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Publication numberCN1146748 A
Publication typeApplication
Application numberCN 95192689
PCT numberPCT/FR1995/000505
Publication date2 Apr 1997
Filing date18 Apr 1995
Priority date19 Apr 1994
Also published asCA2188184A1, DE69510786D1, DE69510786T2, EP0756540A1, EP0756540B1, US5904954, WO1995028278A1
Publication number95192689.6, CN 1146748 A, CN 1146748A, CN 95192689, CN-A-1146748, CN1146748 A, CN1146748A, CN95192689, CN95192689.6, PCT/1995/505, PCT/FR/1995/000505, PCT/FR/1995/00505, PCT/FR/95/000505, PCT/FR/95/00505, PCT/FR1995/000505, PCT/FR1995/00505, PCT/FR1995000505, PCT/FR199500505, PCT/FR95/000505, PCT/FR95/00505, PCT/FR95000505, PCT/FR9500505
InventorsR卡萨特, JP法里
Export CitationBiBTeX, EndNote, RefMan
External Links: SIPO, Espacenet
Composite article and method for making same
CN 1146748 A
Abstract  translated from Chinese
一种复合材料及其制备方法。 A composite material and its preparation method. 包括一种对电和/或热绝缘的基材和置于这种基材每一侧之上的保护层的复合制品,其特征在于其中至少一个保护层是由耐热树脂制成的,这种树脂包括由栽绒在绝缘基材上的耐热材料制成的增强纤维。 Comprises an electrical and / or thermal insulation of the substrate and the substrate is placed on each side of such a protective layer over the composite article, wherein the at least one protective layer is formed of heat-resistant resin, which resins including reinforcing fibers by tufted on an insulating substrate made of heat resistant material. 该保护层具备改进的保护性质,特别是防水性。 The protective layer includes improved protection properties, particularly water resistance. 该复合材料还可被用作形成软性印刷电路的金属层载体。 The composite material may also be used as a support forming a metal layer of the flexible printed circuit.
Claims(17)  translated from Chinese
1.包括一种对电或热绝缘的基材和至少一种置于这种基材的一个面上的保护层的复合制品,其特征在于其中至少一个保护层是由耐热树脂制成的,这种树脂包括由栽绒在基材表面上的耐热材料制成的增强纤维。 1 comprises an electrical or thermal insulation and at least one substrate disposed on one side of this substrate protective layer composite article, wherein the at least one protective layer is made of a heat-resistant resin Such resins include reinforcing fibers by tufted on the substrate surface of the heat-resistant material.
2.根据权利要求1所述的制品,其特征在于耐热纤维是由选自聚酰亚胺、聚芳族聚酰胺和聚酰胺-酰亚胺树脂的耐热材料制得。 2. The article of claim 1, wherein the heat resistant fiber is selected from polyimide, polyamide and aromatic polyamide - imide resin heat resistant material too.
3.根据权利要求1或2所述的制品,其特征在于耐热树脂是选自聚酯、聚烯烃、聚碳酸酯、聚苯硫醚、聚酰亚胺和热致变聚酯的耐热聚合物。 3. The article according to claim 1 or claim 2, wherein the heat-resistant resin is selected from polyester, polyolefin, polycarbonate, polyphenylene sulfide, polyimide and thermotropic polyester heat polymers.
4.根据权利要求3所述的制品,其特征在于耐热树脂不溶于水。 4. The article of claim 3, wherein the heat-resistant resin is insoluble in water.
5.根据前述权利要求中的任意一个所述的制品,其特征在于它包括至少一个保护层,此保护层包括在基材的每个面上栽绒了耐热纤维而被增强的耐热树脂。 5. The article of the preceding claims, wherein any one, characterized in that it comprises at least one protective layer, the protective layer comprises on each side of the tufted substrate is heat-resistant fiber reinforced heat-resistant resin .
6.根据前述权利要求中的任意一个所述的制品,其特征在于保护层包括选自包括颜料、金属化前体和色料的添加剂。 6. The article of the preceding claims, wherein any one of, wherein the protective layer comprises a pigment selected from the group comprising, a metal precursor, and color additives.
7.根据前述权利要求中的任意一个所述的制品,其特征在于基材是电绝缘连续膜,其选自聚酯、聚烯烃、聚碳酸酯、聚苯硫醚、聚酰亚胺和热致变的聚酯膜。 7. The article of the preceding claims, wherein any one of, wherein the substrate is an electrically insulating continuous film selected from polyester, polyolefin, polycarbonate, polyphenylene sulfide, polyimide, and heat polyester film-induced change.
8.根据权利要求1到7所述的复合制品,其特征在于其中至少一个保护层包括附着在其表面的金属层。 8. A composite article according to claim 1 to 7, characterized in that the at least one protective layer comprises a metal layer adhered on the surface.
9.根据权利要求8所述的制品,其特征在于金属层是由用于保护层表面的金属片组成。 9. The article of claim 8, wherein the metal layer is a layer of a metal sheet for protecting the surface of the composition.
10.根据权利要求8所述的制品,其特征在于保护层包括一种添加剂,它是金属化底漆涂区前体,并且其中金属层是通过保护层表面的金属化制得的。 10. The article of claim 8, wherein the protective layer includes an additive, which is coated with a primer before metallization body region, and wherein the metal layer is a protective layer surface by metallization obtained.
11.根据权利要求8到10中任意一个所述的制品,其特征在于电路是通过浸蚀金属层形成的,并且其中形成了软性印刷电路。 According to claim any one of the article 8 to 10, characterized in that the circuit is formed by etching the metal layer, and wherein the flexible printed circuit is formed.
12.权利要求1到7所述的复合制品的生产方法,其特征在于它包括下列步骤:-制备通过在对电和/或热绝缘的基材的一个表面栽绒耐热纤维的方式制备一个层,-用耐热树脂的溶液涂覆此栽绒层,-将树脂沉积在栽绒层之内和/或之上,-干燥制品。 The method for producing a composite article 1 to 7, according to claim 1, characterized in that it comprises the following steps: - preparation by electrical and / or a surface of the thermal insulation of the heat-resistant fibers tufted substrate prepared in a manner layer, - coating the solution of the heat-resistant resin layer of tufted, - the resin is deposited in the tufted layer and / or on, - a dry product.
13.根据权利要求12所述的方法,其特征在于树脂溶液中的树脂重量含量在5%到50%之间。 13. The method according to claim 12, characterized in that the resin solution of the resin weight content of between 5% to 50%.
14.根据权利要求12或13所述的方法,其特征在于树脂溶液的溶剂选自N-甲基吡咯烷酮、二烷基脲如二甲基亚乙基脲或二甲基亚丙基脲、二甲基乙酰胺、二甲基甲酰胺、酮类或类似物。 14. The method according to claim 12 or claim 13, characterized in that the solvent of the resin solution is selected from N- methylpyrrolidone, dialkylureas such as dimethylethyleneurea or dimethylpropyleneurea, two dimethylacetamide, dimethylformamide, ketones, or the like.
15.根据权利要求12到14中任意一个所述的方法,其特征在于树脂的沉淀是通过凝结作用进行的。 15. A method according to any of claim 12 to 14, characterized in that the precipitated resin was carried through coagulation.
16.根据权利要求15所述的方法,其特征在于树脂凝结作用是通过将涂覆的栽绒层与树脂的非溶剂接触进行的。 16. The method according to claim 15, wherein the resin is obtained by coagulation, the coated non-solvent contact with the resin layer of tufted conducted.
17.根据权利要求12到16中任意一个所述的方法,其特征在于在经过栽绒的保护层上加压。 17. A method according to any one of claims 12 to 16 claim, wherein the protective layer after tufted pressurized.
Description  translated from Chinese
复合制品及其制备方法 Composite products and its preparation method

本发明涉及一种复合制品及其制备方法。 The present invention relates to a composite article and its preparation method.

更具体地,本发明涉及一种包括对电和/或热绝缘的基材和置于此基材的每个面上的保护层。 More particularly, the present invention relates to an electrical and / or thermally insulating substrate and the substrate protective layer disposed on each face.

在电子技术领域中,电动机通常采用象聚酯膜一样的柔韧材料来绝缘,如用塑料制成的膜。 In the field of electronic technology, the motor usually used as a polyester film like flexible insulating material, such as a film made of plastic. 但是,这些膜对环境,特别是对湿气是敏感的,或者不具有足够的机械和抗热性能。 However, these films on the environment, particularly moisture sensitive, or does not have sufficient mechanical and thermal properties. 为了克服这些缺点,已有建议制备包括夹在两个由耐热纸制成的保护层之间的电绝缘层的复合材料。 To overcome these drawbacks, it has been proposed preparation sandwiched between two protective layers of paper by a heat-resistant electrically insulating layer of composite material. 这种复合材料一方面要求纸的制备包括例如切断的芳族聚酰胺纤维和芳族聚酰胺的类纤维,另一方面,为了使层之间具有良好的粘接性,要求将纸以连续的方式用于电绝缘支撑层。 Preparation of such a composite sheet material comprising e.g. ask the chopped aramid fibers and aramid fibers, on the other hand, in order to make a good adhesion between the layers, require a continuous paper way for electrically insulating support layer. 这种制备复合材料的方法比较复杂。 This method for preparing a composite material is more complex. 另外,这种保护纸层的特别是与湿气有关的严密性不好。 In addition, this special protective paper layer is closely associated with the moisture is bad.

另外,也可将电绝缘基材,尤其是电绝缘柔韧膜用于软性印刷电路的生产。 In addition, also be an electrically insulating substrate, in particular for the production of electrically insulating flexible film of the flexible printed circuit. 这些制品是通过金属化膜的一个面,优选两个面,接着通过采用例如金属化层的化学浸蚀方法生产电路而制得的。 These articles by a metalized film surface, preferably both surfaces, followed by chemical etching using, for example a process for producing a circuit metallization layers and the obtained. 电子元件如晶体管、二极管或电容器是例如通过镀锡被焊接到这些电路上。 Electronic components such as transistors, diodes or capacitors, for example by being soldered to the tin these circuits.

这种支撑膜必须具有良好的形稳性,特别是在焊接温度下。 This support film must have good dimensional stability, especially at soldering temperatures. 由于这些原因,聚酯膜逐渐地被由具有改进了抗热性和形稳性的塑料如聚酰亚胺或聚芳族聚酰胺树脂制成的膜取代。 For these reasons, a polyester film is gradually improved membrane having heat resistance and dimensional stability of plastics such as polyimide or aramid resin substituted. 但是,生产这些塑料的成本很高。 However, the high cost of production of these plastics.

本发明的一个目的是通过提供一种对热和电绝缘的复合材料而克服这些缺点,这种复合材料包括特别是对湿气不透的保护层,并且可以通过简单使用方法制得。 An object of the present invention is achieved by providing a thermal and electrically insulating composite material which overcome these shortcomings, the composite material comprises particularly to moisture impervious protective layer, and may be obtained by simply using the method. 这种材料可以作为对电绝缘的基材,在通过采用铜层或金属化工艺将金属层沉积于这种复合材料的至少一个面上之后,用于软性印刷电路的生产。 This material can be used as the electrically insulative substrate, after passing through the copper layer or metallization process a metal layer is deposited in such a composite material is at least one surface, for the production of flexible printed circuits.

为此,本发明提供一种复合制品,其中包括一个连续的支撑层和置于这种支撑或基材层至少一个面上的保护层。 To this end, the present invention provides a composite article, which comprises a continuous support layer and such a support or base layer disposed at least one surface of the protective layer.

根据本发明,至少一个保护层是由耐热树脂制成,这种树脂包括被栽绒入支撑层或基材表面的由耐热材料制成的增强纤维。 According to the present invention, at least one protective layer is formed of heat-resistant resin, such resin comprises reinforcing fibers are made of tufted into the support layer or the substrate surface by the heat-resistant material.

根据本发明的优选实施方案,支撑层或基材层是对电和/或热绝缘的连续层。 According to a preferred embodiment of the invention, the support layer or substrate layer is electrically and / or thermally insulating continuous layer.

由对电和/或热绝缘的合成材料如聚酯、聚烯烃、聚碳酸酯、聚苯硫、聚酰亚胺、热致变的聚酯等等制成的膜被以实例的方式提到用作适于本发明的支撑层或基材层。 By electrical and / or thermal insulation of synthetic materials such as films made of polyester, polyolefin, polycarbonate, polyphenylene sulfide, polyimide, thermotropic polyesters and the like are mentioned by way of example used as a suitable support layer or substrate layer of the invention.

由适用于本发明的耐热材料制成的纤维是例如由聚酰亚胺、聚芳族聚酰胺和聚酰胺-酰亚胺制成的纤维。 Fibers useful in the present invention by a heat-resistant material, for example, polyimide, polyamide and polyaromatic polyamide - imide fiber made.

以适用于本发明耐热树脂实例的方式被提到的是聚酰亚胺、聚酰胺-酰亚胺、聚芳族聚酰胺、双马来酰亚胺、环氧和三嗪树脂或其混合物。 Examples of suitable heat-resistant resin in the present invention is the manner mentioned polyimide, polyamide - imide, poly aramid, bismaleimide, epoxy and triazine resin or a mixture thereof .

更有利的是,适用于本发明的树脂是能够以溶液的形式被沉积在栽绒了纤维的层之上的树脂,树脂可以通过与第三种溶剂根据凝结工艺进行溶剂交换,或通过例如以凝胶形式的沉淀作用,或通过溶剂的蒸发而被沉淀。 More advantageously, the resin suitable for the present invention is the ability to be deposited in the form of a solution of the tufted fiber layer above the resin, the resin can be by solvent exchange with a third solvent according to congeal process, or by e.g. precipitation in gel form, or is precipitated by evaporation of the solvent.

可被特别提及的树脂优选是:聚酰胺-酰亚胺和特别是那些通过二异氰酸酯如甲苯二异氰酸酯、4,4'-二苯基甲烷二异氰酸酯、二苯基醚4,4'-二异氰酸酯、间亚苯基二异氰酸酯、1,6-六亚甲基二异氰酸酯、双环己基二异氰酸酯等等,在存在或不存在芳香二酸如间苯二酸或对苯二酸情况下,与一种酸酐如1,2,4-苯三酸酐或一种二酸酐和1,3-二羧苯磺酸酯反应制得的树脂。 Resin preferably may be mentioned in particular are: polyamide - imide, and especially those obtained by diisocyanates such as toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate, m-phenylene diisocyanate, 1,6-hexamethylene diisocyanate, dicyclohexyl diisocyanate and the like, in the presence or absence of an aromatic diacid such as isophthalic acid or terephthalic acid under the conditions, and a kinds of acid anhydride such as trimellitic anhydride or a diacid anhydride and 1,3-dicarboxylic acid ester resin obtained reaction.

根据本发明的另一个特征,根据常规栽绒技术将栽绒纤维置于支撑层或基材层之上,也就是说,通过用粘接剂涂覆有待被栽绒的表面,基本上保持相互平行和与待栽绒表面垂直的纤维层的沉积是通过例如电场作用而被栽绒的。 According to another feature of the invention, according to conventional techniques tufted tufted fibers are placed on top of the supporting layer or the base layer, that is, by using an adhesive coating is to be tufted surface, remain substantially mutually deposition and to be parallel and perpendicular to the surface of tufted fiber layer by, for example electric field was planted velvet.

可被提及的适用于本发明的粘接剂是耐热性粘接剂,例如由Henkel公司出售的聚酯/聚氨酯型的双组份粘接剂。 May be useful in the present invention the adhesive is mentioned heat resistant adhesive, such as sold by Henkel polyester / urethane type two-component adhesive.

在本发明的一个实施方案中,纤维可以具有不同的或相同的长度。 In one embodiment of the present invention, the fibers may have different or the same length. 纤维的长度和栽绒层的密度是根据复合构件的性质和用途,例如根据所需保护层的厚度和表面性质来确定。 The length and density of the layer of tufted fibers according to the nature and use of the composite member, e.g., determined according to the desired thickness and surface properties of the protective layer.

特别是由于栽绒纤维的存在,这样形成的保护层是连续的并具有良好的机械性能,在涂料用树脂的凝结和沉淀作用下,栽绒纤维可以在支撑层上被压平而形成一个增强的保护层。 In particular, since the presence of tufted fibers, the protective layer thus formed is continuous and has good mechanical properties, in the coagulation and precipitation of coating resin, the tufted fibers can be flattened on the support layer to form a reinforced The protective layer.

在本发明的另一实施方案中,对这样形成的复合材料进行后处理,其中特别包括为了使保护层发挥所需的作用而使其成型,在保护层的表面加压。 In another embodiment of the present invention, after the composite material thus formed is treated, including, in particular in order to make the protective layer plays the desired role and to shape, in the surface protective layer of pressure. 这种处理也可以采用轮压的形式,这样可以使保护层的表面和复合材料的厚度具有均一性。 Such treatment may also be employed in the form of wheel pressure, this could make the surface and thickness of the composite material having a protective layer uniformity.

本发明的材料具有良好的粘接性,尤其是将涂料用树脂粘接到支撑层表面的粘接性,这种粘接由于栽绒纤维的存在而得以提高和增强。 Material of the present invention has good adhesiveness, especially the coating resin layer is adhered to the adhesive surface of the support, due to the presence of such adhesive and the tufted fibers can be improved and enhanced.

另外,这种保护层的粘接性通过限制将支撑层如聚酯膜暴露于环境气氛如湿气、辐射等等,而可以提高复合材料的抗老化性。 Further, this protective layer adhesion to the support layer by limiting such as a polyester film is exposed to the ambient atmosphere, such as moisture, radiation, etc., and can improve the aging resistance of the composite material. 这种支撑层的绝缘性质因此而长时间保持在令人满意的水平。 The insulating nature of the support layer thus long maintained at a satisfactory level.

进一步说,涂料用树脂的采用允许将大量的添加剂如防水化合物、润滑剂、色料等等加入到栽绒的保护表面。 Furthermore, the use of coating resins allow a large number of additives such as waterproof compounds, lubricants, pigments, etc. is added to protect the surface of tufted. 这些添加剂可以改善复合材料的性能和外形而用于所需用途。 These additives may improve the performance and appearance of the composite material was used in the desired application.

因此,在将本发明的复合材料用作金属层,特别是用于生产软性印刷电路的支撑层的情况下,这种涂料用树脂可以包括填料,如金属氧化物类,例如氧化亚铜,来对保护层的表面进行金属化处理。 Thus, in the case where the composite material of the present invention is used as a metal layer, in particular for the production of flexible printed circuit supporting layer, this coating resin may include fillers, such as metal oxides, for example cuprous oxide, to the surface of the protective layer metallization processing.

本发明的一个主题特别是结构如上所述并且在其至少一个面上有一个金属层的复合材料。 A subject of the present invention constructed as described above and in particular on at least one surface thereof a composite metal layer. 这种金属层可以通过任何已知的沉积金属的技术沉积在塑料层的表面上。 The metal layer may be deposited by any known technique of metal deposited on the surface of the plastic layer. 一个可以提及的又不暗示限定的实施例是通过在复合材料表面的粘接,或者优选的通过电解和/或电化学的金属化方法形成金属层,而施加金属片如铜的技术。 A may be mentioned without implying embodiments are defined by a metal layer formed on the bonding surface of the composite material, or preferably by electrolytic and / or electrochemical metallization method, a metal sheet such as copper is applied techniques. 实际上,由于可以往涂料用树脂中加入金属化前体添加剂,本发明的复合构件能够简化金属化工艺的运用,如在法国专利2518126中所述的。 In fact, since it is possible to add a metal coating resin precursor additives, the composite member of the present invention can simplify the application of the metallization process, as described in French Patent 2,518,126.

简单的说,在此法国专利中所述的金属化工艺包括往要被金属化的基材中加入能够增加用于金属工艺的表面的金属底漆涂区的填料。 Simply put, in this metallization process described in French patent comprises adding a filler to be added can be used to increase the surface of the metal coating process of the metal primer region metalized substrate. 适用的填料尤其是指非导电性的金属氧化物如氧化铜。 Suitable fillers particularly refers to non-conductive metal oxides such as copper oxide. 将基材的表面用能够将上述金属氧化物还原成可导电的金属的还原剂,如氢硼化物处理。 The surface of the substrate with the metal oxide can be restored so as to be electrically conductive metal reducing agent, such as borohydride treatment. 这种还原的金属形成了与可采用通过电解和/或电化学途径直接金属化相适应的金属底漆涂区。 This reduction of metal and can be formed by electrolysis and / or electrochemical pathways direct metallization adapt metal primer coated area.

本发明的金属化复合材料最适用于一种软性印刷电路的生产,因为整个单元即使在焊接温度都具有良好的形稳性,而不管支撑膜的性质如何。 Metallized composite material of the present invention is most suitable for the production of a flexible printed circuit, because the whole unit even at soldering temperatures have good dimensional stability, regardless of the nature of the support film. 实际上因为保护层是用耐热材料制成的,就防止了支撑膜的收缩。 In fact because the protective layer is a heat-resistant material, is prevented shrinkable support film. 这就能够采用不必具有良好的与温度有关的形稳性的支撑膜,如聚酯膜。 It is possible to employ not have to have good temperature-related dimensional stability of the support film, such as polyester film.

进一步说,本发明的构件具有良好的抗老化性,这就使印刷电路可长时间或在不利的环境下使用。 Further, the member of the present invention have good aging resistance, which makes the printed circuit may be used in a long time or under adverse conditions. 最后,在基材的两个面之间的电绝缘性得以提高。 Finally, between the two faces of the electrically insulating substrate is improved.

本发明的另一目的是一种生产上述复合材料的方法,包括:一将一层栽绒纤维沉积在对电和/或热绝缘的支撑层的至少一个面上,所述的纤维是由耐热纤维组成的,和-用耐热树脂涂覆栽绒纤维,形成对绝缘支撑层的保护层。 Another object of the present invention is a method for producing the above composite material, comprising: a layer of tufted fibers deposited on the electrical and / or thermal insulation of at least one surface of the support layer, wherein the fibers are made resistant Hot fiber composition, and - with a heat-resistant resin-coated tufted fibers formed on the insulating layer, a protective layer support.

根据本发明的一个特征,栽绒层的涂覆是在树脂溶液中进行的,树脂是被沉积到栽绒纤维的层之上和/或之中以制得被纤维增强的树脂层。 According to one feature of the invention, the coating layer is tufted in a resin solution for the resin is deposited on top of the tufted fiber layers and / or being to produce a fiber-reinforced resin layer being.

树脂的沉积尤其可以认为是这样的技术,即能够将树脂溶液沉积在栽绒层上,并使此层与一种不溶解树脂的液体接触,例如将此构件浸在非溶剂液体中;这种技术叫做凝结作用。 Deposition of the resin can be considered in particular such a technique, i.e., the resin solution can be deposited on the tufted layer, and this layer is contacted with a liquid that does not dissolve resins, for example, this member is immersed in a non-solvent liquid; this technique is called coagulation.

但是,其它能够使树脂沉淀或凝结的技术也可在不超出本发明范围的情况下被采用。 However, other resin can be precipitated or coagulated techniques may also be without departing from the scope of the present invention is employed.

接着将复合构件干燥以去除溶剂或非溶剂。 The composite member is then dried to remove the solvent or nonsolvent.

通过树脂凝结作用来涂覆栽绒纤维导致下列事实成为可能:在凝结作用的过程中,用对树脂是非溶剂且具有适当低沸点的其它化合物如水来替代通常具有高沸点的树脂溶剂。 Coated by the resin coagulation tufted fibers causes the following facts became possible: the coagulation process, other compounds with the resin and having an appropriate non-solvent such as water to replace the low boiling point solvent is usually a resin having a high boiling point. 这样复合构件的干燥就可以在较低的温度下进行,减小了破坏支撑膜的危险。 Such drying of the composite member can be carried out at lower temperatures, reduces the risk of destruction of the support film.

根据本发明的实施方案,涂覆溶液中树脂的重量含量在5%和50%之间。 According to embodiments of the present invention, the weight content of the resin in the coating solution of 5% and 50%.

适用于本发明的溶剂是,例如N-甲基吡咯烷酮、二烷基脲如二甲基亚乙基脲(DMEU)或二甲基亚丙基脲、二甲基乙酰胺、二甲基甲酰胺、酮类、二甲基亚砜和它们与其它惰性溶剂如二甲苯、二甲基醚或二甘醇或三甘醇的混合物。 The solvents useful in the present invention are, for example N- methylpyrrolidone, dialkylureas such as dimethylethyleneurea (DMEU) or dimethylpropyleneurea, dimethylacetamide, dimethylformamide , ketones, dimethyl sulfoxide and their other inert solvent such as xylene, diethylene glycol dimethyl ether or triethylene glycol or mixtures thereof.

树脂的凝结作用通常是通过将被树脂溶液涂覆的栽绒层与水接触而进行的。 Coagulation resin is usually the resin solution was applied by the tufted layer in contact with water carried out.

树脂溶液可以含有能够改进湿润栽绒纤维能力的添加剂。 Resin capable of improving the wetting solution may contain fibers tufted ability additives. 但是,为了提高纤维在树脂中的湿润性,它们可以用能够调节表面张力的涂饰剂处理。 However, in order to improve fiber wettability of the resin, they may be treated with a finishing agent capable of adjusting the surface tension.

在干燥后,本发明的复合构件具有良好的粘接性。 After drying, the composite member of the present invention has good adhesion.

本发明的其它优点和细节将借助于下面以说明方式单独给出的实施例的形式,进行更加清楚的说明。 Other advantages and details of the invention will be described by means of the following in the form given by way of a separate embodiment, a more clear description. 实施例具有未涂覆栽绒层的复合材料的制备将由Henkel公司市售的聚酯/聚氨酯型的双组份粘接剂用凹槽辊以50g/m2的速度,附着在厚度为125微米的2GT聚酯膜上。 Prepared by Henkel Corporation embodiment has an uncoated tufted layer of composite material commercially available polyester / polyurethane type of two-component adhesive with a gravure roll at a rate of 50g / m2, and the coating thickness of 125 microns 2GT polyester film.

将放置在刮料板上的有粘接剂涂层的聚酯膜运至装有以商标Kermel出售的聚酰胺-酰亚胺栽绒纤维(支数2.2分特-长度0.3mm)的进料斗的下面。 Will be placed in the scraper plate has adhesive coated polyester film shipped to mark Kermel sold equipped with polyamide - imide tufted fibers (2.2 dtex count - the length of 0.3mm) feed bucket below.

在进料斗和膜之间设置一个能够提供电场的设备,在电场中,通过料斗运送的纤维被加速和定向,这就使它们栽绒到粘接剂中(电场设置在一个料斗出口的栅板和膜支撑板之间)。 Between the feed hopper and the film is provided a device capable of providing an electric field, in the electric field, the fibers are accelerated through a hopper and conveying oriented, which makes them adhesive to the tufted (electric field provided at an outlet of the hopper gate between the plate and the membrane support plate).

在进行栽绒纤维沉积的出口,先用打浆辊随后用吸入排气法去除未被粘接剂固定的纤维。 Conducting export tufted fiber deposition, followed by the first method to remove not inhale exhaust adhesive fixed fiber beating rolls.

这样栽绒后,对膜进行热处理来完成干燥和粘接剂的交联。 After such tufted, the film is heat-treated to complete drying and crosslinking of the adhesive.

在有两个面进行栽绒的情况下,接着对另一个面进行同样的处理。 In the case of two faces conducted tufted case, then to the other surface subjected to the same treatment.

这样制得的完全匀称的材料每单位面积的重量是330g/m2(包括175g的聚酯膜和155g的粘接剂+栽绒纤维)。 Weight of the obtained material is completely symmetrical per unit area is 330g / m2 (including 175g and 155g of polyester film adhesive + tufted fibers). 栽绒层的涂覆在二甲基亚乙基脲(固体含量:27%-在25℃粘度280泊)中,根据在欧洲专利0360707中描述的方法,制备由1,2,4-苯三酸酐和2,4-甲苯二异氰酸酯的缩聚反应生成的聚酰胺-酰亚胺。 Coated tufted layer dimethylethylene urea (solid content: 27% - viscosity 280 poise at 25 ℃) in accordance with the method described in European Patent 0360707, the preparation from trimellitic anhydride and 2,4-polycondensation reaction of toluene diisocyanate generated polyamide - imide.

制备上述树脂在二甲基亚乙基脲中的两种溶液:溶液A1:在30℃粘度为85溶液A2:在30℃粘度为3.2。 Two solutions were prepared in the above-described resin dimethylethylene urea in: Solution A1: a viscosity at 30 ℃ solution 85 A2: 3.2 viscosity at 30 ℃.

上面制得的复合材料的栽绒层用溶液A1和A2涂覆。 The above prepared composite material tufted layer coating solution A1 and A2.

涂覆是通过将栽绒膜浸在盛有这种溶液的槽中,再在两个通过可调弹簧相互挤压的辊之间压制涂覆材料。 Applied by the tufted film immersed in a bath containing the solution, and then between two mutually squeeze through an adjustable spring roll coating material repression.

将压制完的涂覆材料浸在水中,进行聚酰胺-酰亚胺溶液凝结,并接着在缓慢水流下洗涤,去除被树脂夹带的残留溶剂。 After pressing the coating material is immersed in water, and the polyamide - imide solution was coagulated, washed and then under a slow flow of water, to remove residual solvent entrained resin.

在此步骤,通过涂覆-凝结处理的材料具有干燥的和固体感觉,但是,实际上仍含有微量的溶剂和一定百分比的水。 In this step, by coating - material having a dry coagulation process and solid feeling, but, in fact, still containing traces of solvent and a percentage of water. 这些组份(溶剂和水)确保了聚酰胺-酰亚胺具有一定的增塑性。 These components (solvent and water) to ensure that the polyamide - imide having a certain plasticity.

在这种增塑了的状态下,可以通过加压或压延进行产品的稠化作用。 In this plasticized state, may be the product densification by compression or calendering.

也可以仅通过将这种材料在接近100℃的温度下干燥去除残存的水而达到这种稠化作用。 May be provided only by this material at a temperature near 100 ℃ dried to remove residual water to achieve such a thickening effect. 这种水的去除引起了涂料用树脂在厚度方向的收缩。 Removal of this water causes shrinkage of the coating resin in a thickness direction.

由此制得的复合材料的性质列于下表I:表1 Properties of thus obtained composite is shown in Table I: Table 1

夹带的树脂的量是-用溶液A1是230g/m2-用溶液A2是185g/m2。 Is the amount of entrained resin - solution A1 is 230g / m2- solution A2 is 185g / m2.

将前面试验的树脂进行涂覆凝结作用,而稀释之后溶液(溶液C1)的粘度在30℃是34泊。 The resin coated front coagulation tests, and after the viscosity of a dilute solution (solution C1) at 30 ℃ was 34 poise.

从通过100摩尔的2,4-甲苯二异氰酸酯、20摩尔1,2,4-苯三酸酐、76摩尔对苯二酸和4摩尔的1,3-二羧苯磺酸钠在DMEU中的缩合反应生成的聚酰胺-酰亚胺树脂开始,通过在DMEU中稀释制备在30℃粘度是25泊的溶液(C2)。 From through 100 moles 2,4-tolylene diisocyanate, 20 mol of trimellitic anhydride, 76 mol of terephthalic acid and 4 moles of 1,3-dicarboxylic benzene sulfonate of the condensation in DMEU reaction of the polyamide - imide resin starts, by preparing at 30 ℃ solution viscosity was 25 poise (C2) are diluted in DMEU.

将前面采用的330g/m2栽绒膜如已在上述溶液C1和C2中描述了的方法通过涂覆凝结作用进行处理。 To 330g / m2 tufted front film has been described as employed in the above solution C1 and C2 are processed in the method by coating coagulation.

所得产物的性质列于下表II:表II Properties of the resulting product are shown in Table II: Table II

在这些实施例中,每一次浸渍都是单独进行,产生随操作条件而变的树脂含量不同的现象。 In these embodiments, each impregnation is carried out separately, the content of the resin produced with the operating conditions become different phenomena.

下面的实施例说明了本发明的优点,即往浸渍溶液中加入添加剂的可能性。 The following examples illustrate the advantages of the present invention, namely the possibility of additives to the impregnation solution was added.

通过实施例描述了复合材料的制备,其中将保护层的表面金属化,这样就得到了软性印刷电路。 Through examples describe the preparation of composite material, wherein the metal surface protective layer, thus obtained flexible printed circuits.

将由Norddeutsche Affinerie公司出售的Cu2O(氧化亚铜)以相对于溶液中所含干树脂的30%(重)的比例加入到溶液C1和C2。 Sold by the Norddeutsche Affinerie Cu2O (cuprous oxide) with respect to 30% (weight) contained in the solution dry resin was added to the solution ratio of C1 and C2.

将这些被添加的溶液按照与在前面实施例所述方法一样的方法应用,制得复合构件,其性能列于下表III:表III These are added to a solution in accordance with the method described in Example in the same way as the previous application, to obtain a composite member having the properties listed in the following Table III: Table III

涂料凝结之后的材料是暗红色的。 Coating material after condensation was dark red.

为了去除在表面的纯树脂膜,并暴露Cu2O颗粒,将基材通过采用Vapor Blast(商用名)设备,在AVB90(商标)磨料喷砂压力为4巴、距离为15-20cm的条件下进行湿的喷砂处理。 In order to remove the pure resin film surface, and exposed Cu2O particles, the substrate by using Vapor Blast (trade name) device, in AVB90 (trademark) abrasive blasting pressure of 4 bar, the distance of 15-20cm under wet conditions The sandblasting. 接着将基材清洗干净,并在热空气流中干燥。 Then the substrate is cleaned and dried in a hot air stream. 表面粗糙度系数如下Ra>3,Rt>28。 Surface roughness coefficient as Ra> 3, Rt> 28.

将栽绒纤维的表面接着进行金属化工艺。 The surface of the tufted fibers followed by metallization process.

Cu2O还原浴是水溶液,其中含有:-0.7g的Rhodopol(杂多糖)-5g的氢氧化钾-20g的二酒石酸Na Kc-20g碘化钠,和-50g的NaBH4。 Cu2O reduction bath is an aqueous solution containing: -0.7g of Rhodopol (heteropolysaccharide) -5g two tartrate Na Kc-20g -20g of potassium hydroxide, sodium iodide, and -50g of NaBH4.

为了使反应物在基材表面形成的膜是均一的,将待金属化的材料浸渍在浴中,并立即取出,速度为约1cm/s。 To the film surface of the substrate forming reactants is uniform, the material to be immersed in the metallization bath, and removed immediately, the speed of about 1cm / s. 将从还原浴中取出的基材置于空气中,接着用水清洗。 Substrate from the bath removed reduction in air, followed by washing with water.

将清洗了的未干燥的基材在40℃的由Kemifer公司出售的化学形式为EC580(商用参考号)铜浴浸渍15分钟。 Washing the substrate in the undried chemical form sold by Kemifer 40 ℃ for EC580 (Commercial reference number) copper bath immersion for 15 minutes.

清洗后,将铜涂覆的基材通过浸渍在由Kemifar公司出售的KEM1044(商品名)水中浓度为3%的钝化溶液中,进行钝化处理以防止氧化。 After washing, the substrate is coated by immersion in the copper by Kemifar sold KEM1044 concentration (trade name) water 3% passivating solution, passivation treatment to prevent oxidation.

不论溶液C1或C2的性质如何,化学铜沉积的厚度是1.5到1.8微米。 Irrespective of the nature of a solution of C1 or C2, the thickness of the electroless copper deposition is 1.5 to 1.8 microns. 这种金属化的复合材料可以通过已知的方法处理来制备软性印刷电路。 This metallized composite can be prepared by known flexible printed circuit manner.

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CN101243615B14 Aug 200612 Dec 2012丹佛大学Testing procedure for evaluating diffusion and leakage currents in insulators
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