供体混合。 [0123] If the electron acceptor is the oxidation state of the metal ions, peroxides, persulfates, or a combination thereof, then the initiator system, prior to the use of the electron acceptor is generally not mixed with an electron donor. 这些电子受体经常可以与电子供体在室温(即,20C〜25C )或高温(例如,150 0C )下在相对较短时间内(例如,小于1小时,小于30分钟,小于10分钟,或小于5分钟)反应。 These electron acceptor and electron donor can often be at room temperature (i.e., 20 C~25 C) or high temperatures (e.g., 150 0C) in a relatively short period of time at (e.g., less than one hour, less than 30 minutes, less than 10 minutes, or less than 5 minutes) the reaction. 这种引发剂体系可以在没有光活化的情况下引发(即,引发剂体系是热(例如氧化还原)体系)。 Such an initiator system can initiate (i.e., initiator system is thermally (e.g. redox) system) in the case of the absence of photoactivation.

14[0124] 适合的电子受体金属离子包括例如III族金属,过渡金属,和镧系金属的离子。 14 [0124] Suitable metal ions include, for example, an electron acceptor III metals, transition metals, and lanthanide metal ions. 具体的金属离子包括但不限于Fe (III),Co (III),Ag(I),Ag(II),Cu (II),Ce (IV),Al (III), Mo(VI),和Zn(II)。 Specific metal ions include, but are not limited to, Fe (III), Co (III), Ag (I), Ag (II), Cu (II), Ce (IV), Al (III), Mo (VI), and Zn (II). 具有这种金属离子的适合电子受体盐的实例包括醋酸铜(II),氯化钴(III),氯化铁(III),和硫酸铈(IV)。 Examples of such a metal ion having a suitable electron acceptor salts include copper acetate (II), cobalt (III) chloride, iron (III), and cerium sulfate (IV).

[0125] 适合的电子受体过氧化物包括苯甲酰过氧化物,月桂基过氧化物等。 [0125] Suitable electron acceptor peroxides include benzoyl peroxide, lauryl peroxide and the like. 适合的氢过氧化物包括枯基氢过氧化物,叔丁基氢过氧化物,过氧化钠,过氧化氢,和戊基氢过氧化物等。 Suitable hydroperoxides include cumyl hydroperoxide, t-butyl hydroperoxide, sodium peroxide, hydrogen peroxide, and amyl hydroperoxide and the like. 适合的电子受体过硫酸盐包括例如钠,钾,铯,铵,和烷基铵盐。 Suitable electron acceptor include persulfates such as sodium, potassium, cesium, ammonium, and alkyl ammonium salts.

[0126] 需要时可以使用多于一种氧化剂或多于一种芳基亚磺酸盐。 [0126] You can use more than one oxidizing agent or more than one aryl-sulfonate when needed. 也可以加入少量过渡金属化合物,以加速聚合(例如氧化还原固化)的速率。 It may also be added a small amount of transition metal compound to accelerate polymerization (e.g., redox cure) rate.

[0127] 芳基亚磺酸盐和电子受体(例如氧化剂)的存在量需足以允许足够的自由基反应速率。 [0127] arylalkylene sulfonates and electron acceptor (e.g., an oxidant) is present in an amount sufficient to allow for an adequate free-radical reaction rate. 这可通过混合除了可选择的填料之外的可硬化的组合物的所有成分,并观察是否得到硬化的物质来分析。 This optional addition by mixing all the ingredients of the filler of the hardenable composition and observing whether the hardened material analyzed.

[0128] 如果引发剂体系用在光聚合方法中(即,引发剂体系是光引发剂体系),那么选择的可选择的电子受体通常在室温下不与电子供体(即芳基亚磺酸盐)直接反应。 [0128] If the initiator system used in the photopolymerization process (i.e., initiator system is a photoinitiator system), then select the alternative electron acceptor is usually at room temperature without the electron donor (i.e., sulfonic arylalkylene salt) direct reaction. 在一些实施方案中,在用光活化引发剂体系之前,含有电子受体,电子供体,和敏化剂的组合物通常可以贮存至少1天,并优选组合物是化学稳定的。 In some embodiments before, in light-activated initiator system containing an electron acceptor, an electron donor and a sensitizer compositions generally may be stored at least one day, and the preferred compositions are chemically stable. 适用于光引发剂体系中的电子受体包括但不限于碘鐺盐,六芳基二咪唑,或其组合。 Suitable photoinitiator systems include an electron acceptor, but are not limited to pan iodide salt, six diaryl imidazole, or combinations thereof.

[0129] 在一些实施方案中,该电子受体在N,N" 二甲基甲酰胺中相对于银/硝酸银参考电极的还原电势最多为+0. 1伏,优选最多0. 0伏,更优选最多-0. 1伏,最优选最多-0. 5伏。 在一些实施方案中,该电子受体在N,N-二甲基甲酰胺中相对于银/硝酸银参考电极的还原电势至少为-1.0伏。具有这种还原电势的电子受体包括碘鐺盐。碘鐺盐经常是二芳基碘鐺盐。二芳基碘鐺盐通常是保存稳定的。即,在与电子供体混合或与电子供体和敏化剂混合时,在没有光时,二芳基碘鐺盐通常不会自发地与电子供体反应,或促进与电子供体的聚 [0129] In some embodiments, the electron acceptor in N, N "dimethylformamide reduction potential with respect to a silver / silver nitrate reference electrode up to +0. 1 volt, preferably at most 0.0 volts, more preferably at most -0. 1 volt, and most preferably at most -0. 5 volts. In some embodiments, the electron acceptor in N, N- dimethylformamide with respect to the reduction potential of the silver / silver nitrate reference electrode at least -1.0 volts with such reduction potential of the electron acceptor include iodine pan salt pan salt iodine is often diaryliodonium salt pan. diaryliodonium salt pan is usually stored stable. That is, in the electron donor When blended or mixed polymer body with an electron donor and a sensitizer, in the absence of light, diaryliodonium pan salt usually does not spontaneously react with an electron donor, or the promotion of an electron donor

I=IO I = IO

[0130] 适合的碘鐺盐更详细地公开在美国专利3,729,313 (Smith) ;3, 741,769 (Smith); 3,808,006(Smith) ;4,250,053 (Smith) ;4,394,403(Smith) ;5,545,676 (Palazzotto 等人);和5,998,495 (Oxman等人)中。 [0130] Suitable salt pan iodine disclosed in more detail in U.S. Patent No. 3,729,313 (Smith); 3, 741,769 (Smith); 3,808,006 (Smith); 4,250,053 (Smith) ; 4,394,403 (Smith); 5,545,676 (Palazzotto et al.); and 5,998,495 (Oxman et al.). 碘鐺盐可以是简单盐,金属配合盐,或其组合。 Iodide salt can be a simple pan salt, metal complex salts, or combinations thereof. 简单盐的例子包括具有阴离子的那些(如卤化物,磺酸盐,羧酸盐,或其组合)。 Examples of simple salts include those having an anion (e.g. halide, sulfonate, carboxylate, or combinations thereof). 金属配合盐的例子包括具有阴离子的那些,如六氟磷酸盐,六氟砷酸盐,六氟锑酸盐,五氟羟基锑酸盐,四氟硼酸盐,四(五氟苯基)硼酸盐,或其组合。 Examples of the metal complex salts include those having anions such as hexafluorophosphate and hexafluoroarsenate, hexafluoroantimonate, pentafluoroethyl hydroxy antimonate, tetrafluoroborate, tetrakis (pentafluorophenyl) boron salt, or combinations thereof.

[0131] 可以根据Beringer等人,J. Am. Chem. Soc. ,81,342(1959)的教导,通过使相应简单的碘鐺盐(如,例如,二苯基碘鐺氯化物或二苯基碘鐺亚硫酸盐)易位来制备碘鐺金属配合盐。 [0131] according to Beringer et al., J. Am. Chem. Soc., 81,342 (1959) the teachings, by reacting the corresponding iodine pan simple salt (e.g., e.g., diphenyliodonium chloride or diphenyliodonium pan clang sulfite) translocation to prepare iodine clang of metal complex salts. 在具体例子中,可以通过将含有氟硼酸银,氟硼酸,和磷酸的水溶液加到二苯基碘鐺氯化物的水溶液中,从而来制备金属配合盐二苯基碘鐺四氟硼酸盐。 In a specific example, it can be obtained by containing silver fluoroborate, fluoroboric acid, phosphoric acid, and the aqueous solution was added to an aqueous solution of diphenyliodonium chloride in the pan, so as to prepare a metal complex salt diphenyliodonium tetrafluoroborate pan. 可以过滤出沉淀的卤化银,浓缩滤液,得到二苯基碘鐺四氟硼酸盐,可用重结晶进行纯化。 The silver halide can be precipitated was filtered off, the filtrate was concentrated to yield diphenyliodonium tetrafluoroborate pan, purified by recrystallization.

[0132] 可以根据Beringer等人所述的来制备简单的二芳基碘鐺盐,该方法包括在硫酸中使两种芳香化合物与硫酸碘酰偶联;在乙酸-乙酸酐中使两种芳香化合物与碘酸盐偶联;在酸存在下使两种芳香化合物与碘丙烯酸酯偶联;或在酸存在下使亚碘酰化合物(例如,亚碘酰二乙酸酯)或碘酰化合物与其他芳香化合物缩合。 [0132] can be prepared according to Beringer, who simply said diaryliodonium salt pan, which comprises two aromatic compounds manipulation sulfuric acid and sulfuric acid conjugates iodine; in acetic acid - acetic anhydride mixing two aromatic coupled with the iodate compound; in the presence of two aromatic acid compound and an iodine acrylate coupled; or in the presence of an acid to make iodosylbenzoic compounds (for example, iodosylbenzoic diacetate) or iodine acid compound and Other aromatic compound condensation.

15[0133] 示例性二芳基碘鐺盐包括二苯基碘鐺氯化物,二苯基碘鐺四氟硼酸盐,二(4-甲基苯基)碘鐺四氟硼酸盐,苯基-4-甲基苯基碘鐺四氟硼酸盐,二(4-庚基苯基)碘鐺四氟硼酸盐,苯基-4-庚基苯基碘鐺四氟硼酸盐,二(3-硝基苯基)碘鐺六氟磷酸盐,二(4-氯苯基)碘鐺六氟磷酸盐,二(萘基)碘鐺四氟硼酸盐,二(4-三氟甲基苯基)碘鐺四氟硼酸盐,二苯基碘鐺六氟磷酸盐,二(4-甲基苯基)碘鐺六氟磷酸盐,二苯基碘鐺六氟砷酸盐, 二(4-苯氧基苯基)碘鐺四氟硼酸盐,苯基-2-噻吩基碘鐺六氟磷酸盐,3,5-二甲基吡唑基-4-苯基碘鐺六氟磷酸盐,二苯基碘鐺六氟锑酸盐,2,2' - 二苯基碘鐺四氟硼酸盐,二(2,4-二氯苯基)碘鐺六氟磷酸盐,二(4-溴苯基)碘鐺六氟磷酸盐,二(4-甲氧基苯基) 碘鐺六氟磷酸盐,二(3-羧基苯基)碘鐺六氟磷酸盐,二(3-甲氧基羰基苯基)碘鐺六氟磷酸盐,二(3-甲氧基磺酰基苯基)碘鐺六氟磷酸盐,二(4-乙酰氨基苯基)碘鐺六氟磷酸盐,二(2-苯并噻吩基)碘鐺六氟磷酸盐,二苯基碘鐺六氟锑酸盐,和二苯基碘鐺四(五氟苯基)硼酸盐。 15 [0133] Examples of diaryliodonium salts include diphenyliodonium pan pan chloride, diphenyliodonium pan tetrafluoroborate, bis (4-methylphenyl) iodonium tetrafluoroborate pan, benzene pan-iodo-4-methylphenyl tetrafluoroborate, bis (4-heptyloxy-phenyl) iodonium tetrafluoroborate pan, heptyl-phenyl-4-iodo-phenyl pan tetrafluoroborate, bis (3-nitrophenyl) iodonium hexafluorophosphate pan, bis (4-chlorophenyl) iodonium hexafluorophosphate pan, di (naphthyl) iodonium tetrafluoroborate pan, bis (4-trifluoromethyl methyl phenyl) iodonium tetrafluoroborate clang, clang diphenyliodonium hexafluorophosphate, bis (4-methyl-phenyl) iodonium hexafluorophosphate clang, clang diphenyliodonium hexafluoroarsenate, bis (4-phenoxyphenyl) iodonium tetrafluoroborate pan, phenyl-2-thienyl pan iodide hexafluorophosphate, 3,5-dimethyl-4-phenyl-pyrazol iodo six pan hexafluorophosphate, diphenyliodonium hexafluoroantimonate pan, 2,2 '- pan diphenyliodonium tetrafluoroborate, di (2,4-dichlorophenyl) iodonium hexafluorophosphate pan, two (4-bromophenyl) iodonium hexafluorophosphate pan, bis (4-methoxyphenyl) iodonium hexafluorophosphate pan, bis (3-carboxyphenyl) iodonium hexafluorophosphate pan, bis (3- methoxycarbonyl phenyl) iodonium hexafluorophosphate pan, bis (3-methoxy-phenyl-sulfonyl) iodide pan hexafluorophosphate, bis (4-acetamidophenyl) iodonium hexafluorophosphate pan, two (2-benzothienyl) iodonium hexafluorophosphate pan, pan diphenyliodonium hexafluoroantimonate, diphenyliodonium pan and tetrakis (pentafluorophenyl) borate.

[0134] 在一些应用中,电子受体是二苯基碘鐺氯化物,二苯基碘鐺六氟磷酸盐,二苯基碘鐺四氟硼酸盐,二苯基碘鐺六氟锑酸盐,二苯基碘鐺四(五氟苯基)硼酸盐,或其组合。 [0134] In some applications, the electron acceptor is diphenyliodonium chloride clang, clang diphenyliodonium hexafluorophosphate, diphenyliodonium tetrafluoroborate clang, clang diphenyliodonium hexafluoroantimonate salts, diphenyliodonium pan tetrakis (pentafluorophenyl) borate, or combinations thereof. 这些二芳基碘鐺盐可以促进快速反应,并且与一些其他碘鐺盐相比,更易溶解在惰性有机溶剂中。 These pan diaryliodonium salts may promote rapid reaction, and compared to some other pan iodine salt, is more soluble in an inert organic solvent.

[0135] 引发剂体系可以包括六芳基二咪唑化合物作为电子受体。 [0135] The initiator system may comprise six diaryl imidazole compound as an electron acceptor. 这种化合物可按照J. Org. Chem.,36,2762 (1971)所述的来合成。 Such compounds may be in accordance with J. Org. Chem., 36,2762 (1971) to synthesize said. 六芳基二咪唑商业上可以商品名SPEEDCURE BCIM 从Lambson, West Yorkshire, England 得至lj。 Hexaaryl imidazole is commercially available under the trade name SPEEDCURE BCIM from Lambson, West Yorkshire, England have to lj.

[0136] 在引发剂体系是光引发剂体系的实施方案中,选择的电子受体,使得电子受体溶解在适合的溶剂如醇或烯键式不饱和单体中时,形成对眼睛是无色的溶液。 [0136] When the initiator system is a photoinitiator embodiment of the agent system, select the electron acceptor, so that the electron acceptor is dissolved in a suitable solvent such as an alcohol or ethylenically unsaturated monomers, the formation of the eye is not colored solution. 电子受体在醇中的溶液通常在电磁光谱的可见光区域不吸收。 Electron acceptor in an alcohol solution generally does not absorb in the visible region of the electromagnetic spectrum. 即,在350nm时电子受体的摩尔消光系数可以小于100或小于50 1-moIe-1 cm_1o That is, the molar extinction coefficient at 350nm electron acceptor may be less than 100 or less than 50 1-moIe-1 cm_1o

[0137] 优选地,如果用于组合物中,那么按可硬化的组合物成分的总重(包括水)计,电子受体存在量为至少0. Olwt-%,更优选至少0. lOwt-%。 [0137] Preferably, if used in the composition, the total can be cured by weight of the composition components (including water) meter, electron acceptor present in an amount of at least 0. Olwt-%, more preferably at least 0. lOwt- %. 优选地,按可硬化的组合物成分的总重(包括水)计,电子受体存在量不大于lOwt-%,更优选不大于5wt-%。 Preferably, the hardenable compositions according to the total weight of components (including water) gauge, the electron acceptor present in an amount of not more than lOwt-%, more preferably not more than 5wt-%.

[0138] 还原剂(例如,芳基亚磺酸盐和/或次级还原剂)或氧化剂可以按美国专利5,154,762 (Mitra等人)所述的进行微封装。 [0138] a reducing agent (for example, aryl-sulfonate and / or secondary reducing agent) or an oxidizing agent can be microencapsulated in U.S. Patent 5,154,762 (Mitra et al.) Said. 这通常会增强可聚合的组合物的贮存稳定性, 并在需要时可将还原剂和氧化剂包装在一起。 This usually enhances the storage stability of the composition can be polymerized and, if necessary, reducing and oxidizing agents are packaged together. 例如,通过适当地选择密封剂,氧化剂和还原剂可以与酸官能化的成分和可选择的填料混合,并保持在贮存稳定态。 For example, by appropriately selecting the sealant, oxidizing and reducing agents may be acid functionalized component and optional fillers, and kept in a storage stable form. 同样,通过适当地选择水不溶密封剂,还原剂和氧化剂可以与FAS玻璃和水混合,并保持在贮存稳定态。 Also, by appropriately selecting a water-insoluble encapsulant, the reducing agent and oxidizing agent can be mixed with the FAS glass and water and maintained in a stable storage state.

[0139] 氧化还原固化体系可以与其他固化体系混合,例如,与美国专利5,154,762 (Mitra 等人)中所述的可光聚合的组合物混合。 [0139] redox cure system can be mixed with other cure systems, e.g., mixed with U.S. Patent 5,154,762 (Mitra et al.) The photopolymerizable composition.

[0140] 敏化剂 [0140] sensitizer

[0141] 本发明的可光聚合的组合物还可以包括敏化化合物(即敏化剂)作为引发剂体系的一部分。 Photopolymerizable composition [0141] The present invention may further comprise a sensitizer compound (ie, sensitizer) as part of the initiator system. 250〜1000纳米的电磁射线(例如,光化射线)通常可用于形成受激的敏化剂。 250~1000 nm electromagnetic radiation (e.g., actinic radiation) can generally be used to form the excited sensitizer. 敏化剂可以是二酮,染料,颜料,或其组合。 Diketone sensitizer may be, dyes, pigments, or combinations thereof.

[0142] 适合的敏化剂包括但不限于酮(例如,单酮和二酮),香豆素染料(例如,酮代香豆素,如Coumarin 153),氧杂蒽染料(例如,Rose Bengal和Rhodamine 6G),吖啶染料,噻 [0142] Suitable sensitizers include, but are not limited to, ketones (e.g., ketones and single-dione), coumarin dyes (e.g., keto coumarins behalf, such as Coumarin 153), xanthene dyes (e.g., Rose Bengal and Rhodamine 6G), acridine dyes, thiazole

16唑染料,噻嗪染料(例如,亚甲基蓝和亚甲基紫),噁嗪染料(例如,Basic Blue 3和Nile Blue Chloride),吖嗪染料(例如,甲基橙),氨基酮染料,卟啉(例如,四氮杂卟啉),芳香多环烃,P-取代的氨基苯乙烯基酮化合物,氨基三芳基甲烷,菁染料(例如,Biochemistry, 12,3315(1974)中所述的菁染料),方酸菁(squarylium)染料,吡啶鐺染料,苯并吡啶鐺染料,和三芳基甲烷(例如,MalachiteGreen)。 16 oxazole dyes, thiazine dyes (for example, methylene blue and methylene violet), oxazine dyes (for example, Basic Blue 3 and Nile Blue Chloride), azine dyes (for example, methyl orange), aminoketone dyes, porphyrins (e.g., porphyrazine), polycyclic aromatic hydrocarbons, P- substituted aminostyryl ketone compounds, amino triarylmethane, cyanine dyes (e.g., Biochemistry, 12,3315 (1974) in the cyanine dye ), squarylium (squarylium) dyes, dye pyridine clang, clang benzopyridine dyes, and triarylmethane (eg, MalachiteGreen). 在一些应用中,敏化剂包括氧杂蒽,单酮,二酮,或其组合。 In some applications, sensitizers include xanthene, single ketones, diketones, or combinations thereof. 其他适合的敏化染料公开在FJ,Green, The Sigma-Aldrich HandbookoF Stains, Dyes and Indicators, Aldrich Chemical Company, Inc., Milwaukee, WI (1990) 中。 Other suitable sensitizing dyes are disclosed in FJ, Green, The Sigma-Aldrich HandbookoF Stains, Dyes and Indicators, Aldrich Chemical Company, Inc., Milwaukee, WI (1990). 在一些实施方案中,敏化剂是氧杂蒽染料,如荧光素,若丹明,曙红,和派若宁。 In some embodiments, the sensitizers are xanthene dyes such as fluorescein, rhodamine, eosin, and pyronine.

[0143] 示例性单酮包括2,2- 二羟基苯甲酮,4,4- 二羟基苯甲酮,和2,4_ 二羟基苯甲酮, 二-2-吡啶基酮,二-2-呋喃基酮,二-2-巯基苯基酮,苯偶姻,芴酮,查耳酮,Michler酮, 2_氟-9-芴酮,2-氯巯基吨酮,苯乙酮,苯甲酮,1-或2-萘乙酮,9-乙酰基蒽,2-,3_,或9-乙酰基菲,4-乙酰基联苯,苯丙酮,苯正丁酮,苯戊酮,2_,3_,或4-乙酰基吡啶,3-乙酰基香豆素等。 [0143] Exemplary single ketones include 2,2-dihydroxybenzophenone, 4,4-dihydroxybenzophenone, and 2,4_-dihydroxybenzophenone, di-2-pyridyl ketone, di-2- furanyl ketone, di-2-mercapto-phenyl ketone, benzoin, fluorenone, chalcone, Michler ketone, 2_ fluoro-9-fluorenone, 2-chloro-mercapto thioxanthone, acetophenone, benzophenone , 1- or 2-acetonaphthone, 9-acetyl-anthracene, 2-, 3_, or 9-acetyl-phenanthrene, 4-acetyl biphenyl, benzene, acetone, benzene, n-butanone, benzene pentanone, 2_, 3_ or 4-acetyl-pyridine, 3-acetyl coumarin.

[0144] 示例性二酮包括芳烷基二酮如蒽醌,菲醌,ο-, m-,和ρ-二乙酰基苯,1,3_,1,4_, 1,5-,1,6-,1,7_,和1-8 二乙酰基萘,1,5_,1,8_,和9,10-二乙酰基蒽等。 [0144] Exemplary aralkyl groups include dione dione as anthraquinone, phenanthrenequinone, ο-, m-, and ρ- diacetylbenzene, 1,3_, 1,4_, 1,5, 1,6 -, 1,7_, and 1-8 diacetyl naphthalene, 1,5_, 1,8_, and 9,10-diacetyl anthracene. 示例性α-二酮包括2,3-丁二酮,2,3-戊二酮,2,3-己二酮,3,4_己二酮,2,3-庚二酮,3,4-庚二酮,2, 3-辛二酮,4,5-辛二酮,苯偶酰,2,2' -,3,3'-,和4,4' - 二羟基苯偶酰,糠偶酰,二_3, 3'-吲哚基乙二酮,2,3_硼烷二酮(樟脑醌),二乙酰基,1,2_环己二酮,3,3,6,6_四甲基环己二酮,1,2-萘醌,苊醌等。 Exemplary α- diketone include 2,3-butanedione, 2,3-pentanedione, 2,3-cyclohexanedione, 3,4_ hexanedione, 2,3-heptanedione, 3,4 - heptanedione, 2, 3 octanedione, 4,5 octanedione, benzil, 2,2 '-, 3,3, and 4,4' - dihydroxybenzene benzil, bran benzil, two _3, 3'-indolyl acetic dione, 2,3_ borane-dione (camphorquinone), diacetyl, 1,2_ cyclohexanedione, 3,3,6,6 _-tetramethyl-cyclohexanedione, 1,2-naphthoquinone, acenaphthene quinone. 其他二酮包括1-芳基-2-烷基-1,2-乙烷二酮,如1-苯基-1,2-丙烷二酮,公开在例如美国专利6,204,302 (Rawls等人)中。 Other diketone group include 1-aryl-2-ethane-1,2-dione, such as 1-phenyl-propane-1,2-dione, for example, disclosed in U.S. Patent No. 6,204,302 (Rawls et al.).

[0145] 适于用作敏化剂的其他酮代香豆素和P-取代的氨基苯乙烯基酮化合物列于美国专利5,545,676 (Palazzotto)的表II 中。 [0145] suitably used as sensitizer substituting other ketones substituted coumarin and P- aminostyryl ketone compounds are listed in U.S. Patent No. 5,545,676 (Palazzotto) of Table II.

[0146] 敏化剂的摩尔消光系数高达150,000 l-molfcnT1。 [0146] The molar extinction coefficient of the sensitizer up to 150,000 l-molfcnT1. 在一些应用中,敏化剂的摩尔消光系数高达85,000 l-mole—cnT1,高达70,000,高达50,000,高达30,000,高达10,000, 或高达5,000 1-mole^cnT1。 In some applications, the molar extinction coefficient of the sensitizer up to 85,000 l-mole-cnT1, up to 70,000, up to 50,000, up to 30,000, up 10,000, or up to 5,000 1-mole ^ cnT1.

[0147] 对于需要深层固化的应用而言(例如,高度填充的牙科复合体的固化)),通常选择的敏化剂其消光系数小于1000 1-mole-1 cm-10在其他应用中,在光聚合用的光化射线的波长下,消光系数小于500或小于lOOl-mol^cnT1。 [0147] For applications requiring deep cure applications (e.g., cure of highly filled dental composite)), generally chosen sensitizer extinction coefficient less than 1000 1-mole-1 cm-10 in the other applications, the wavelength of the light polymerization under actinic radiation, the extinction coefficient of less than 500 or less than lOOl-mol ^ cnT1. α - 二酮是适于这种应用的敏化剂。 α - dione is suitable for such applications sensitizer. 可选择地,可以使用经光照射消光系数降低,光吸收降低,或在激励波长下光漂白的染料。 Alternatively, you can use when exposed to light extinction coefficient decreases, the light absorption is diminished, or at the excitation wavelength of the light bleached dye.

[0148] 敏化剂也可以是美国专利4,959,297 (Palazzotto等人)和4,257,915 (Eaton)中所述的颜料。 [0148] sensitizer may also be a United States Patent 4,959,297 (Palazzotto et al.) And 4,257,915 (Eaton) said pigment. 适合的无机颜料包括但不限于二氧化钛,钛酸锶,钛酸钡,氧化锌,硫化锌,硒化锌,硫化镉,硒化镉,碲化镉,或其组合。 Suitable inorganic pigments include, but are not limited to, titanium dioxide, strontium titanate, barium titanate, zinc oxide, zinc sulfide, zinc selenide, cadmium sulfide, cadmium selenide, cadmium telluride, or combinations thereof. 适合的有机颜料包括但不限于酞菁蓝(颜料蓝15),铜多氯酞菁绿(颜料绿7),铜多溴氯酞菁(颜料绿36),花猩红(染红29),朱红(颜料红23),栗红,枣红,和茈二酸酐(茈红),在〃 Pigments-Inorganic" and" Pigments-O rganic" , Kirk-Othmer Encyclopedia of Chemical Technology,第三版,Volume 17,页788-817,John Wiley和Sons,New York, 1982中公开。有机颜料也可以是半导体聚合物, 公开在YM Paushkin等人,Organic Polymeric Semiconductors, John Wiley & Sons,New York,1974 和JM Pearson, Pure and App1. Chem.,49,463-477(1977)中。 Suitable organic pigments include, but are not limited to, phthalocyanine blue (Pigment Blue 15), polychlorinated copper phthalocyanine green (Pigment Green 7), polybrominated chloro copper phthalocyanine (Pigment Green 36), flowers scarlet (red 29), vermilion (Pigment Red 23), chestnut red, purplish red, and water chestnut anhydride (water chestnut red), in 〃 Pigments-Inorganic "and" Pigments-O rganic ", Kirk-Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 17, pages 788-817, John Wiley and Sons, New York, 1982 discloses organic pigments can also be a semiconducting polymers are disclosed in YM Paushkin et al., Organic Polymeric Semiconductors, John Wiley & Sons, New York, 1974 and JM Pearson, Pure and App1. Chem., 49,463-477 (1977) in.

[0149] 优选的敏化剂包括樟脑酮,苯偶酰,糠偶酰,3,3,6,6-四甲基环己二酮,菲醌,1-苯基-1,2-丙烷二酮,和其组合。 [0149] Preferred sensitizers include camphor ketone, benzil, benzil bran, 3,3,6,6-tetramethyl-cyclohexanedione, phenanthrenequinone, 1-phenyl-1,2-propane di ketones, and combinations thereof. 更优选的敏化剂是樟脑酮。 More preferably, the sensitizer is a ketone camphor.

[0150] 优选地,如果用在组合物中,那么按可硬化的组合物成分的总重(包括水)计,敏化剂存在量至少为0. 001wt-%,更优选至少0. 01wt-%。 [0150] Preferably, if used in the composition, the total can be cured by weight of the composition components (including water) meter, the sensitizer present in an amount of at least 0. 001wt-%, more preferably at least 0. 01wt- %. 优选地,按可硬化的组合物成分的总重(包括水)计,电子受体存在量不大于3. Owt-%,更优选不大于1. Owt-%。 Preferably, the hardenable compositions according to the total weight of components (including water) gauge, the electron acceptor present in an amount of not more than 3. Owt-%, more preferably not more than 1. Owt-%.

[0151] 可聚合的烯键式不饱和化合物 [0151] The compound ethylenically unsaturated polymerizable

[0152] 本发明的组合物包括一种或多种可聚合的成分,从而形成可聚合的(即可硬化的)组合物。 [0152] The composition of the present invention comprises one or more polymerizable component, thereby forming a polymerizable (i.e. hardened) composition. 可聚合的成分通常是烯键式不饱和化合物,并可以是单体,低聚物,或聚合物。 The polymerizable composition is usually an ethylenically unsaturated compound, and can be monomeric, oligomeric, or polymeric.

[0153] 在某些实施方案中,组合物是可光聚合的,S卩,组合物含有通常是烯键式不饱和化合物的可光聚合的成分和光引发剂(即,光引发剂体系),从而在用光化射线照射时,引发组合物的聚合(或硬化)。 [0153] In some embodiments, the compositions are photopolymerizable, S Jie, the composition comprises usually photopolymerizable ethylenically unsaturated compound component and a photoinitiator (ie, a photoinitiator system), so that when actinic rays to initiate the polymerization of the composition (or hardening). 这种可光聚合的组合物可以是自由基可聚合的。 Such photopolymerizable compositions can be free radically polymerizable.

[0154] 在某些实施方案中,组合物是化学可聚合的,即,组合物含有通常是烯键式不饱和化合物的化学可聚合的成分和化学引发剂(即,引发剂体系),从而未用光化射线照射就能聚合,固化,或硬化组合物。 [0154] In certain embodiments, the compositions are chemically polymerizable, i.e., the composition contains the chemical component and are usually ethylenically unsaturated compounds polymerizable chemical initiator (i.e., initiator system), whereby not irradiated with actinic rays can be polymerized and cured or hardened composition. 这种化学可聚合的组合物有时称作"自固化"组合物,可以包括树脂_改进的玻璃离聚物胶合剂,氧化还原固化体系,和其组合。 Such chemically polymerizable compositions are sometimes referred to as "self-cure" compositions can include a resin _ improved glass ionomer cement, redox cure systems, and combinations thereof.

[0155] 本发明的烯键式不饱和化合物(即,含有至少一个烯键式不饱和双键的化合物) 包括可以使用自由基聚合反应机理进行聚合的单体,低聚物,和聚合物。 [0155] ethylenically unsaturated compound of the present invention (ie, a compound of at least one ethylenically unsaturated double bond, a) including the ability to use the mechanism of radical polymerization of monomers, oligomers, and polymers polymerized. 烯键式不饱和化合物的实例包括(甲基)丙烯酸酯(即,丙烯酸酯和甲基丙烯酸酯),包括单(甲基)丙烯酸酯,二(甲基)丙烯酸酯,聚(甲基)丙烯酸酯,或其组合。 Ethylenically unsaturated compounds include (meth) acrylate (i.e., acrylate and methacrylate), comprising mono (meth) acrylate, di (meth) acrylates, poly (meth) acrylic acid ester, or a combination thereof. 这种化合物可以是未取代的或用羟基所取代。 Such compounds may be unsubstituted or substituted with a hydroxyl group. 这种化合物可以含有酸官能团(如下面部分所述)或没有酸官能团。 Such compounds may contain acid functional groups (as described in the following section) or no acid functional groups.

[0156] 示例性烯键式不饱和化合物包括(甲基)丙烯酸甲酯,(甲基)丙烯酸乙酯,(甲基)丙烯酸异丙基酯,(甲基)丙烯酸正己基酯,(甲基)丙烯酸硬脂基酯,(甲基)丙烯酸烯丙基酯,三(甲基)丙烯酸甘油酯,二(甲基)丙烯酸乙二醇酯,二(甲基)丙烯酸二乙二醇酯,二(甲基)丙烯酸三乙二醇酯,二(甲基)丙烯酸1,3_丙二醇酯,三(甲基) 丙烯酸三羟甲基丙烷酯,三(甲基)丙烯酸1,2,4_ 丁三醇酯,二(甲基)丙烯酸1,4_环己二醇酯,四(甲基)丙烯酸季戊四醇酯,六(甲基)丙烯酸山梨糖醇酯,(甲基)丙烯酸四氢呋喃基酯,双[1-(2_丙烯酰氧基)]-p_乙氧基苯基二甲基甲烷,双[1-(3_丙烯酰氧基-2-羟基)]-p_丙氧基苯基二甲基甲烷,二(甲基)丙烯酸乙氧基化的双酚A酯,和三羟乙基_异氰脲酸酯三(甲基)丙烯酸酯;(甲基)丙烯酰胺(即,丙烯酰胺和甲基丙烯酰胺),如(甲基)丙烯酰胺,亚甲基双_(甲基)丙烯酰胺,和乙酰丙酮(甲基)丙烯酰胺;氨基甲酸酯(甲基)丙烯酸酯;聚乙二醇的双_(甲基)丙烯酸酯(优选分子量为200-500), 丙烯酸酯的单体的可共聚合的混合物,如公开在美国专利4,652,274 (Boettcher等人)中的那些,和丙烯酸酯的低聚物,如公开在美国专利4,642,126(Zad0r等人)中的那些;和乙烯基化合物,如苯乙烯,邻苯二甲酸二烯丙基酯,琥珀酸二乙烯基酯,己二酸二乙烯基酯和邻苯二甲酸二乙烯基酯。 [0156] Exemplary ethylenically unsaturated compounds include (meth) acrylate, ethyl (meth) acrylate, ethyl (meth) acrylate, isopropyl acrylate, (meth) acrylate, n-hexyl acrylate, (meth ) acrylate, stearyl (meth) acrylate, allyl acrylate, tri (meth) acrylate, di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol 1,3_, tri (meth) acrylate, trimethylolpropane ester, tri (meth) acrylate, butyl three 1,2,4_ alcohol esters, di (meth) acrylate, cyclohexyl 1,4_ glycol, tetra (meth) acrylate, pentaerythritol hexa (meth) acrylate, sorbitol esters, (meth) acrylate, tetrahydrofuryl acrylate, bis [ 1- (2_ acryloxy)] - p_-ethoxyphenyl dimethylmethane, bis [1- (3_ acryloxy-2-hydroxy)] - p_ propoxyphenyl two methyl methane, di (meth) acrylate esters of ethoxylated bisphenol A, and trishydroxyethyl _ isocyanurate tri (meth) acrylate; (meth) acrylamides (ie, acrylamides and methacrylamides) such as (meth) acrylamide, methylene bis _ (meth) acrylamide, and acetylacetone (meth) acrylamide; urethane (meth) acrylate; polyethylene _ Those glycol bis (meth) acrylate (preferably molecular weight 200-500), copolymerizable mixtures of acrylate monomers, as disclosed in U.S. Patent No. 4,652,274 (Boettcher et al.) , and acrylate oligomers, as disclosed in U.S. Patent No. 4,642,126 (Zad0r et al) those; and vinyl compounds such as styrene, diallyl phthalate esters, dimethyl succinate vinyl esters, divinyl adipate and divinyl phthalate esters. 其他适合的自由基可聚合的化合物包括硅氧烷官能化的(甲基)丙烯酸酯,例如,公开在W0-00/38619 (Guggenberger 等人),W0-01/92271 (Weinmann 等人),WO-01/07444 (Guggenberger 等人),W0-00/42092 (Guggenberger 等人)中,和氟聚物官能化的(甲基)丙烯酸酯,例如,公开在美国专利5,076,844(Fock等人),美国专利4, 356, 296 (Griffith 等人),EP_0373 384 (ffagenknecht 等人),EP-O2Ol 031 (Reiners 等人),和EP-0201 778 (Reiners等人)中。 Other suitable free radically polymerizable compounds include siloxane-functional (meth) acrylates, e.g., as disclosed in W0-00 / 38619 (Guggenberger et al.), W0-01 / 92271 (Weinmann et al.), WO -01/07444 (Guggenberger et al.), W0-00 / 42092 (Guggenberger et al.), and fluoropolymer-functional (meth) acrylate, for example, disclosed in U.S. Patent No. 5,076,844 (Fock et al.), US Patent No. 4, 356, 296 (Griffith et al.), EP_0373 384 (ffagenknecht et al.), EP-O2Ol 031 (Reiners et al.), and EP-0201 778 (Reiners et al.). 需要时可以使用两种或多种自由基可聚合的化合 There are two or more free radical polymerizable compound when required

18物的混合物。 18 mixture thereof.

[0157] 烯键式不饱和化合物在一个分子中也可以含有羟基和自由基活性的官能团。 [0157] ethylenically unsaturated compound in one molecule may also contain a hydroxyl group and a radical reactive functional groups. 这种材料的实例包括(甲基)丙烯酸羟烷基酯,如(甲基)丙烯酸2-羟乙基酯和(甲基)丙烯酸2-羟丙基酯;甘油单-和二_(甲基)丙烯酸酯;三羟甲基丙烷单-和二_(甲基)丙烯酸酯;季戊四醇单_,二_,和三_(甲基)丙烯酸酯;山梨糖醇单_,二_,三_,四_,和五_(甲基)丙烯酸酯;和2,2-双[4-(2-羟基-3-甲基丙烯酰氧基丙氧基)苯基]丙烷(bisGMA)。 Examples of such materials include (meth) acrylic acid hydroxyalkyl esters such as (meth) acrylate, 2-hydroxyethyl acrylate and (meth) acrylate, 2-hydroxypropyl acrylate; mono- - _ and di (meth ) acrylate; trimethylolpropane single - and two _ (meth) acrylate; pentaerythritol single _, _ two, and three _ (meth) acrylate; sorbitol single _, _ two or three _, _ four, and five _ (meth) acrylate; and 2,2-bis [4- (2-hydroxy-3-methacryloxy-propoxy) phenyl] propane (bisGMA). 适合的烯键式不饱和化合物也可从各种商业源得到,如Sigma-Aldrich,St. Louis,MO,Rhom 和Tech,Inc.,Darmstadt, Germany。 Suitable ethylenically unsaturated compounds are also available from various commercial sources such as Sigma-Aldrich, St. Louis, MO, Rhom and Tech, Inc., Darmstadt, Germany. 需要时可以使用烯键式不饱和化合物的混合物。 You can use the ethylenically unsaturated compound mixture as needed.

[0158] 牙科组合物中优选的烯键式不饱和化合物包括包括甲基丙烯酸2-羟基乙基酯(HEMA) ,PEGDMA(二甲基丙烯酸聚乙二醇酯,分子量约400),bisGMA,UDMA(氨基甲酸酯二甲基丙烯酸酯),GDMA ( 二甲基丙烯酸甘油酯),TEGDMA (二甲基丙烯酸三乙二醇酯),公开在美国专利6,030,606 (Holmes)中的bisEMA6,和NPGDMA (新戊二醇二甲基丙烯酸酯)。 [0158] Dental compositions preferred ethylenically unsaturated compounds include methyl acrylate include 2-hydroxyethyl acrylate (HEMA), PEGDMA (polyethylene glycol dimethacrylate having a molecular weight of approximately 400), bisGMA, UDMA (urethane dimethacrylate), GDMA (glycerol dimethacrylate), TEGDMA (triethylene glycol dimethacrylate), bisEMA6 disclosed in U.S. Patent 6,030,606 (Holmes) in the , and NPGDMA (neopentylglycol dimethacrylate). 需要时可以使用烯键式不饱和化合物的各种组合。 You can use various combinations of ethylenically unsaturated compounds of formula when needed.

[0159] 优选地,按未充填的组合物总重计,本发明的组合物包括至少,更优选至少lOwt-%,最优选至少15wt-%的烯键式不饱和化合物。 [0159] Preferably, the composition according to unfilled total weight of the composition of the present invention comprises at least, more preferably at least lOwt-%, most preferably at least 15wt-% of ethylenically unsaturated compounds. 优选地,按未充填的组合物总重计, 本发明的组合物包括至多95wt-%,更优选至多90wt-%,最优选至多80wt-%的烯键式不饱和化合物。 Preferably, according to unfilled weight of the total composition, the composition of the present invention comprises up 95wt-%, more preferably at most 90wt-%, most preferably at most 80wt-% of ethylenically unsaturated compounds.

[0160] 可聚合的带有酸官能团的烯键式不饱和化合物 [0160] polymerizable ethylenically acid functional group with an unsaturated compound

[0161] 本文中,带有酸官能团的烯键式不饱和化合物包括具有烯键不饱和键及酸和/或酸前体官能团的单体,低聚物,和聚合物。 [0161] As used herein, ethylenic acid functional groups with unsaturated compounds include those having ethylenic unsaturated bond and acid and / or acid precursor functional monomers, oligomers, and polymers. 酸前体官能团包括例如酸酐,酰卤,和焦磷酸酯。 Acid precursor functional groups include for example acid anhydride, and pyrophosphate. 这种带有酸官能团的烯键式不饱和化合物存在于本发明的某些实施方案中。 Such compounds with ethylenically unsaturated acid functional groups present in certain embodiments of the present invention.

[0162] 示例性带有酸官能团的烯键式不饱和化合物包括例如α,β-不饱和酸性化合物,如甘油磷酸酯单(甲基)丙烯酸酯,甘油磷酸酯二(甲基)丙烯酸酯,羟乙基(甲基) 丙烯酸酯磷酸酯,柠檬酸二或三(甲基)丙烯酸酯,聚(甲基)丙烯酸酯的低聚马来酸,聚(甲基)丙烯酸酯的聚马来酸,聚(甲基)丙烯酸酯的聚(甲基)丙烯酸,聚(甲基)丙烯酸酯的多羧基-多膦酸,聚(甲基)丙烯酸酯的多氯磷酸,聚(甲基)丙烯酸酯的多磺酸酯,聚(甲基)丙烯酸酯的多硼酸等。 Ethylenically unsaturated compound [0162] Exemplary having acid functional groups include, for example α, β- unsaturated acidic compounds such as glycerol phosphate mono (meth) acrylate, glycerol phosphate di (meth) acrylate, polymaleic acid, hydroxyethyl (meth) acrylate phosphate, citric acid di- or tri (meth) acrylate, poly (meth) acrylate oligomeric maleic acid, poly (meth) acrylate , poly (meth) acrylate, poly (meth) acrylic acid, polycarboxylic poly (meth) acrylate - polyphosphonic acids, polychlorinated phosphate poly (meth) acrylate, poly (meth) acrylates multi-sulfonate, poly (meth) acrylate, etc. Multi borate. 本发明某些优选的组合物包括具有至少一个P-OH部分的带有酸官能团的烯键式不饱和化合物。 Certain preferred compositions of the present invention include those having at least one P-OH part of ethylenic acid functional groups with unsaturated compounds.

[0163] 这些化合物中的某些例如可以作为(甲基)丙烯酸异氰酸酯基烷基酯和羧酸的反应产物得到(例如,二羟基甲基丙酸的二异氰酸酯基乙基甲基丙烯酸酯衍生物(PDMA)或柠檬酸的二异氰酸酯基乙基甲基丙烯酸酯衍生物(CDMA))。 [0163] Some of these compounds can be used as such as (meth) acrylic acid alkyl ester of an isocyanate group and a carboxylic acid reaction product (for example, di-hydroxy acid methyl diisocyanate ethyl methacrylate derivatives (PDMA) or di-isocyanate ethyl methacrylate derivatives of citric acid (CDMA)). 其他具有酸官能团和烯键式不饱和成分的化合物公开在美国专利4,872,936 (Engelbrecht)和5,130,347 (Mitra)中。 Other compounds having acid functional groups and ethylenically unsaturated components are disclosed in U.S. Patent No. 4,872,936 (Engelbrecht) and 5,130,347 (Mitra) in. 可以使用各种含有烯键式不饱和键和酸部分的化合物。 Various compounds containing an ethylenically unsaturated bond and acid moieties can be used. 需要时可以使用这类化合物的混合物。 A mixture of such compounds can be used when needed.

[0164] 其他带有酸官能团的烯键式不饱和化合物包括例如可聚合的双膦酸,公开在例如2002年12月30日提交的美国临时申请60/437,106中;AA: ITA: IEM(通过使AA: ITA共聚物与足够甲基丙烯酸2-异氰酸酯基乙基酯反应,将共聚物的部分酸基团转化成悬挂的甲基丙烯酸酯基团,而得到的带有悬挂的甲基丙烯酸酯的丙烯酸:衣康酸的共聚物,例如,公开在美国专利5,130,347(Mitra))的实施例11中;和美国专利4,259,075(Yamauchi 等人),4,499,251(Omura 等人),4,537,940(Omura 等人), [0164] Other unsaturated compounds with acid functionality include, for example ethylenically polymerizable bisphosphonate, disclosed, for example the United States December 30, 2002 filed provisional application 60 / 437,106 in; AA: ITA: IEM (by AA: ITA copolymer with sufficient methyl acrylate, 2-ethyl ester isocyanate reaction, part of the acid groups of the copolymer is converted to suspension of methacrylate groups, and with the resulting suspension of methyl acrylic acrylate: itaconic acid copolymers, for example, disclosed in Example 11 in U.S. Patent 5,130,347 (Mitra)); and a U.S. Patent 4,259,075 (Yamauchi et al.), 4,499 , 251 (Omura et al.), 4,537,940 (Omura et al.),

194,539, 382 (Omura 等人),5, 530, 038 (Yamamoto 等人),6, 458, 868 (Okada 等人),和欧洲专利申请公开EP 712, 622 (Tokuyama Corp.)和EPl, 051,961 (Kuraray Co. , Ltd.)中所述的那些。 194,539, 382 (Omura et al.), 5, 530, 038 (Yamamoto et al.), 6, 458, 868 (Okada et al.), And European Patent Application Publication No. EP 712, 622 (Tokuyama Corp.) and EPl, 051,961 (Kuraray Co., Ltd.) in those described. 此外,烯键式不饱和磷酰基化的化合物和羧酸功官聚合物的组合公开在例如美国专利5,256,447 (Oxman 等人)中。 In addition, ethylenically unsaturated phosphorus acylated combination of compounds and carboxylic acid functions officer polymers are disclosed in, for example, U.S. Patent 5,256,447 (Oxman et al.).

[0165] 优选地,当一种或多种带有酸官能团的烯键式不饱和化合物存在于本发明的组合物中时,按未充填的组合物总重计,组合物包括至少lwt-%,更优选至少3wt_%,和最优选至少5wt-%的带有酸官能团的烯键式不饱和化合物。 [0165] Preferably, when one or more ethylenically unsaturated compounds with acid functional group more present in the compositions of the present invention, the press unfilled weight of the total composition, the composition comprises at least lwt-% more preferably at least 3wt_%, and most preferably at least 5wt-% of ethylenic acid functional groups with unsaturated compounds. 优选地,按未充填的组合物总重计,本发明的组合物包括至多80wt-%,更优选至多70wt-%,和最优选至多60wt-%的带有酸官能团的烯键式不饱和化合物。 Preferably, according to unfilled weight of the total composition, the composition of the present invention comprises up 80wt-%, more preferably at most 70wt-%, and most preferably at most 60wt-% of ethylenic acid functional group with an unsaturated compound .

[0166] 牙科添加剂 [0166] Dental additive

[0167] 本发明某些实施方案可以包括一种或多种牙科添加剂。 Certain embodiments of the invention [0167] This may include one or more dental additives. 示例性牙科添加剂包括氟化物,增白剂,抗龋齿剂(例如,木糖醇),再矿化剂(例如,磷酸钙化合物),酶,呼吸清凉剂,麻醉剂,凝块剂,酸中和剂,化学治疗剂,免疫反应调节剂,药物,指示剂,染料,颜料,润湿剂,表面活性剂,缓冲剂,粘度改性剂,触变胶,填料,多元醇,抗菌剂,抗真菌剂,稳定剂, 治疗口腔干燥的药剂,脱敏剂,和其组合。 Exemplary additives include fluoride dental, whitening agents, anticaries agents (e.g., xylitol), remineralizing agents (e.g., calcium phosphate compounds), enzymes, breath fresheners, anesthetics, clot agent, acid and agents, chemotherapeutic agents, immune response modifiers, medicaments, indicators, dyes, pigments, wetting agents, surfactants, buffering agents, viscosity modifiers, thixotropes, fillers, polyols, antimicrobial agents, antifungal agents, stabilizers, treat xerostomia agents, desensitizing agents, and combinations thereof. 下面更详细地说明上述添加剂中的一些。 Will be described in more detail some of the above-described additives.

[0168] 氟化物 [0168] fluoride

[0169] 适合的氟化物包括例如在美国专利5,607,663 (Rozzi等人),5,662,887 (Rozzi 等人),5,866,630 (Mitra 等人),5,876,208 (Mitra 等人),5,888,491 (Mitra 等人),禾口6,312,668 (Mitra等人)中所述的氟化物盐类。 [0169] Examples of suitable fluorides include, for example, in U.S. Patent 5,607,663 (Rozzi et al.), 5,662,887 (Rozzi et al.), 5,866,630 (Mitra et al.), 5,876,208 (Mitra et al.), 5,888,491 (Mitra et al.), Hekou 6,312,668 (Mitra et al.) fluoride salts. 优选的氟化物释放源包括例如公开在美国专利4,871,786 (Aasen等人)中的四氟硼酸盐阴离子。 Preferred fluoride sources include, for example, release tetrafluoroborate anion is disclosed in U.S. Patent 4,871,786 (Aasen et al.) In the. 氟化物释放源的优选重复单元包括三甲基铵甲基甲基丙烯酸酯。 Preferably repeating units include fluoride releasing source trimethyl ammonium methacrylate.

[0170] 填料 [0170] packing

[0171] 本发明的组合物可含有填料。 [0171] The compositions of the invention may contain fillers. 填料可以选自牙科应用中所用的组合物中的各种材料中的一种或多种,如现在牙科修复组合物中所用的填料等。 Fillers may be selected from the compositions used for dental applications in a variety of materials in one or more, such as dental restorative compositions now used in the filler.

[0172] 填料优选是精细分散的。 [0172] Preferably the filler is finely divided. 填料可以具有单峰或多峰(例如,双峰)粒径分布。 The filler can have a unimodal or multimodal (e.g., bimodal) particle size distribution. 优选地,填料的最大粒径(粒子最大尺寸,通常指直径)小于5微米,更优选小于0.5微米,最优选小于0. 1微米。 Preferably, the filler is the maximum particle size (maximum particle size, generally refers to the diameter) of less than 5 microns, more preferably less than 0.5 microns, most preferably less than 0.1 micron. 优选地,填料的平均粒径小于0. 1微米,更优选小于0. 075微米。 Preferably, the average particle size of the filler is less than 0.1 microns, more preferably less than 0.075 microns.

[0173] 填料可以是无机材料。 [0173] The filler can be an inorganic material. 也可以是在树脂体系中不溶的交联有机材料,并可选择地用无机填料充填。 It may also be cross-linked organic material insoluble in the resin system, and optionally filled with inorganic filler. 在任何情况下,填料应该是无毒的,并适用于口腔中。 In any case, the filler should be non-toxic and suitable for use in the oral cavity. 填料可能透不过射线或者可以透过射线。 Radiopaque fillers may or may transmit the radiation rays. 填料通常在水中基本上不溶。 Filler typically is substantially insoluble in water.

[0174] 适合的无机填料实例是天然或合成材料,包括但不限于:石英;氮化物(例如,氮化硅);衍生于例如Zr,Sr,Ce, Sb,Sn, Ba, Zn,和Al的玻璃;长石;硼硅酸盐玻璃;高岭石; 滑石;氧化钛;低Mohs硬度填料,如公开在美国专利4,695,251 (Randklev)中的那些;和亚微型氧化硅粒子(例如,热解氧化硅,如以商品名AER0SIL从DegussaCorp.,Akron,0H得到的那些,包括〃 OX 50",“ 130",“ 150"和〃 200"氧化硅,从Cabot Corp. ,Tuscola, IL得到的CAB-O-SIL M5氧化硅)。 [0174] Suitable examples of the inorganic filler is a natural or synthetic materials, including but not limited to: quartz; nitrides (e.g., silicon nitride); derived from e.g. Zr, Sr, Ce, Sb, Sn, Ba, Zn, and Al glass; feldspar; borosilicate glass; kaolinite; talc; titanium oxide; low Mohs hardness fillers such as those disclosed in U.S. Patent 4,695,251 (Randklev) in the; and submicron silica particles ( For example, fumed silica, such as the trade name AER0SIL from DegussaCorp., Akron, those, "200 and 〃" 0H resulting silicon oxide include 〃 OX 50 "," 130 "," 150, from Cabot Corp., Tuscola, IL was CAB-O-SIL M5 silica). 适合的有机填料粒子实例包括充填或未充填的粉状聚碳酸酯、降环氧化物等。 Examples of suitable organic filler particles include filled or unfilled polycarbonate powder, the lower epoxides and the like.

[0175] 优选的非酸反应性填料粒子是石英,亚微型氧化硅,和美国专利4,503,169 (Randklev)中所述的非玻璃质微粒子。 [0175] Preferred non-acid-reactive filler particles are quartz, submicron non-vitreous silica fine particles, and U.S. Patent 4,503,169 (Randklev) described. 还可使用这些非酸反应性填料的混合物,及从有机和无机材料制得的混合填料。 You can also use these non-acid-reactive filler mixture, and mix the filler from organic and inorganic materials prepared.

[0176] 填料粒子的表面也可以用偶联剂处理,从而增强填料和树脂间的键合。 [0176] surface of the filler particles may be treated with a coupling agent to enhance the bonding between the filler and the resin. 适用的偶 Even applicable

联剂包括Y-甲基丙烯酰氧基丙基三甲氧基硅烷,Y-巯基丙基三乙氧基硅烷,Y-氨基丙基三甲氧基硅烷等。 Y- linking agents include methacryloxy propyl trimethoxy silane, Y- mercaptopropyl triethoxy silane, Y- aminopropyl trimethoxysilane.

[0177] 填料也可以是酸反应性填料。 [0177] fillers may also be an acid-reactive filler. 酸反应性填料通常与酸功能树脂成分混合使用,并可以与非反应性填料混合使用,或不与其混合。 Acid-reactive filler is typically mixed with an acid functional resin component and a non-reactive filler may be used in combination, or mixed therewith. 如果需要,酸反应性填料也可以具有释放氟化物的性能。 If desired, the acid-reactive filler may also have fluoride-releasing properties. 适合的酸反应性填料包括金属氧化物,玻璃,和金属盐。 Suitable acid-reactive fillers include metal oxides, glass, and metal salts. 优选的金属氧化物包括氧化钡,氧化钙,氧化镁,和氧化锌。 Preferred metal oxides include barium oxide, calcium oxide, magnesium oxide, and zinc oxide. 优选的玻璃包括硼酸盐玻璃,磷酸盐玻璃,和氟铝硅酸盐(“FAS")玻璃。 Preferred glasses include borate glasses, phosphate glasses, and fluoroaluminosilicate ("FAS") glass. FAS玻璃是特别优选的。 FAS glasses are particularly preferred. FAS玻璃优选含有足量可洗脱的阳离子, 从而当玻璃与可硬化的组合物的成分混合时,将形成硬化的牙科组合物。 FAS glass preferably contains sufficient elutable cations so that when the composition of the glass and the hardenable composition are mixed, will form a hardened dental composition. 玻璃优选也含有足量可洗脱的氟离子,从而硬化的组合物将具有防龋性能。 Preferably the glass can also contain a sufficient amount of fluoride ions eluted, whereby the hardened composition will have anticariogenic properties. 使用FAS玻璃制造领域中的技术人员所熟悉的技术,也可从含有氟化物,氧化铝,和其他玻璃成分的熔融体制造玻璃。 Use FAS glass manufacturing in the art are familiar with the technology, but also from the group consisting of fluoride, alumina, and other glass components melt glassmaking. FAS 玻璃优选是足够分散的粒子形式,从而它们能够方便地与其他胶合剂成分混合,并且当生成的混合物被用于口中时效果的更好。 FAS glass preferably is in the form of particles dispersed enough so that they can be easily mixed with other binder ingredients and the resulting mixture is better when the effect when used in the mouth.

[0178] 优选地,使用例如沉淀式分析仪测得,FAS玻璃的平均粒径(通常,直径)不大于约10微米,更优选不大于5微米。 [0178] Preferably, for example, precipitation analyzers measured, the average particle diameter of FAS glass (typically, diameter) of no greater than about 10 microns, more preferably not more than 5 microns. 适合的FAS玻璃对于本领域所属技术人员而言是熟悉的, 并可从各种商业源得到,许多可从现有玻璃离聚物胶合剂中得到,如可按商品名VITREMER, VITREBOND, RELY X LUTING CEMENT 和KETAC-FIL(3M ESPEDental Product, St. Paul, MN), FUJI II,GC FUJI LC禾口FUJI IX(G_CDental Industrial Corp.,Tokyo,Japan)和CHEMFIL Superior(Dentsplylnternational,York,PA)得到的那些。 Suitable FAS glass for this skill in the art will be familiar, and can be obtained from various commercial sources, many available from existing glass ionomer cement, as available under the trade name VITREMER, VITREBOND, RELY X LUTING CEMENT and KETAC-FIL (3M ESPEDental Product, St. Paul, MN), FUJI II, GC FUJI LC Hekou FUJI IX (G_CDental Industrial Corp., Tokyo, Japan) and CHEMFIL Superior (Dentsplylnternational, York, PA) obtained Those ones. 需要时可以使用填料混合物。 You can use the filler mixture as needed.

[0179] FAS玻璃可选择地被进行表面处理。 [0179] FAS glass optionally be subjected to a surface treatment. 适合的表面处理包括但不限于酸洗(例如,用磷酸处理),用磷酸盐处理,用螯合剂(如酒石酸)处理,和用硅烷或者用酸性或碱性硅烷醇溶液处理。 Suitable surface treatments include but are not limited to acid (e.g., treatment with phosphoric acid), treatment with phosphates, treatment with chelating agents (e.g., tartaric acid), and treated with a silane or an acidic or basic silanol solution. 优选地,处理溶液或处理的玻璃的PH被调节到中性或接近中性,因为这样可以提高可硬化的组合物的保存稳定性。 Preferably, PH treating solution or the treated glass is adjusted to neutral or near-neutral, as this can increase storage stability of the hardenable composition.

[0180] 在某些组合物中,在可硬化的组合物中可以使用酸反应性和非酸反应性填料的混合物。 [0180] In some compositions, the compositions can be hardened mixture can be used in the acid-reactive and non-acid-reactive filler.

[0181] 其他适合的填料公开在美国专利6,387,981 (Zhang等人)和6,572,693 (Wu等人) 及国际公开WO 01/30306 (Windisch等人)和W001/30307 (Zhang等人)中。 [0181] Other suitable fillers Publication Publication WO 01/30306 (Windisch et al.) And W001 / 30307 (Zhang in U.S. Patent 6,387,981 (Zhang et al.) And 6,572,693 (Wu et al.) And International et al.). 这些文献中所述的填料成分包括纳米尺寸的氧化硅粒子和金属氧化物粒子,如钇,锶,钡,锆,铪,铌,钽, 钨,铋,钼,锡,锌,镧系元素(即原子序数为57〜71的元素),和铈的氧化物,和其组合。 The filler component described in the literature which include nano-sized silica particles and metal oxide particles, such as yttrium, strontium, barium, zirconium, hafnium, niobium, tantalum, tungsten, bismuth, molybdenum, tin, zinc, lanthanides ( That is the atomic number of the element 57~71), and oxide, cerium, and combinations thereof.

[0182] 对于包括填料(例如,牙科粘合组合物)的本发明实施方案而言,按组合物总重计,组合物优选地包括至少Iwt-%,更优选至少,和最优选至少的填料。 [0182] For include fillers (e.g., dental adhesive compositions) of the embodiments of the present invention, the total weight of the composition, the composition preferably comprises at least Iwt-%, more preferably at least, and most preferably at least of the filler . 对于这种实施方案,按组合物总重计,本发明的组合物优选地包括至多40wt-%,更优选至多20wt-%,和最优选至多15wt-%的填料。 For this embodiment, the total weight of the composition, the composition of the present invention preferably comprises up to 40wt-%, more preferably up to 20wt-%, and most preferably up to 15wt-% of a filler.

[0183] 对于其他实施方案(例如,其中组合物是牙科修复剂或正牙粘合剂)而言,按组合物总重计,本发明的组合物优选地包括至少40wt-%,更优选至少45wt-%,和最优选至少50wt-%的填料。 [0183] For other embodiments (e.g., wherein the composition is a dental restorative or an orthodontic adhesive), the total weight of the composition, the composition of the present invention preferably comprises at least 40wt-%, more preferably at least 45wt-%, and most preferably at least 50wt-% filler. 对于这种实施方案而言,按组合物总重计,本发明的组合物优选地包括至多90wt-%,更优选至多80wt-%,再更优选至多70wt-%的填料,和最优选至多50wt-%的填料。 For this embodiment, the total weight of the composition, the composition of the present invention preferably comprises up to 90wt-%, more preferably up to 80wt-%, still more preferably up to 70wt-% of a filler, and most preferably at most 50wt -% filler.

21[0184] 表面活性剂,乳化剂,和油包水乳液 21 [0184] surfactants, emulsifiers, and water in oil emulsions

[0185] 在本发明的一些实施方案中使用表面活性剂,例如,有助于制备稳定乳液形式的牙科组合物。 [0185] the use of surfactants In some embodiments of the present invention, for example, helps to form a stable emulsion prepared dental compositions.

[0186] 按乳液总重计,乳液优选地包括至少lwt-%的水,更优选至少的水,对于某些实施方案而言,最优选乳液包括至少的水。 [0186] the total weight of the emulsion, the emulsion preferably comprises at least lwt-% of water, more preferably at least water, for some embodiments, the most preferred emulsion comprises at least water. 按乳液总重计,其优选地包括不超过70wt-%的水,更优选不超过50wt-%的水。 The total weight of the emulsion, which preferably comprises no more than 70wt-% of water, more preferably not more than 50wt-% of water.

[0187] 通常,乳化剂和/或表面活性剂用于制备本发明的乳液。 [0187] Typically, emulsifiers and / or surfactants used in the preparation of the emulsion of the present invention. 在水相中加入低水平的稳定化成分也是有利的。 In the aqueous phase of the low levels of stabilizing ingredients also advantageous. 盐如硫酸镁可能是有用的乳液稳定化剂。 Salts such as magnesium sulfate may be useful emulsion stabilizers. 加入水溶性树胶,如瓜尔胶衍生物,黄原胶,和增稠剂,如羟基乙基纤维素,羟基丙基纤维素和羧基乙烯基聚合物, 可能有助于稳定乳液。 Add water-soluble gums such as guar derivatives, xanthan gum, and thickeners such as hydroxyethyl cellulose, hydroxypropyl cellulose and carboxyvinyl polymer, may help stabilize the emulsion.

[0188] 制备油包水微乳液的一般方法包括分别加热油相(含有聚合物和可选择的成分,例如,表面活性剂)和水相(含有可选择的成分,例如,表面活性剂和/或稳定化成分), 在良好搅拌下将水相缓慢加到油相中。 [0188] General method for the preparation of water in oil microemulsion comprising an oil phase were heated (comprising a polymer and optional ingredients, e.g., surfactants) and water phase (containing optional ingredients, e.g., surfactants and / or stabilization component), with good stirring to the oil phase slowly added to the aqueous phase. 均质化是优选的,但不是必须的。 Homogenization is preferred, but not necessary. 经冷却,可以加入其他可选择的成分,例如,填料。 Upon cooling, other optional ingredients may be added, for example, fillers. 为制备其他油包水微乳液,不需要加热。 To prepare other oil-in-water microemulsion, no heating. 通常成功地制备微乳液取决于各种因素,如温度、混合比和时间,剪切力等 Various factors often successfully prepared microemulsion depends, such as temperature, mixing ratio and time, shear force, etc.

[0189] 微乳液可以是水包油(0/1)或油包水(W/0)型,但后一种对于本发明是特别有利的。 [0189] microemulsion may be water-in-oil (0/1) or oil-in-water (W / 0) type, but the latter for the present invention is particularly advantageous. 在分散至多100纳米的水滴的条件下形成油包水型微乳液,通常通过在水/油界面上吸附表面活性剂和共表面活性剂以降低界面表面张力来得到。 Up to 100 nm in the dispersed droplets of water-in-oil conditions for forming microemulsion, typically by adsorption of surfactant and co-surfactant in the water / oil interface to reduce the interfacial surface tension obtained. 微乳液理论公开在科学文献中,包括例如Leung 等人,第9 章,“Surfactants in Chemical Process Engineering", MarcelDekker (1988) ;Overbeek 等人,"Surfactants “ in Microemulsions, Academic Press (1984) ;Safran 等人,Phys. Rev. Lett.,50 : 1930 (1983) ;Ruckenstein 等人,J. Chem. Soc. Faraday Trans, 2, 71 : 1690 (1975);禾口Ostrovsky 等人,J. Colloid. Interface Sci., 102 :206(1984)。 Microemulsion theory has been publicized in the scientific literature, including for example, Leung et al., Chapter 9, "Surfactants in Chemical Process Engineering", MarcelDekker (1988); Overbeek et al., "Surfactants" in Microemulsions, Academic Press (1984); Safran, etc. . man, Phys Rev. Lett, 50: 1930 (1983); Ruckenstein et al., J Chem Soc Faraday Trans, 2, 71:... 1690 (1975); Hekou Ostrovsky et al., J Colloid Interface Sci... ., 102: 206 (1984).

[0190] 在制备油包水微乳液的一般过程中,在最终步骤中,缓慢将水加到组合物的其余成分中,直到形成初始浑浊。 [0190] In a typical process for preparing an oil-in-water microemulsion, in the final step, slowly adding water to the remaining components of the composition until the formation of the initial cloudy. 通过在此"滴定"过程中,微乳液在初始浑浊时形成。 By this "titration" procedure, the micro-emulsion is formed during the initial cloudy. 这通常需要按组合物总重计8wt-%〜12wt-%的水。 This usually requires the total weight of the composition 8wt-% ~12wt-% of water. 通常,通过简单的混合形成微乳液,在加入水之前不需要单独地预混合或加热组合物的油和水成分。 Typically, the formation of microemulsions by simple mixing, prior to the addition of water is unnecessary to separately or pre-mixed oil and heated water components of the composition.

[0191] 可光漂白的染料 [0191] photobleachable dye

[0192] 在一些实施方案中,本发明的组合物优选其开始颜色明显不同于牙齿结构。 [0192] In some embodiments, the compositions of the present invention is preferably significantly different from its starting color to tooth structure. 优选通过使用光漂白的染料使组合物具有颜色。 Preferably by using a dye photobleaching the composition has a color. 按组合物总重计,组合物优选地包括至少0. 001wt-%的可光漂白的染料,更优选至少0. 002wt-%可光漂白的染料。 The total weight of the composition, compositions preferably comprise at least 0. 001wt-% of photobleachable dye, more preferably at least 0. 002wt-% photobleachable dye. 按组合物总重计, 组合物优选地包括至多lwt-%的可光漂白的染料,和更优选至多0. lwt-%的可光漂白的染料。 The total weight of the composition, compositions preferably comprise at most lwt-% of photobleachable dye, and more preferably up to 0. lwt-% of photobleachable dye. 可光漂白的染料的量可根据其消光系数,人眼辨别开始颜色的能力,和所需的颜色变化而变化。 Amount of dye photobleachable according to their extinction coefficient, the human eye to distinguish colors start capability, and color change needed change.

[0193] 可光漂白的染料的颜色形成和漂白特性随各种因素变化,包括例如空气中的酸强度,介电常数,极性,氧量,和湿度。 [0193] The dye can bleach the color of light is formed and bleaching characteristics vary depending upon various factors, including, for example air, acid strength, dielectric constant, polarity, amount of oxygen and humidity. 然而,通过照射组合物并分析颜色变化,可以容易地测定染料的漂白性能。 However, by irradiating the composition and analysis of the color change can be easily measured dye bleaching performance. 优选地,至少一种可光漂白的染料至少部分地溶解在可硬化的树脂中。 Preferably, at least one dye photobleachable at least partially soluble in a hardenable resin.

[0194] 示例性的可光漂白的染料公开在例如美国专利6,331,080 (Cole等人), 6,444,725 (Trom等人),和6,528,555 (Nikutowski等人)中。 [0194] Exemplary photobleachable dyes are disclosed in, for example, U.S. Patent 6,331,080 (Cole et al.), 6,444,725 (Trom et al), and 6,528,555 (Nikutowski et al.) . 优选的染料包括例如玫瑰红,亚甲基紫,亚甲基蓝,荧光素,曙红黄,曙红Y,乙基曙红,曙红蓝,曙红B,赤藓红B,赤藓红黄色共混物,甲苯胺蓝,4' ,5' -二溴荧光素,和其组合。 Preferred dyes include, for example Rose Bengal, methylene violet, methylene blue, fluorescein, eosin red, yellow, eosin Y, ethyl eosin, eosin and blue, eosin B, erythrosine B, erythrosine yellow blend material, toluidine blue, 4 ', 5' - dibromofluorescein, and combinations thereof.

[0195] 本发明组合物的颜色变化可用光引发。 Color change [0195] The present composition of the invention may be a photo-initiator. 优选地,使用光化射线引发组合物的颜色变化,使用例如在足够时间内发射可见或近红外(IR)光的牙科固化光。 Preferably, actinic radiation caused color change of the composition, for example, emits visible or near infrared dental curing light (IR) light for a sufficient time. 引发本发明组合物中颜色变化的机理可以与硬化树脂的硬化机理分开或基本上同时进行。 Mechanism of the primer composition of the present invention, the color change can be separated or substantially simultaneously with the hardening mechanism hardening resin. 例如,当化学(例如,氧化还原引发)或热引发聚合时,组合物可以硬化,从开始颜色到最终颜色的颜色变化可以在经光化射线照射而发生硬化过程之后发生。 For example, when a chemical (for example, a redox initiator) or thermal initiated polymerization, the composition may harden, the final color of the color change can take place from the start color to actinic radiation after irradiation hardening process.

[0196] 组合物颜色从开始颜色到最终颜色的变化优选地通过下面的颜色测试来量化。 [0196] The composition changes from the start color to the color of the final color is preferably quantified by the following color test. 使用颜色测试,测定ΔΕ*值,其表明3-维颜色空间的总颜色变化。 Use color test, measurement ΔΕ * value, which indicates the total color change in the 3-dimensional color space. 在正常照明条件下,人眼可以检测到约3 ΔE*单位的颜色变化。 Under normal lighting conditions, the human eye can detect a color change of approximately 3 ΔE * units. 本发明的牙科组合物优选地颜色变化ΔΕ*为至少20; 更优选,ΔΕ*为至少30;最优选Δ Ε*为至少40。 The dental composition of the present invention are preferably color change ΔΕ * is at least 20; more preferably, ΔΕ * of at least 30; most preferably at least 40 Δ Ε *.

[0197] 其他添加剂 [0197] Other additives

[0198] 可选择地,本发明的组合物含有稀释剂(例如,水)和/或溶剂(例如,醇(例如, 丙醇,乙醇),酮(例如,丙酮,甲基乙基酮),酯(例如,乙酸乙酯),和其他非水性溶剂(例如,二甲基甲酰胺,二甲基乙酰胺,二甲基亚砜,1-甲基-2-吡咯烷酮))。 [0198] Alternatively, the compositions of the present invention contain a diluent (e.g., water), and / or solvent (e.g., alcohols (e.g., propanol, ethanol), ketones (e.g., acetone, methyl ethyl ketone), esters (e.g., ethyl acetate), and other non-aqueous solvents (e.g., dimethylformamide, dimethylacetamide, dimethylsulfoxide, 1-methyl-2-pyrrolidone)). 需要时,本发明的组合物可以含有其他可选择的添加剂,如抑制剂,加速剂,和本领域所属技术人员熟悉的其他成分。 When required, the compositions of the present invention may contain other optional additives, such as inhibitors, accelerators, and in this skilled in the art are familiar with other ingredients.

[0199] 牙科组合物的制备和用途 [0199] The dental composition of the preparation and use

[0200] 使用常规混合技术,通过使至少一种烯键式不饱和化合物,芳基亚磺酸盐,可选择的电子受体,和可选择的敏化剂混合,来制备本发明的可聚合的(即,可硬化的)牙科组合物。 [0200] Using conventional mixing techniques, by reacting a compound of at least one ethylenically unsaturated arylalkylene salt, optional electron acceptor, and optionally mixed with a sensitizer, the present invention can be prepared by polymerization (i.e., hardenable) dental composition. 生成的组合物可选择地含有牙科添加剂(例如,填料,表面活性剂,可漂白的染料),水, 共溶剂,和上述其他添加剂。 Resulting dental composition optionally containing additives (e.g., fillers, surfactants, bleachable dyes), water, co-solvent, and the above-mentioned other additives. 在使用时,组合物可以含有光引发剂体系(例如,包括芳基亚磺酸盐电子供体,敏化剂,和可选择地电子受体),并通过光引发硬化,或可以含有热引发剂体系(例如,包括芳基亚磺酸盐电子供体和电子受体),并通过化学聚合如氧化还原固化机理来硬化。 In use, the composition may contain photoinitiator system (for example, including arylimine salt electron donor, a sensitizer, and optionally an electron acceptor), and trigger hardened by light, or may contain a thermal initiator agent system (for example, including arylimine salt electron donor and an electron acceptor), and hardened by chemical polymerization such as redox cure mechanism. 可选择地,可硬化的组合物可以含有引发剂体系(例如,包括芳基亚磺酸盐电子供体,敏化剂,和电子受体),使得组合物可以是可光聚合的和可化学聚合的组合物。 Alternatively, the hardenable composition may contain an initiator system (e.g., including arylalkylene sulfonates electron donor, sensitizer, and electron acceptor), such that the composition may be photopolymerizable and chemical polymerized composition.

[0201] 本发明的可聚合的组合物可以各种形式供给,包括一部分体系和多部分体系,例如,两部分粉末/液体,糊状物/液体,和糊状物/糊状物体系。 The composition of the invention can be polymerized [0201] This can be supplied in various forms, including a portion of the system and the multi-part system, for example, two-part powder / liquid, paste / liquid, and paste / paste system. 也可以使用其他利用多部分组合的形式(即,两部分或多部分的组合),每一部分是粉末,液体,凝胶,或糊状物形式。 You can also use other combinations utilizing a multi-part forms (ie, a combination of two or more parts), each of which is a powder, liquid, gel or paste form. 在氧化还原多部分体系中,一部分通常含有电子受体(例如,氧化剂),另一部分通常含有还原剂(例如,芳基亚磺酸盐)。 In a redox multi-part system, a part generally contains an electron acceptor (e.g., an oxidant), another part typically contains the reducing agent (e.g., aryl-sulfonate).

[0202] 可硬化的组合物的成分可以包括在试剂盒中,其中包装了组合物,从而保存成分, 直到需要时为止。 Component [0202] hardenable composition may be included in the kit, which packed composition, thereby preserving ingredients, until needed.

[0203] 当用作牙科组合物时,可以使用常规技术混合可硬化的组合物的各成分并临床应用。 [0203] When used as a dental composition, using conventional techniques by mixing the components of the hardenable composition and clinical applications. 通常需要固化光来引发可光聚合的组合物。 Typically require light to initiate curing photopolymerizable composition. 组合物可以是复合体或修复材料的形式, 并与牙科结构极好地粘合。 The compositions may be in the form of composite or restorative materials, and with very good adhesion to the dental structure. 可选择地,在牙科结构上可以使用底物层,在其上使用可硬化的组合物。 Alternatively, the structure may be used in the dental substrate layer, a hardenable composition thereon. 例如含有FAS玻璃或其他氟化物释放材料的组合物也可以提供极好的长期氟化物释放。 For example compositions containing FAS glass or other fluoride releasing material may also provide excellent long-term fluoride release. 本发明的一些实施方案可以提供树脂改性的玻璃离聚物胶合剂或粘合剂,它们能够固化,而不需要使用光或其他外部固化能量,不需要预处理,具有改进的物理性能,包括 Some embodiments of the present invention can provide a resin-modified glass ionomer cement or adhesive, they can be cured without the use of light or other external curing energy, do not need pre-treatment, have improved physical properties, comprising

23弯折强度,并具有较高的氟化物释放,从而防止龋齿。 23 bending strength, and has a high fluoride release, thereby preventing dental caries.

[0204] 本发明的组合物特别适用于各种形式的牙科材料,其可以是填充或未填充的。 [0204] The compositions of the invention are particularly applicable to all forms of dental materials, which may be filled or unfilled. 它们可以用在密封剂或粘合剂中,通常是略微填充的复合体(按组合物总重计,25wt-%填料)或未填充的组合物,它们在与牙齿相连之后固化(即,使牙科材料临时或永久地粘合或接触牙齿)。 They can be used in sealants or adhesives, usually slightly filled composite body (by weight of the total composition, 25wt-% filler) or unfilled compositions, they are connected to the teeth after curing (that is, Dental material temporarily or permanently bonded or touching the teeth). 它们可以用在胶合剂中,通常是填充的组合物(优选地含有大于25wt-%的填料,更优选大于40wt-%的填料;优选含有90wt-%的填料)。 They can be used in cement, usually filled compositions (preferably containing greater than 25wt-% filler, more preferably greater than 40wt-% of a filler; preferably 90wt-% filler). 它们也可以用在修复材料中, 包括在与牙齿相连之后聚合的复合体,如填充材料。 They can also be used in the repair material, including dental polymerizable connected after complex, such as fill material. 它们也用在修补物中,在与牙齿相连之前成形并聚合以最终使用(例如,作为牙冠,牙桥,胶合板,镶嵌物,裱贴物等)。 They are also used in prostheses, before connected to the tooth shape and polymerized to end use (such as crowns, bridges, veneer, inlays, onlays, etc.).

[0205] 组合物可以用于临床应用中,其中难于固化常规可光固化的胶合剂。 [0205] The composition can be used in clinical applications, which can be difficult to solidify the conventional light-curable adhesive. 这种应用包括但不限于深度修复,大牙冠或中心积累,牙髓修复,正牙牙环(包括预涂覆的牙环,其中例如糊状物部分可预涂覆到牙环上,液体部分可以稍后刷到牙齿上),牙带,颊管,和其他装置的安装,金属牙冠或其他不透光的修补装置与牙齿的接合,和不能到达口腔的其他修复材料的应用。 Such applications include, but are not limited to the depth of the repair, the accumulation of a large crown or center, pulp repair, n-tooth ring (including pre-coated tooth ring, which moiety may be for example a paste on precoated tooth ring, the liquid portion may Later brush the teeth), tooth engagement with installation, buccal tubes, and other devices, metal crowns or other opaque teeth repair device, and the application of other restorative material does not reach the mouth.

[0206] 使用本发明组合物的示例性方法公开在实施例中。 [0206] The compositions of the invention are disclosed in the exemplary embodiment. 在本发明一些实施方案中,使组合物(优选地,粘合剂)有效地浸蚀牙齿结构表面的条件包括用刷子涂粘合剂和/或粘合剂/稀释剂混合物,从而混合/摩擦牙齿结构表面,时间要有效地浸蚀(即,至少3秒), 通常至少5秒,经常至少10秒,和有时至少20秒。 In some embodiments of the present invention, the composition (preferably, adhesive) effectively etching conditions including dental structure surface with a brush coated with an adhesive and / or a binder / diluent mixture, thus mixing / friction dental structure surface, to effectively etch time (i.e., at least 3 seconds), typically at least 5 seconds, often at least 10 seconds, and sometimes at least 20 seconds.

[0207] 使牙科材料与牙齿结构表面粘接的方法优选地在至少7MPa,更优选至少15MPa, 最优选至少20Mpa下粘接牙釉质或牙本质(或优选地,二者都有)。 [0207] so that the dental surface of the adhesive material and the dental structure of the method is preferably at least 7MPa, more preferably at least 15MPa, most preferably at least 20Mpa adhesive enamel or dentin (or preferably both).

[0208] 下面的实施例进一步阐明本发明的目的和优点,但是这些实施例中所述的特定材料和其量以及其他条件和细节不应被解释为不适当地限制本发明。 [0208] The following examples further illustrate the objects and advantages of the present invention, these specific embodiments described in the material and the amount thereof as well as other conditions and details, should not be construed to unduly limit this invention. 除非另有所指,所有的份数和百分比都是按重量计,所有的水都是去离子水,和所有的分子量都是重均分子量。 Unless otherwise indicated, all parts and percentages are by weight, all of the water is deionized water, and all molecular weights are weight average molecular weight.

[0209] 实施例 [0209] Example

[0210] 测试方法 [0210] Test Method

[0211] 自固化效率 [0211] self-curing efficiency

[0212] 两部分"自固化"试样由树脂或糊状物形式的(即,填充的糊状物)部分A和部分B组成。 [0212] two-part "self-cure" a sample of a resin or paste form (that is, filled paste) Part A and Part B components. 在室温下,将部分A的一部分(0. Ig)和部分B的一部分(0. Ig)分配到两个珠形式的牙科混合垫上。 At room temperature, a portion of Part A (0. Ig) and a portion of part B (0. Ig) assigned to the two beads in the form of a dental mixing pad. 用抹刀混合两部分20秒,并立即转移到37C炉中。 Mix two parts with a spatula for 20 seconds, and immediately transferred to a 37 C oven. 通过使球形涂覆器在每约30秒通过混合物,直到球形涂覆器拉动混合物本身并将其撕裂,或当到达10分钟最大测试时间,从而测定得到的混合物的胶凝点。 By coating spherical in every through the mixture for about 30 seconds, until the ball coater pulling and tearing the mixture itself, or when the maximum test time is reached 10 minutes, thereby determining the gel point of the resulting mixture.

[0213] 光固化效率 [0213] The photocurable efficiency

[0214] 将树脂或树脂加填料(即,充填的糊)的试样(0. Ig)从注射器中注射至珠形的牙科混合垫上。 [0214] The resin or resin plus filler (ie, filling paste) sample (0. Ig) injection from the syringe to the bead-shaped dental mixing pad. 用XL 3000卤素牙科灯(3M Company)照射试样40秒。 With XL 3000 halogen dental light (3M Company) applied to the sample 40 seconds. 照射后,用牙科不锈钢抹刀的刀刃以约2Kgf的力切割固化的试样。 After irradiation with a dental stainless steel spatula blade cutting force of about 2Kgf cured samples. 没有锯齿时固化记为"0K";当在较少或没有锯齿但试样碎成片时记为"BrittleUt)";或当试样为液体或糊状物态时记为"N0Setting(未固化)“。 When there is no record of sawtooth cured "0K"; when little or no jagged pieces and films, but the sample referred to as "BrittleUt)"; or when the sample is a liquid or paste state when referred to as "N0Setting (uncured ). " 在表1中,“YES"等于〃 0K" ; “ NO"等于〃 No Setting" ο In Table 1, "YES" equal 〃 0K ";" NO "equal 〃 No Setting" ο

[0215] 保存稳定性 [0215] storage stability

[0216] 将试样贮存在45C (30%相对湿度),每天进行分析,3天后按周分析,以测定试样 [0216] The samples were stored at 45 C (30% relative humidity) for analysis per day, 3 days weekly analysis to determine sample

24的贮存稳定性。 24 in storage stability. 如果试样是未硬化的形式,并且如果样品与新制相对糊状物(两部分"自固化"组合物的部分A或部分B)以部分A(具有还原剂)/部分B(具有氧化剂)=3/1 的重量比混合20秒时,形成硬化的组合物,则确定给定时间下的糊状物试样(两部分"自固化"(即,氧化还原)组合物的部分A或部分B)的稳定性。 If the sample is unhardened form, and if the sample relative to the fresh paste (two-part "self-curable" compositions Part A or Part B) in section A (having a reducing agent) / Part B (having oxidant) = 3/1 weight ratio of 20 seconds to form a hardened composition, is determined to paste the sample at a given time (the two-part "self-cure" (ie, redox) the composition of Part A or Part B ) stability. 记录试样保持稳定的天数。 Record sample is kept stable for several days.

[0217]“光固化"组合物与牙釉质或牙本质的粘合 [0217] "Light-cure" compositions and enamel or dentin bonding

[0218] 对于给定试样而言,对牙釉质或牙本质的粘合剂强度按下面的过程分析。 For a given sample analysis [0218] The adhesive strength of the enamel or dentin according to the following procedure.

[0219] 准备牙齿。 [0219] prepared teeth. 对于每个试样而言,将相似年龄和外观的5个牛齿部分地嵌在圆丙烯酸盘中。 For each sample, will be of similar age and appearance of the five bovine tooth partially embedded in circular acrylic plate. 使用安装在宝石轮上的Grade 120碳化硅纸衬研磨器将每个牙齿露出的部分磨平,并平行于丙烯酸盘,从而露出牙本质或牙釉质。 Use Grade gem wheel mounted on 120 silicon carbide abrasive paper lining will expose a portion of each tooth removed, and parallel to the acrylic disc, thereby exposing the dentin or enamel. 在此步骤和随后的研磨和抛光步骤中, 用水连续漂洗牙齿。 In this step and subsequent grinding and polishing steps, the teeth rinsed with water continuously. 使用安装在宝石轮上的Grade 600碳化硅纸衬研磨器进一步研磨和抛光牙齿。 Use Grade gem wheel mounted on 600 silicon carbide abrasive paper lining further grinding and polishing teeth. 将抛光的牙齿贮存在去离子水中,在抛光后2小时内进行测试。 The polished teeth were stored in deionized water for testing within 2 hours after polishing. 从水中取出抛光的牙齿,并吸干。 The polished teeth were removed from the water, and dry.

[0220] 牙齿处理。 [0220] dental treatment. 预先制备带有穿透的5-mm直径孔的2_mm厚聚四氟乙烯片模具,向其内充填ZlOO复合物试样(3M Company)。 2_mm thick Teflon sheet prepared in advance with a 5-mm die diameter hole penetrating, at their inner filling ZlOO composite samples (3M Company). 用XL 3000牙科固化灯照射ZlOO复合物试样60 秒。 With XL 3000 dental curing light irradiation ZlOO composite sample for 60 seconds. 从模具上取下硬化的ZlOO测试牙扣,每个扣的一侧用320-筛目沙纸粗糙化。 Remove from the mold hardened ZlOO test dental deduction, the deduction for each side with a 320- mesh sand paper roughened. 在24C 和50%相对湿度的可控环境中,在制备试样的1分钟内,用抹刀将一层试样涂覆到ZlOO扣的粗糙侧。 At 24 C and 50% relative humidity controlled environment, in one minute preparation of the sample, use spatula to level the sample is applied to the rough side ZlOO buckle. 将面对牙齿并带有涂覆的试样的扣压到牙齿表面上,产生组件。 The face of the tooth with a sample of the coated snapped onto the tooth surface, producing components. 将组件静置1 分钟。 The assembly was allowed to stand for 1 minute. 随后,用XL 3000牙科固化灯(3MCompany)照射试样层40秒。 Subsequently, XL 3000 dental curing light (3MCompany) irradiating the sample layer 40 seconds. 将整个组件放在97% 相对湿度和37C的湿室中15分钟。 The entire assembly is placed in 97% relative humidity and 37 C in a moist chamber for 15 minutes. 然后将组件置于37C的去离子水中达24小时。 The assembly was then placed in 37 C deionized water for 24 hours.

[0221] 粘合剂粘接强度测试。 [0221] adhesive bond strength test. 通过将组件(上述)安装在夹于InstronTM (Instron 4505, Instron Corp. Canton,Ma)钳子上的固持器中,来分析固化的测试实施例的粘合剂强度,其中抛光的牙齿表面平行于拉力方向。 By mounting the assembly (described above) in sandwiched InstronTM (Instron 4505, Instron Corp. Canton, Ma) holder on the forceps, to analyze the adhesive strength of the cured test embodiment, wherein the polished tooth surface parallel to the tension direction. 将一圈正牙线(0.44-mm直径)置于与抛光的牙齿表面相邻的ZlOO扣周围。 The circle being floss (0.44-mm diameter) is placed with the polished tooth surface adjacent ZlOO buckle around. 将正牙线的端部夹在Instron装置的拉钳中,并以2mm/min的十字头速度拉动,从而粘合处于剪切应力下。 The ends of the floss being caught in pull clamp Instron device, and 2mm / min crosshead speed boost, so that the adhesive is under shear stress. 记录粘合失效的力千克(kg),使用扣的已知表面积,将该值换算成力/单位面积(单位是kg/cm2或MPa)。 Recording adhesive failure known surface area kilogram force (kg), the use of deduction, the value is converted into a force / unit area (units of kg / cm2 or MPa). 对牙釉质的粘合或对牙本质的粘合的每一个记录值代表5次试验的平均值。 Enamel or adhesion to dentin bond each record represents the average of five trials.

[0222]“自固化〃组合物的耐压强度(CS) [0222] "self-curable composition 〃 compressive strength (CS)

[0223] 在24C和50%相对湿度的可控制环境中,通过涂抹3g糊状物A (具有还原剂)和Ig糊状物B (具有氧化剂)25秒,制备"自固化"(即,氧化还原固化)组合物。 [0223] at 24 C and 50% relative humidity controlled environment, by smearing paste 3g A (with a reducing agent) and Ig paste B (having oxidant) 25 seconds to prepare a "self-curable" (i.e. , redox cure) composition. 通过将混合的糊状物试样注射进4-mm内直径的玻璃管中制备耐压强度样品。 The compressive strength of samples were prepared by mixing the paste sample is injected into the 4-mm inner diameter glass tube preparation. 玻璃管的端部用硅树脂塞塞住。 The ends of the glass tube to live with silicone Sese. 对充填的管施加0.275兆帕(MPa)的压力5分钟。 Filled tube is applied to 0.275 MPa (MPa) pressure for 5 minutes. 随后,将管放在97%相对湿度和37C的湿室中,达20分钟。 Subsequently, the tube was placed in a moist chamber at 97 percent relative humidity and 37 C, the up to 20 minutes. 然后将管从湿室中取出,置于37C的去离子水中达24小时。 The tube was then removed from the humidity chamber and placed in 37 C deionized water for 24 hours. 将5个固化的试样切成8mm长。 The five-cured samples cut 8mm long. 根据ISO标准7489,使用INSTR0N通用测试仪(Instron Corp.,Canton, ΜΑ),以1毫米/分钟(mm/min)的十字头速度操作,来测定耐压强度。 7489, using INSTR0N universal tester (Instron Corp., Canton, ΜΑ), to 1 millimeter / minute (mm / min) crosshead speed operation according to ISO standards, compressive strength was determined.

[0224]“光固化〃组合物的耐压强度(CS) [0224] "photocurable composition 〃 compressive strength (CS)

[0225] 通过将试样注射进4-mm内直径的玻璃管中。 [0225] The sample was injected into 4-mm inner diameter of the glass tube. 玻璃管的端部用硅树脂塞塞住。 The ends of the glass tube to live with silicone Sese. 对充填的管施加0. 275兆帕(MPa)的压力5分钟,用XL1500固化灯(3M Company)照射80秒,并置于KULZER UniXS (Kulzer, Inc.,Germany)灯盒中达180秒。 Applied to the filling tube 0.275 megapascals (MPa) pressure for 5 minutes, 80 seconds irradiation with XL1500 curing light (3M Company), and placed KULZER UniXS (Kulzer, Inc., Germany) lamp box of 180 seconds. 将5个固化的试样切成8mm 长,并置于37C水中1天。 The five-cured samples cut 8mm long, and placed in 37 C water for one day. 根据ISO标准7489,使用INSTR0N通用测试仪(Instron Corp.,Canton, ΜΑ),以1毫米/分钟(mm/min)的十字速度操作,来测定耐压强度。 7489, using INSTR0N universal tester (Instron Corp., Canton, ΜΑ), to 1 millimeter / minute (mm / min) Cross-speed operation according to ISO standards, compressive strength was determined.

[0226]''自固化〃和〃光固化〃的径向拉伸强度(DTS) [0226] '' from radial curing light curing 〃 〃 〃 and tensile strength (DTS)

[0227] 以于"自固化"或"光固化"组合物而言,使用上述耐压强度测试方法测量组合物的径向拉伸强度,但是使用的试样被切成2mm长。 [0227] In at "self-cure" or "light-cure" composition, the use of radial direction of the compressive strength test method for measuring the tensile strength of the composition, but the sample is cut using 2mm long. 结果代表5次试验的平均值。 Results represent the average of five trials.

[0228] 表A.缩写,说明,和材料来源 [0228] Table A. abbreviation, description, and source material

缩写 说明和材料来源BHT 2,6-二-叔丁基-4-甲基苯酚(Sigma-Aldrich, St. Louis, MO)Zr-Si 硅烷处理的氧化锆-氧化硅(Zr-Si)填料,按国专利4,503,169 (Randklev)所述的制备FAS玻璃 S/T (硅烷-处理的)4087和S/T湿磨的4087氟铝硅酸盐玻璃(都被中和)的50/50共混物;按共同未决的专利制备;USPTO 10/121329 ;2003年4月12日提交;代理机构号57435US002(Mitra等人)TiO2 二氧化铁(Degussa,Germany)AER0SILA200 发烟氧化硅(Degussa)CPQ 樟脑酮(Sigma-Aldrich)Cu(II)Ac 醋酸铜(II) 一水合物(Sigma-Aldrich)DPIPF6 六氟磷酸二苯基碘(Johnson Matthey, Alpha Aesar Division, Ward Hill, NJ)NaP 过硫酸钠(Sigma-Aldrich)TEGDMA 二甲基丙烯酸三乙二醇酯(Sartomer, Exton, PA)BisEMA6 乙氧基化的双酚A 二甲基丙烯酸酯(Sartomer)GDMA-P 甘油二甲基丙烯酸酯磷酸酯,根据EP〇237 233 (Oxman)中引述的J. Dent. Res.,35,8466 (1956)…来制备; (也参见,国际公开WO 02/092021 (Hecht等人)中的实施例3)HEMA-P 单-,二-,三-HEMA磷酸酯和四HEMA焦磷酸酯的混合物(参见所述的制备方法)CBSA TBA 4-氰基苯亚磺酸四丁基铵盐(参见制备方法)CEBSA TBA 4-乙氧羰基苯亚磺酸四丁基铵盐(参见制备方法)EDMAB 4-(N,N-二甲基氨基)苯甲酸乙酯(Sigma-Aldrich)t-BDMA 4-叔丁基二甲基苯胺(Sigma-Aldrich)DMAPE 4-二甲基氨基苯乙醇(Sigma-Aldrich)DHEPT 二羟乙基P-甲苯胺(Gefachem-Prochemie, Leverkusen, Germany)DMAEMA 2- 二甲基氨基乙基甲基丙烯酸酯(Sigma-Aldrich)TEA 三乙胺(JT Baker, Phillipsburg, NJ)DMA N, N- 二甲基苯胺(Sigma-Aldrich)DMABN N,N-二甲基氨基苄腈(Sigma-Aldrich)DMABA 4" (Sigma—Aldrich)4-DMAB 4-二甲基氨基苯甲酸(Alfa Aesar,Wardhill,ΜΑ)3-DMAB 3—二甲胃甲 (Lancaster Synthesis Ltd. , Windham,NH)4-DMABn 4- (Sigma—Aldrich)N-PhG N- (Sigma—Aldrich)N-PhGEE N—苯基甘氨酸乙基酉旨(Eastman Kodak, Rochester, NY) Abbreviation Description and origin BHT 2,6- two - tert-butyl-4-methylphenol (Sigma-Aldrich, St. Louis, MO) zirconium silane-treated Zr-Si - silica (Zr-Si) filler, According to the national patent 4,503,169 (Randklev) prepared according to FAS glass S / T (silane - treated) 4087 and S / T 4087 fluoroaluminosilicate wet grinding of glass (and are in) 50 / 50 blends; prepared by the co-pending patent; USPTO 10/121329; 2003 年 4 月 12 filed; Agency No. 57435US002 (Mitra et al.) TiO2 iron dioxide (Degussa, Germany) AER0SILA200 fumed silica ( Degussa) CPQ camphor -one (Sigma-Aldrich) Cu (II) Ac copper (II) acetate monohydrate (Sigma-Aldrich) DPIPF6 diphenyliodonium hexafluorophosphate (Johnson Matthey, Alpha Aesar Division, Ward Hill, NJ) NaP sodium persulfate (Sigma-Aldrich) TEGDMA triethylene glycol dimethacrylate (Sartomer, Exton, PA) BisEMA6 Ethoxylated bisphenol A dimethacrylate (Sartomer) GDMA-P glycerol dimethacrylate . phosphate esters, according EP〇237 233 (Oxman) cited J. Dent Res, 35,8466 (1956) ... prepared;. (See also, International Publication WO 02/092021 (Hecht et al.) Implementation Example 3) HEMA-P single -, two -, a mixture of three -HEMA phosphate and four HEMA pyrophosphate (prepared according see) CBSA TBA 4- Cyanophenylimino acid tetrabutylammonium salt (see Preparation method) CEBSA TBA 4- ethoxycarbonyl benzene sulfinate tetrabutylammonium salt (see Preparation method) EDMAB 4- (N, N- dimethylamino) benzoate (Sigma-Aldrich) t-BDMA 4 - tert-butyl dimethylaniline (Sigma-Aldrich) DMAPE 4- dimethylamino-phenyl ethanol (Sigma-Aldrich) DHEPT dihydroxyethyl P- toluidine (Gefachem-Prochemie, Leverkusen, Germany) DMAEMA 2- dimethyl amino ethyl methacrylate (Sigma-Aldrich) TEA Triethylamine (JT Baker, Phillipsburg, NJ) DMA N, N- dimethylaniline (Sigma-Aldrich) DMABN N, N- dimethylamino benzonitrile (Sigma-Aldrich) DMABA 4 "(Sigma-Aldrich) 4-DMAB 4- dimethylaminobenzoate (Alfa Aesar, Wardhill, ΜΑ) 3-DMAB 3- dimethyl stomach A (Lancaster Synthesis Ltd., Windham, NH) 4-DMABn 4- (Sigma-Aldrich) N-PhG N- (Sigma-Aldrich) N-PhGEE N- phenylglycine ethyl unitary purpose (Eastman Kodak, Rochester, NY)

[0229] 原料制备 [0229] feedstock preparation

[0230] 制备芳基亚磺酸盐 [0230] Production of aryl-sulfonate

[0231] 按与本申请同一天提交的受让人的共同未决的美国申请10/672,762(代理机构卷号58634US002)所述,制备4-氰基苯亚磺酸四丁基铵盐(CBSA TBA)和4-乙氧羰基苯亚磺酸四丁基铵盐(CEBSA TBA)。 [0231] by the assignee of the present application and filed on the same day of the co-pending U.S. Application No. 10 / 672,762 (Attorney Docket No. 58634US002) said, Preparation of 4-cyano-benzene sulfinate tetrabutylammonium salt (CBSA TBA) and 4-ethoxycarbonyl phenyl sulfinate tetrabutylammonium salt (CEBSA TBA).

[0232] 简言之,通过用乙酸乙酯从碱金属苯亚磺酸盐的酸性水溶液中萃取出相应的苯亚磺酸,来从相应的碱金属苯亚磺酸盐制备每种四丁基铵苯亚磺酸盐。 [0232] Briefly, extracted with ethyl benzene sulfinate from the corresponding acidic aqueous solution of alkali metal salt of benzene in Asia, to the corresponding alkali metal salt of each of four sub-butyl benzene ammonium benzene sulfinate. 将有机相蒸发至干,将得到的固体溶解在50% (ν/ν)甲醇水溶液中。 The organic phase was evaporated to dryness and the resulting solid was dissolved in 50% (ν / ν) aqueous methanol. 然后用氢氧化四丁基铵水溶液滴定上述溶液。 Then treated with an aqueous solution of tetrabutylammonium hydroxide titration the solution. 混合物蒸发至干,得到四丁基铵苯亚磺酸盐,黄色油。 The mixture was evaporated to dryness to give tetrabutyl ammonium benzene sulfinate, yellow oil.

[0233] 通过使相应的苯磺酰基氯化物水解形成相应的苯亚磺酸(无色固体),制备每种碱金属苯亚磺酸盐。 [0233] by reacting the appropriate benzenesulfonyl chloride hydrolysis to form the corresponding benzene sulfinate (colorless solid) was prepared for each of alkali metal benzene sulfinate. 用碱金属氢氧化物中和苯亚磺酸的甲醇水溶液,得到碱金属苯亚磺酸盐。 With an alkali metal hydroxide in aqueous methanol and benzene sulfinic acid, an alkali metal benzene sulfinate obtained.

[0234] 制备HEMA-P (ΗΕΜΑ磷酸酯和四HEMA焦磷酸酯的混合物) [0234] Preparation of HEMA-P (ΗΕΜΑ phosphate and four HEMA pyrophosphate mixtures)

[0235] 向安装有带进气口的回流冷凝管、机械搅拌器和带有出气口的加料漏斗的1-升3- 口圆底烧瓶中加入76. 7g POCl3 和500ml THF。 [0235] is attached to the air inlet into the reflux condenser, mechanical stirrer and addition funnel with an outlet of a 1-liter 3- necked round bottom flask 76. 7g POCl3 and 500ml THF. 将130. 5g ΗΕΜΑ, 101. 5g 三乙胺(TMA)和87g THF的溶液置于加料漏斗中。 The 130. 5g ΗΕΜΑ, 101. 5g triethylamine (TMA) and 87g THF was placed in an addition funnel. 用冰-水-盐浴将烧瓶冷却至约_5C。 With ice - water - salt bath and the flask is cooled to approximately _5 C. 搅拌下于25分钟内滴加溶液,此期间内温度保持在0C〜_5C。 Stirring solution was added dropwise over 25 minutes, during which the inner temperature was kept at 0 C~_5 C. 将混合物搅拌3小时,升至室温。 The mixture was stirred for 3 hours, warmed to room temperature. 向烧瓶中再加入200ml THF以加速搅拌。 To the flask was added 200ml THF was stirred to accelerate. 向加料漏斗中加入51g TEA和6. 8g水在50ml THF中的溶液。 6. 8g 51g TEA and water solution in 50ml THF was added to the addition funnel. 用冰-水-盐浴将烧瓶冷却至0-5C后,在16分钟内滴加溶液。 With ice - water - salt bath the flask was cooled to 0-5 C after dropping the solution within 16 minutes. 混合物升至室温,搅拌18小时。 The mixture was warmed to room temperature and stirred for 18 hours. 过滤混合物,除去得到沉淀的盐,真空除去THF。 The mixture was filtered to remove the precipitated salt to give vacuo remove THF. 得到的产物是浅桔色液体,168g,通过1H, 13C和31P NMR表征,是单-,二-,和三-HEMA磷酸酯和四HEMA焦磷酸酯的混合物。 The product obtained is a pale orange liquid, 168g, by 1H, 13C and 31P NMR characterization, is single -, two -, and mixtures of phosphates and four three -HEMA HEMA pyrophosphate.

[0236] 实施例1-4 [0236] Examples 1-4

[0237] 分析引发剂体系中的各种电子供体(光固化模式) [0237] Analysis of the initiator system in a variety of electron donor (light-curing mode)

[0238]通过混合 TEGDMA (24. 85 份),BisEMA6 (24. 85 份),HEMA-P (49. 70 份),CPQ (0. 30 份),和BHT (0. 30份)得到均勻组合物来制备树脂A。 [0238] By mixing TEGDMA (24. 85 parts), BisEMA6 (24. 85 parts), HEMA-P (49. 70 parts), CPQ (0. 30 parts), and BHT (0. 30 parts) to obtain a homogeneous composition It was used to prepare a resin A.

[0239] 各种电子供体化合物与树脂A或树脂B混合,根据所述光固化效率测试方法分析得到的组合物的固化。 [0239] various electron donor compound A or the resin is mixed with a resin B, the analysis of the composition obtained by curing the photocurable efficiency according to Test Method. 电子供体化合物,其在树脂A中的浓度和溶解度,和光固化结果列于表1中。 Electron donor compound, its concentration and the solubility in the resin A, and light-curing results are shown in Table 1 below. 用加到组合物中的DPIPF6(1份)重复研究,固化结果基本上与未加入DPIPF6的结果相同。 With added to the composition of DPIPF6 (1 part) duplication of research, the results substantially cured not join DPIPF6 the same result. 树脂A与3%和10% CBSA TBA及与3%和10% CEBSA TBA的混合物分别被称为实施例1,2,3,和4。 Resin A and 3% and 10% CBSA TBA and a mixture of 3% and 10% CEBSA TBA are referred to in Example 2, 3, and 4.

[0240] 应该注意到,树脂A加芳基亚磺酸四丁基铵盐(CBSA TBA或CEBSA TBA)的光固化效率与树脂中的亚磺酸盐浓度相关。 [0240] It should be noted, resin A plus arylsulfinate tetrabutylammonium salt (CBSA TBA or CEBSA TBA) light curing efficiency and resin sulfinates concentration.

表1 含有各种电子供体化合物的树脂A光固化结果 电子供体化合物 化合物的物理状态 树脂A中的化合物浓度(wt-%) 溶解性/ 混溶性观察 固化结果DMAPE 固体 2% 溶解 NODHEPT 固体 2% 溶解 NOEDMAB 固体 2% 溶解 YES4-DMAB 固体 2% 不全溶 Brittlet-BDMA 液体 2% 可混溶 NODMA 液体 2% 可混溶 YESDMABN 固体 2% 溶解 YESDMABA 固体 2% 溶解 Brittle3-DMAB 固体 2% 不全溶 NO4-DMABn 固体 2% 不全溶 NON-PhG 固体 2% 不全溶 NON-PhGEE 固体 2% 溶解 BrittleDMAEMA 液体 2% 可混溶 NOTEA 液体 2% 可混溶 NOCBSA TBA (实施例1) 液体 3% 可混溶 BrittleCBSA TBA (实施例2) 液体 10% 可混溶 YESCEBSA TBA (实施例3) 蜡 3% 溶解 NOCEBSA TBA (实施例4) 蜡 10% 溶解 Brittle Table 1 concentration of compound A photocurable resin results of the physical state of the electron donor compound resin A containing various electron donor compounds in the (wt-%) the solubility / miscibility observed results DMAPE curing NODHEPT solids dissolved solids 2% 2 NOEDMAB% dissolved solids dissolved YES4-DMAB 2% 2% solids solution Brittlet-BDMA insufficiency liquid miscible NODMA 2% 2% liquid miscible YESDMABN solids 2% 2% dissolved solids dissolved YESDMABA Brittle3-DMAB 2% solids solution insufficiency NO4 Not completely dissolved at 2% solids -DMABn NON-PhG insufficiency dissolved solids 2% 2% NON-PhGEE solid was dissolved BrittleDMAEMA miscible liquid 2% 2% NOTEA liquid miscible NOCBSA TBA (Example 1) 3% liquid miscible BrittleCBSA TBA (Example 2) 10% liquid miscible YESCEBSA TBA (Example 3) was dissolved wax 3% NOCEBSA TBA (Example 4) was dissolved Brittle wax 10%

27[0241] 实施例5-6 27 [0241] Example 5-6

[0242] 分析在引发剂体系中作为电子供体的芳基亚磺酸盐(自固化和光固化模式) [0242] In the initiator system analysis as an electron donor arylalkylene sulfonate (self-curing and light-curing mode)

[0243] 实施例5和6是从两部分糊状物/糊状物成分制备的"自粘合剂"组合物。 [0243] Examples 5 and 6 are "self-adhesive" compositions from the two-part paste / paste ingredients prepared. 通过混合表2中所示浓度的成分,制备糊状物Al和糊状物A2 (每种含有可聚合的成分,EDMAB和CBSA TBA电子供体,和填料)。 Concentration shown in Table 2 by mixing the ingredients, the preparation of the paste and paste Al A2 (each containing a polymerizable component, EDMAB CBSA TBA and an electron donor, and a filler). 通过混合表3中所示浓度的成分,制备糊状物B (含有酸性和非酸性可聚合的成分,CPQ敏化剂,Cu(II)Ac和NaP氧化剂(S卩,电子受体),和填料)。 By concentration of the ingredients shown in Table 3 were mixed to prepare a paste composition B (containing an acidic and non-acidic polymerizable component, CPQ sensitizer, Cu (II) Ac and NaP oxidant (S Jie, electron acceptor), and filler).

Figure CN1859894BD00291

[0244] [0244]

Figure CN1859894BD00292

[0245] 通过涂抹3g糊状物Al和Ig糊状物B20秒制备实施例5。 [0245] The applicator 3g Al and Ig paste pastes B20 Preparation Example 5 seconds. 通过涂抹3g糊状物A2和Ig糊状物B20秒,制备实施例6。 3g paste by smearing paste Ig A2 and B20 seconds, Preparation Example 6. 根据所述的〃自固化〃测试方法,以〃 自固化"模式(即,没有用外部牙科固化灯进行照射)分析实施例5和6的耐压强度(CS)和径向拉伸强度(DTS)。根据所述的〃光固化〃测试方法,以〃光固化〃模式(即,用外部牙科固化灯进行照射)分析实施例5的耐压强度(CS),径向拉伸强度(DTS),和对牙釉质和牙本质的粘合。测试结果列于表4中,标准偏差记录在括号中。 According to self-curing 〃 〃 test method according to 〃 self-cure "mode (ie, no external dental curing light irradiation) analysis of compressive strength 5 and 6 cases (CS) implementation and radial tensile strength (DTS ). According to the photocuring 〃 〃 test method to photocurable 〃 〃 mode (i.e., irradiated with a dental curing light external) Analysis compressive strength (CS) of Example 5, radial tensile strength (DTS) , and enamel and dentin bonding. The test results are shown in Table 4, the standard deviation is recorded in parentheses.

Figure CN1859894BD00301

[0246] *NT-未测试 [0246] * NT- untested

[0247] 保存稳定性分析 [0247] storage stability analysis

[0248] 使用所述的保存稳定性测试方法,糊状物Al在45 C下稳定超过80天,在室温(230C )下稳定超过9个月;糊状物A2在45C下稳定约2周。 [0248] The method of using the storage stability test, the Al paste was stable at 45 C over 80 days at room temperature (230C) stable over 9 months; paste A2 stable at approximately 45 C 2 weeks. 糊状物B用于测试方法中。 Paste B used in the test method.

[0249] 实施例7-8 [0249] Examples 7-8

[0250] 分析引发剂体系中作为电子供体的芳基亚磺酸盐(自固化模式) [0250] Analysis of the initiator system as an electron donor arylalkylene sulfonate (self-curing mode)

[0251]通过混合 TEGDMA(62. 31 份),BisEMA6(37. 38 份),和BHT (0. 31 份)得到均勻组合物来制备树脂B。 [0251] By mixing TEGDMA (62. 31 parts), BisEMA6 (37. 38 parts), and BHT (0. 31 parts) to prepare a homogeneous resin composition B.

[0252]通过混合 TEGDMA (6. 65 份),BisEMA6 (3. 99 份),BHT (0. 10 份),CPQ (0. 32 份), GDMA-P (73. 15份),Cu (II) Ac (0. 16份),NaP (10. 64 份),和AEROSIL A200 (5. 32 份)得到均匀组合物来制备树脂C。 [0252] By mixing TEGDMA (6. 65 parts), BisEMA6 (3. 99 parts), BHT (0. 10 parts), CPQ (0. 32 parts), GDMA-P (73. 15 parts), Cu (II ) Ac (0. 16 parts), NaP (10. 64 parts), and AEROSIL A200 (5. 32 parts) to obtain a homogeneous composition to prepare a resin C.

[0253] 各种电子供体化合物与树脂B混合,得到的混合物以1 : 1的重量比与糊状物C 混合。 [0253] various electron donor compound is mixed with the resin B, the mixture obtained in 1: 1 ratio by weight C and mixed paste. 根据所述的自固化效率测试方法,分析得到的组合物的固化。 The self-test method according to the curing efficiency, analyzing the resulting cured composition. 电子供体化合物,在树脂B中的浓度和溶解度,和自固化结果列于表5中。 Electron donor compound, the concentration in the resin B and solubility, and self-curing results are shown in Table 5. 树脂B与5% CBSA TBA及糊状物C的组合物称作实施例7,树脂B与5% CEBSA TBA及糊状物C的组合物称作实施例8。 Resin composition B and 5% CBSA TBA C paste and referred Example 7, the resin composition B and 5% CEBSA TBA C paste and referred Example 8.

Figure CN1859894BD00302

[0254] 很显然,本领域所属技术人员可以本发明的精神和范围内作出各种修改和变化。 [0254] Obviously, this skilled in the art may fall within the spirit and scope of the invention and that various modifications and changes. 应该理解,本发明不意图限制于示例性的实施方案和实施例,这种实施例和实施方案仅用于举例说明本发明的范围,本发明的范围仅由下面的权利要求限制。 It should be understood that the invention is not intended to be limited to the exemplary embodiments and examples, examples and embodiments of this embodiment is only intended to illustrate the scope of the invention, the scope of the present invention is limited only by the following claims.

30 30

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Classifications
International ClassificationA61K6/083, C08F2/10, C08F2/50, A61K6/00
Cooperative ClassificationY10S522/908, A61K6/083, C08F2/50, A61K6/0017, A61K6/0023
European ClassificationC08F2/50, A61K6/083, A61K6/00B, A61K6/00A5
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