CA1298565C - Organopolysiloxane materials having decreased surface tack - Google Patents
Organopolysiloxane materials having decreased surface tackInfo
- Publication number
- CA1298565C CA1298565C CA000508126A CA508126A CA1298565C CA 1298565 C CA1298565 C CA 1298565C CA 000508126 A CA000508126 A CA 000508126A CA 508126 A CA508126 A CA 508126A CA 1298565 C CA1298565 C CA 1298565C
- Authority
- CA
- Canada
- Prior art keywords
- organopolysiloxane
- crosslinking
- fluid
- irradiating
- tack
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/16—Chemical modification with polymerisable compounds
- C08J7/18—Chemical modification with polymerisable compounds using wave energy or particle radiation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C71/00—After-treatment of articles without altering their shape; Apparatus therefor
- B29C71/04—After-treatment of articles without altering their shape; Apparatus therefor by wave energy or particle radiation, e.g. for curing or vulcanising preformed articles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
- B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
- B29C2035/0827—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation using UV radiation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2083/00—Use of polymers having silicon, with or without sulfur, nitrogen, oxygen, or carbon only, in the main chain, as moulding material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31652—Of asbestos
- Y10T428/31663—As siloxane, silicone or silane
Abstract
Abstract This invention provides organopolysiloxane materials having cone penetration between about 100 and about 350 (10-1mm) and ultimate elongation of at least 100% and having reduced surface tack. This invention provides three methods of obtaining said materials with reduced surface tack. The first method comprises applying to the surface of such material an organic peroxide or a photoinitiator and irradiating the surface with ultraviolet light to crosslink the surface to reduce or eliminate the tack of the surface. The second method comprises mixing a photoini-tiator, such as benzophenone, in an organopolysiloxane fluid, thermally crosslinking the organopolysiloxane fluid to produce the material with the above cone penetration and ultimate elonga-tion then irradiating the surface of the material with ultra-violet light to reduce or eliminate the tack of the surface. The third method comprises mixing a photoinitiator, such as ben-zophenone, in an organopolysiloxane fluid, crosslinking the fluid by irradiating a layer of the fluid with ultraviolet light to produce the above cone penetration and ultimate elongation pro-perties then further irradiating the crosslinked material to reduce or eliminate the surface tack; this method can be carried out by simultaneous irradiation with ultraviolet light from two sides of a layer of the organopolysiloxane wherein one surface is irradiated at a higher intensity than the other surface. The materials produced by this invention are useful as tapes and sealants.
Description
12~85~
This in~ention relates to organopoly~iloxane materials haYing a cone penetration between about lOo and about 350 (lO 1mm) (A5TN NoO D217~-68) and ultimate elongation of at least 100% (ASTM No~ 638-80) and in particular is related to redu~ing the surface tack of thes~ material~.
A wide variety of organopolysiloxanes are known in the art and have been used for a wide variety of purposes. This invention relates to those organopolysiloxanes having the abvve cone penetration and ultimate elongation properties which materials also have a very high surface tackiness. These materials are useful as sealants and encapsulants to protect substrates from environmental exposure and are particularly useful in thin sheets or tapes having a thickness of 5 mm or less~ Due to the surface tackiness and other properties of these materials, they are difficult to handle. The handling qualities can be improved by crosslinking the organopolysiloxane in a flexible matrix as disclosed in copending Canadian application No. 505,038 filed March 25, 1986. When such materials are wrapped around a substrate or applied to a substrate the exposed surface of the material remains tackyO It is desirable to provide such a material which has a reduced or non-tacky surface when installed on a substrate.
U.S. Patent 4,163~082 to Romenesko discloses reducing or eliminating surface tacX on organopolysiloxanP gels or greases by applying to the surface of the gel or grease an additional layer of a liquid organopolysiloxane composition which is W curable then curing the coating by ultraviolet radiation. U.S.
Patent 4,364,809 to Sato et al. relates to ~ , ,~`'., `' ~Z985~5 organopolysiloxanes cured to rubbery elastomer thin sheets but does not particularly address the desirability of having a non-tacky surface thereon.
Other references which illustrate the general background o~ organopolysiloxane materials, their preparation, curing, and the like include U.S. Patent 4,196,273 to Imai et al.; 3,624,022 to Ross; 4J064~027 to Gant and 4,163,081 to Schulz.
U.S. Patent 2,762,609 to Lewis et al. relates to organopolysiloxanes which in one aspect are partially cured on one sur~ace and le~t uncured on the other surface then installed on a substrate and then fully vulcanized in place.
The disclosures of the above patents illustrate the conventional and general background relative to the types of organopolysiloxane materials which may be crosslinked, the methods of crosslinking polysiloxanes, the initiators used to initiate the cros~linking and other conventional aspects of the organopolysiloxane art.
In one aspect, this invention relates to a method of reducing the sur~ace tack of crosslinked organopolysiloxane materials having cone penetration between about 100 and about 350 (10 lmm) and ultimate elongation at least about 10Q% which comprises:
applying to the surface of said material an effective amount of an organic peroxide or a photoinitiator; and 5~
irradiating the surface with ultraviolet light to effect a further crosslinking o~ the surface of said material to reduce the surface tack thereof without effecting significant further crosslinking of said material below said surface.
In another aspect, this invention relates to a method of producing a crosslinked organopolysiloxane material having cone penetration between about lO0 and about 350 (lO~lmm) and ultimate elongation of at least about lO0~ and having reduced surface tack which comprises:
mixing in an organopolysiloxane fluid an effective amount of a photoinitiator;
thermally crosslinking said organopolysiloxane fluid to a cone penetration between about 100 and about 350 (lO~lmm) and an ultimate elongation of at least about 100%; and irradiating the surface with ultraviolet light to effect a further crosslinking of the surface of said material to reduce the surface tack thereof without effecting signifi-cant further crosslinking of said material below said surface.
In another aspect, this invention relates to a method of producing a crosslinked organopolysiloxane material having cone penetration between about 100 and 350 (lO~lmm) and ultimate elongation of at least about 100% and having reduce surface tack which comprisesO
mixing in an organopolysiloxane fluid an effective amount of a photoinitiator;
3~29~56~i crosslinking said organopolysiloxane fluid to a material having cone penetration between about lO0 and about 350 (lO~lmm) and an ultimate elongation of at least about 100%
by irradiating said fluid with ultraviolet light; and irradiating a surface of said material with ultraviolet light to effect a further crosslinking of the surface of said material to reduce the surface tack thereof without effecting significant further crosslinking of said material below said surface.
As part of this aspect of the invention an organic peroxide can also be mixed in the organopolysiloxane fluid, the fluid crosslinked then the surface irradiated to reduce the surface tack. As another part of this aspect of the invention, the crosslinking of said fluid and the irradiating of a surface to reduce surface tack may be performed simultaneously by irra-diating the fluid from two sides with different intensity irradiation.
In another aspect, this invention relates to organopolysi-loxane materials which are produced by the above methods and have reduced or eliminated surface tack on at least one surface.
In another aspect, this invention relates to substrates having the above materials disposed thereon to provide environ-mental or other sealing or protection of the substrate.
The organopolysiloxanes useful in this invention may be any general purpose organopolysiloxane fluid which can be crosslinked to provide a cone penetration between about lO0 and about 350 tlO~lmm) and an ultimate elongation of at least lO0~. These ~:9~35~5 organopolysiloxanes may have various substituents thereon to provide particularly desired properties known in the prior art. A preferred class of organopolysiloxanes are the polydimethylsiloxanes which may be trimethyl terminated, vinyl terminated, methyl terminated, and the like. Other preferred classes of organopolysiloxane fluids include the polyvinylmethylsiloxanes copolymer with dimethylsiloxanes or methylsiloxanes with similar termination groups. A particularly preferred organopolysiloxane is the vinyl crosslinked organopolysiloxanes disclosed in copending Canadian application No. 508,129 filed on even date herewith.
In general the organopolysiloxanes crosslinked to provide the above cone penetration and ultimate elongation properties which make them useful as sealants and materials for protecting substrates. The high surface tackiness of these materials provides a good seal with the substrate to prevent water or other contamination of the substrate. These materials also have good elastic recovery forces and self-healing properties as well as other characteristics which make them particularly useful.
The organic peroxides useful in the method of this invention includes conventional organic peroxides which are useful in the photocuring of organopolysiloxanes, such as benzoyl peroxide, ditert-butyl peroxide, tert-butyl cumyl peroxide, dicumyl peroxide, and peroxyesters such as tert-butyl peroxy, isopropylcarbonate, tert-butylpero~y benzoate and the like, Various other organic background patents referred to above.
The photoinitiators useful in the methods of this invention are likewise well known in the art as conventional photoini-~'"
~g~s~-p~
tiators for ultraviolet radiation curing of organopolysiloxanes and include such compounds as benzophenone, acetophenone, p h ~ n ~ n e.
r anthraquinone, benzaldehyde, ~he~ e, l-hydroxycyclohexylphenyl ketone, diethyoxyacetophenone, ben-zoinethers, 2-chlorothioxanthone, benzil and benzil ketals.
Other similar photoinitiators will be be apparent from the background patents cited above as well as other sources.
When the organic peroxide or photoinitiator is applied to the surface of a crosslinked organopolysiloxane material according to this invention, the application may be by spraying, rolling, brushing, or other method of evenly distributing the organic peroxide or photoinitiator on the surface of said material. ~ pxeferred method of applying the organic peroxide or photoinitiator is in a solvent solution wherein the solvent is not incompatible with the crosslinked organopolysiloxane material and does not advexsely affect the UV radiation crosslinking of the surface of the material. rrhe organic peroxide or photoini-tiator may be applied as a 0.1% by weight or higher solution pro-vided that the sur~ace of the crosslinked organopolysiloxane material is sufficiently coated with an effective amount thereof to effect the UV crosslinking of said surface. It is generally useful to use about 3% to about 10% solutions.
When the photoinitiator is mixed with the organopolysiloxane fluid before it is crosslinked, the photoinitiator can be present in any amount effective to provide efficient UV crosslinkiny of the organopolysiloxane fluid and/or the surface of the crosslinked material. An effective amount may range from about 0.05% to about 5.0% by weight based on the organopolysiloxane fluid. In general an effective amount will range from about 0.1%
to about 1~0% and in many applications an effective amount will be about 0.5% by weight.
.
. .
lZ~
_9_ When the organopolysiloxane fluid is thermally crosslinked according to this invention, temperatures in the range of about 50C ts about 250C are useful for most general purpose organopo-lysiloxane 1uids.
The ultraviolet light used for crosslinking according to this invention is conventional high intensity W radiation used for curing organopolysiloxane fluids~ The intensity and time of exposure to achieve the crosslinking of the surface of the orga-nopolysiloxane materials according to this invention will vary depending on the characteristics of the organopolysiloxane material as well as the organic peroxide or the photoinitiator used. In general, ultraviolet light having a power of 100 to 1500 watts and can be applied for a period of about 1 to about 300 seconds while from about 5 to about 120 seconds will in general produce the desired result according to this invention.
When ultraviolet light is used to crosslink the organopolysi-loxane fluid according to this invention as well as crosslink the surface of the resulting material conventional levels of irra-diation with the ultraviolet light may be used to obtain the cone penetration and elongation by use desired according to this invention. It should also be noted that when ultraviolet light is used to crosslink the organopolysiloxane fluid as well as to crosslink the surface thereof these curing mechanisms may be per-formed simultaneously by providing ultraviolet light on both sides of a layer of the organopolysiloxane and providing a higher intensity on the side where it is desired to reduce or eliminate the surface tack.
The materials produced according to this invention may be used as sheets or tapes for environmental or other protection of c., ~7 substrates. When applied to ~he substrate the materials of this ~;~9~
invention will have a surface exposed which has reduc~d or no surface tack.
This invention may be further illustrated by reference to the following examples:
Example 1 An organopolysiloxane fluid, commercially available as KE
104 Gel from Shin-Etsu Chemical Co. Ltd of Tokoyo, Japan, and l v ze d which is a platinum e~ed addition cure, was thermally cured .. 4 ~
at a temperature of 150C to a cone penetration of 262 (ASTM No.
D217-68) and ultimate elongation of 450~ ~ASTM No. D638-80) in the form of sheets 2, 3 and 4 mm ~hick, respectively, no additive was used in this example. Side 1 of each sheet was exposed to ultraviolet light at a power o 1500 watts, 12 inches from the sample, for up to 180 seconds as indicated in the following table. After exposure to the ultraviolet light, the surface tackiness or adhesion was measured on a Voland-Stevens LFRA
Texture Analyzer. A tape or strip of each sheet is placed on a stage with a 0.5 inch hole. A 0,25 inch ball probe is pressed against the strip over the hole at a speed of 2~0 mm/sec. to a depth o~ 1.0 mm then retracted at the same speed of 2.0 m/sec.
The adhesion values are given in grams in the following table for side 1 and side 2 o each of the three sheetsO
5~5 Table 1 _ _ _ Sample Side Adheslo_ time=0 lOsec30sec 60sec120sec180sec ~ __ __ _ _ __ __ 2 mm 111.~ 11.3 11.7 9.8 10.6 10.8 2 6.6 703 7~1 6.3 7.5 7.1 __ ___ _ _ __ ____ __ _ 3 mm 1 5.0 4.7 4.7 5.5 4.9 5.2 : 2 7.4 5.5 7.4 7.8 7.8 7.6 ___ _ __ mm 1 4.3 3.8 4.0 4.7 4.9 4.4 2 5.9 6.1 7.2 7.3 6.7 6.3 _ __ ~
Exam e_e 2 In this example, the same organopolysiloxane material from Example 1 and having the same cone penetration and elongation values was used. In this example side 1 of each sheet was coated with a 3% solution of ~ ~4p ~ e in 2~propanol and allowed to dry. Side 1 of each sheet was then exposed to the same W light source used in Example 1 for the time periods indicated up to 18 seconds. After the exposure the surface tackiness or adhesion of side 1 and side 2 of each sheet was measured in accordance with Example 1. The results are set forth in the following Table 2.
~LZ985~
~.~Pl054 Table_2 __ _ _ __ _ _ S_~e~e Sid_ Adhesion t_me=0 lOsec 30sec 60sec 120sec 180sec _ __ _ ___ ___ _ _ 2 mm 1 4.5 4.3 3.7 1.~ l.0 0,5 2 4.5 4.2 4.4 4.7 4.8 4.3 ___ _ __ _~
3 mm 1 4.4 3.7 3.5 2.7 1.5 0.8 2 4.7 4.3 5.0 5.2 5.7 5.3 _ _ __ 4 mm l 4.4 3.4 1.4 1.2 1.0 0.08 2 4.7 4.3 4.2 4.7 ~.5 4.3 E mple 3 In this example, the same organopolysiloxane fluid was used as in Example 1 except ~ 0.5% by weight benzophenone was mixed with the fluid before it was cured to the cone penetration and ultimat~ elongation values set forth in Example l. A 3 mm thick sheet of the crosslinked material was exposed to the same W
light source used in Examples 1 and 2 for the time periods indi-cated in the following table up to 180 seconds. After the UV
light exposure the surface tackiness or adhesion of each side of the sheet was measured in accordance with Example 1. The results are set forth in the following Table 3.
~2~3S6~
S~2le Side Adhesion _ _ _ time=0lOsec 30sec 60s__ 120sec 180sec __.__ ___ _ __ _ _ __ 3 mm 1 9.4 8.6 4.8 ~.8 2.1 1.8 _ 2 5.1 5.7 5.3 5.9 5.3 _ _ Exa~ ple 4 In this example, an organopolysiloxane fluid ~hich is a mix-ture of trimethyl terminated poly dimethylsiloxane with 5% by weight divinyl terminated dimethylpolysiloxane and 0.5~ benzoyl peroxide was heat cured under nitrogen at a temperature of 150C
to a cone penetration of 260 and ultimate elongation of 850~.
The material was crosslink~d in a sheet 3 ~m thick. No additives were applied to the surface of the sheet in this example. Side 1 of the sheet was exposed to the same ultraviolet light source as in the above examples for the periods of time indicated in the following table. After the UV light exposure the surface tacki-ness or adhesion was measured in accordance with Example l and the results are set forth below in Table 4.
s~
Table 4 _ ___ _ _ _ __ Time of UV ~ _ _ _ _ Exposure:
(Seconds) 0 10 30 60 120 180 __ __ __ __ ____._ _ _ _ _____ ADHESION
No additives Side 1 2.5 2.8 2.8 2.9 3.2 3.6 __. _~ _ _ _ _ _ _ _ Side 2 3.1 2.9 2.7 2.8 2.9 2.7 ___ _ _ ___ __ _ _ ___ Ratlo tSide 1/2) 0.81 0.96 0.97 1.04 1.10 1.33 Example 5 The same organopolysiloxane fluid of Example 4 was cured to the same cone penetration and ultimate elongation values as Example 4 and a sheet 3 mm thick. A 3% solution oE benzophenone and 2-propanol was applied to side 1 of the sheet then side 1 was exposed to the same ultraviolet light source as in the previous examples. After exposure to the UV light the surface tackiness or adhesion was measured in accordance with Example 1 and the results are set forth in the following Table 5.
~29~
Table 5 __ __ __ ___ ___ __ __ _ Time of UV _ _ _ _ _ _ Exposure:
(Seconds) 0 10 30 60 120 180 . ___ . _ _ _ __ _ _ __ ___ ADHE-SION
Benzophenone or Side 1 3.0 1.9 0.8 0.4 0.2 0.1 _ __ _ _ _ _ ___ Side 2 2.8 2.5 2.7 206 2~8 2~8 _ ____ _ ___ Ratio (Side 1/2) 1.07 0.76 0.30 0.15 0.07 0.03 Exam e~ 6 In this example, the same organopolysiloxana fluid as in Example 4 was used with 0.5~ benzophenone mixed in the fluid then cured to the above cone penetration and ultimate elongation values in Example 4. Side 1 of the sheet, which is 3 mm thick, was exposed to the same ultraviolet light source as indicated above for the periods of time set forth below. The surface tackiness or adhesion was then measured on both sides of the sheet and the results are set forth below in Table 6.
~85~5 MP1~54 Table 6 Time of W _ Exposure:
(Seconds) 0 10 30 60 120 180 _ _ _ ADHESION
Benzophenone ir Side 1 3.22.2 1.3 0.6 0.3 0.1 _ _ Side 2 3.83.8 3.6 3.4 3.6 3.7 _ _ ___ .
Ratlo ~ Sida 1/2 ) 0.840.5B 0.36 0.18 0.08 0.05
This in~ention relates to organopoly~iloxane materials haYing a cone penetration between about lOo and about 350 (lO 1mm) (A5TN NoO D217~-68) and ultimate elongation of at least 100% (ASTM No~ 638-80) and in particular is related to redu~ing the surface tack of thes~ material~.
A wide variety of organopolysiloxanes are known in the art and have been used for a wide variety of purposes. This invention relates to those organopolysiloxanes having the abvve cone penetration and ultimate elongation properties which materials also have a very high surface tackiness. These materials are useful as sealants and encapsulants to protect substrates from environmental exposure and are particularly useful in thin sheets or tapes having a thickness of 5 mm or less~ Due to the surface tackiness and other properties of these materials, they are difficult to handle. The handling qualities can be improved by crosslinking the organopolysiloxane in a flexible matrix as disclosed in copending Canadian application No. 505,038 filed March 25, 1986. When such materials are wrapped around a substrate or applied to a substrate the exposed surface of the material remains tackyO It is desirable to provide such a material which has a reduced or non-tacky surface when installed on a substrate.
U.S. Patent 4,163~082 to Romenesko discloses reducing or eliminating surface tacX on organopolysiloxanP gels or greases by applying to the surface of the gel or grease an additional layer of a liquid organopolysiloxane composition which is W curable then curing the coating by ultraviolet radiation. U.S.
Patent 4,364,809 to Sato et al. relates to ~ , ,~`'., `' ~Z985~5 organopolysiloxanes cured to rubbery elastomer thin sheets but does not particularly address the desirability of having a non-tacky surface thereon.
Other references which illustrate the general background o~ organopolysiloxane materials, their preparation, curing, and the like include U.S. Patent 4,196,273 to Imai et al.; 3,624,022 to Ross; 4J064~027 to Gant and 4,163,081 to Schulz.
U.S. Patent 2,762,609 to Lewis et al. relates to organopolysiloxanes which in one aspect are partially cured on one sur~ace and le~t uncured on the other surface then installed on a substrate and then fully vulcanized in place.
The disclosures of the above patents illustrate the conventional and general background relative to the types of organopolysiloxane materials which may be crosslinked, the methods of crosslinking polysiloxanes, the initiators used to initiate the cros~linking and other conventional aspects of the organopolysiloxane art.
In one aspect, this invention relates to a method of reducing the sur~ace tack of crosslinked organopolysiloxane materials having cone penetration between about 100 and about 350 (10 lmm) and ultimate elongation at least about 10Q% which comprises:
applying to the surface of said material an effective amount of an organic peroxide or a photoinitiator; and 5~
irradiating the surface with ultraviolet light to effect a further crosslinking o~ the surface of said material to reduce the surface tack thereof without effecting significant further crosslinking of said material below said surface.
In another aspect, this invention relates to a method of producing a crosslinked organopolysiloxane material having cone penetration between about lO0 and about 350 (lO~lmm) and ultimate elongation of at least about lO0~ and having reduced surface tack which comprises:
mixing in an organopolysiloxane fluid an effective amount of a photoinitiator;
thermally crosslinking said organopolysiloxane fluid to a cone penetration between about 100 and about 350 (lO~lmm) and an ultimate elongation of at least about 100%; and irradiating the surface with ultraviolet light to effect a further crosslinking of the surface of said material to reduce the surface tack thereof without effecting signifi-cant further crosslinking of said material below said surface.
In another aspect, this invention relates to a method of producing a crosslinked organopolysiloxane material having cone penetration between about 100 and 350 (lO~lmm) and ultimate elongation of at least about 100% and having reduce surface tack which comprisesO
mixing in an organopolysiloxane fluid an effective amount of a photoinitiator;
3~29~56~i crosslinking said organopolysiloxane fluid to a material having cone penetration between about lO0 and about 350 (lO~lmm) and an ultimate elongation of at least about 100%
by irradiating said fluid with ultraviolet light; and irradiating a surface of said material with ultraviolet light to effect a further crosslinking of the surface of said material to reduce the surface tack thereof without effecting significant further crosslinking of said material below said surface.
As part of this aspect of the invention an organic peroxide can also be mixed in the organopolysiloxane fluid, the fluid crosslinked then the surface irradiated to reduce the surface tack. As another part of this aspect of the invention, the crosslinking of said fluid and the irradiating of a surface to reduce surface tack may be performed simultaneously by irra-diating the fluid from two sides with different intensity irradiation.
In another aspect, this invention relates to organopolysi-loxane materials which are produced by the above methods and have reduced or eliminated surface tack on at least one surface.
In another aspect, this invention relates to substrates having the above materials disposed thereon to provide environ-mental or other sealing or protection of the substrate.
The organopolysiloxanes useful in this invention may be any general purpose organopolysiloxane fluid which can be crosslinked to provide a cone penetration between about lO0 and about 350 tlO~lmm) and an ultimate elongation of at least lO0~. These ~:9~35~5 organopolysiloxanes may have various substituents thereon to provide particularly desired properties known in the prior art. A preferred class of organopolysiloxanes are the polydimethylsiloxanes which may be trimethyl terminated, vinyl terminated, methyl terminated, and the like. Other preferred classes of organopolysiloxane fluids include the polyvinylmethylsiloxanes copolymer with dimethylsiloxanes or methylsiloxanes with similar termination groups. A particularly preferred organopolysiloxane is the vinyl crosslinked organopolysiloxanes disclosed in copending Canadian application No. 508,129 filed on even date herewith.
In general the organopolysiloxanes crosslinked to provide the above cone penetration and ultimate elongation properties which make them useful as sealants and materials for protecting substrates. The high surface tackiness of these materials provides a good seal with the substrate to prevent water or other contamination of the substrate. These materials also have good elastic recovery forces and self-healing properties as well as other characteristics which make them particularly useful.
The organic peroxides useful in the method of this invention includes conventional organic peroxides which are useful in the photocuring of organopolysiloxanes, such as benzoyl peroxide, ditert-butyl peroxide, tert-butyl cumyl peroxide, dicumyl peroxide, and peroxyesters such as tert-butyl peroxy, isopropylcarbonate, tert-butylpero~y benzoate and the like, Various other organic background patents referred to above.
The photoinitiators useful in the methods of this invention are likewise well known in the art as conventional photoini-~'"
~g~s~-p~
tiators for ultraviolet radiation curing of organopolysiloxanes and include such compounds as benzophenone, acetophenone, p h ~ n ~ n e.
r anthraquinone, benzaldehyde, ~he~ e, l-hydroxycyclohexylphenyl ketone, diethyoxyacetophenone, ben-zoinethers, 2-chlorothioxanthone, benzil and benzil ketals.
Other similar photoinitiators will be be apparent from the background patents cited above as well as other sources.
When the organic peroxide or photoinitiator is applied to the surface of a crosslinked organopolysiloxane material according to this invention, the application may be by spraying, rolling, brushing, or other method of evenly distributing the organic peroxide or photoinitiator on the surface of said material. ~ pxeferred method of applying the organic peroxide or photoinitiator is in a solvent solution wherein the solvent is not incompatible with the crosslinked organopolysiloxane material and does not advexsely affect the UV radiation crosslinking of the surface of the material. rrhe organic peroxide or photoini-tiator may be applied as a 0.1% by weight or higher solution pro-vided that the sur~ace of the crosslinked organopolysiloxane material is sufficiently coated with an effective amount thereof to effect the UV crosslinking of said surface. It is generally useful to use about 3% to about 10% solutions.
When the photoinitiator is mixed with the organopolysiloxane fluid before it is crosslinked, the photoinitiator can be present in any amount effective to provide efficient UV crosslinkiny of the organopolysiloxane fluid and/or the surface of the crosslinked material. An effective amount may range from about 0.05% to about 5.0% by weight based on the organopolysiloxane fluid. In general an effective amount will range from about 0.1%
to about 1~0% and in many applications an effective amount will be about 0.5% by weight.
.
. .
lZ~
_9_ When the organopolysiloxane fluid is thermally crosslinked according to this invention, temperatures in the range of about 50C ts about 250C are useful for most general purpose organopo-lysiloxane 1uids.
The ultraviolet light used for crosslinking according to this invention is conventional high intensity W radiation used for curing organopolysiloxane fluids~ The intensity and time of exposure to achieve the crosslinking of the surface of the orga-nopolysiloxane materials according to this invention will vary depending on the characteristics of the organopolysiloxane material as well as the organic peroxide or the photoinitiator used. In general, ultraviolet light having a power of 100 to 1500 watts and can be applied for a period of about 1 to about 300 seconds while from about 5 to about 120 seconds will in general produce the desired result according to this invention.
When ultraviolet light is used to crosslink the organopolysi-loxane fluid according to this invention as well as crosslink the surface of the resulting material conventional levels of irra-diation with the ultraviolet light may be used to obtain the cone penetration and elongation by use desired according to this invention. It should also be noted that when ultraviolet light is used to crosslink the organopolysiloxane fluid as well as to crosslink the surface thereof these curing mechanisms may be per-formed simultaneously by providing ultraviolet light on both sides of a layer of the organopolysiloxane and providing a higher intensity on the side where it is desired to reduce or eliminate the surface tack.
The materials produced according to this invention may be used as sheets or tapes for environmental or other protection of c., ~7 substrates. When applied to ~he substrate the materials of this ~;~9~
invention will have a surface exposed which has reduc~d or no surface tack.
This invention may be further illustrated by reference to the following examples:
Example 1 An organopolysiloxane fluid, commercially available as KE
104 Gel from Shin-Etsu Chemical Co. Ltd of Tokoyo, Japan, and l v ze d which is a platinum e~ed addition cure, was thermally cured .. 4 ~
at a temperature of 150C to a cone penetration of 262 (ASTM No.
D217-68) and ultimate elongation of 450~ ~ASTM No. D638-80) in the form of sheets 2, 3 and 4 mm ~hick, respectively, no additive was used in this example. Side 1 of each sheet was exposed to ultraviolet light at a power o 1500 watts, 12 inches from the sample, for up to 180 seconds as indicated in the following table. After exposure to the ultraviolet light, the surface tackiness or adhesion was measured on a Voland-Stevens LFRA
Texture Analyzer. A tape or strip of each sheet is placed on a stage with a 0.5 inch hole. A 0,25 inch ball probe is pressed against the strip over the hole at a speed of 2~0 mm/sec. to a depth o~ 1.0 mm then retracted at the same speed of 2.0 m/sec.
The adhesion values are given in grams in the following table for side 1 and side 2 o each of the three sheetsO
5~5 Table 1 _ _ _ Sample Side Adheslo_ time=0 lOsec30sec 60sec120sec180sec ~ __ __ _ _ __ __ 2 mm 111.~ 11.3 11.7 9.8 10.6 10.8 2 6.6 703 7~1 6.3 7.5 7.1 __ ___ _ _ __ ____ __ _ 3 mm 1 5.0 4.7 4.7 5.5 4.9 5.2 : 2 7.4 5.5 7.4 7.8 7.8 7.6 ___ _ __ mm 1 4.3 3.8 4.0 4.7 4.9 4.4 2 5.9 6.1 7.2 7.3 6.7 6.3 _ __ ~
Exam e_e 2 In this example, the same organopolysiloxane material from Example 1 and having the same cone penetration and elongation values was used. In this example side 1 of each sheet was coated with a 3% solution of ~ ~4p ~ e in 2~propanol and allowed to dry. Side 1 of each sheet was then exposed to the same W light source used in Example 1 for the time periods indicated up to 18 seconds. After the exposure the surface tackiness or adhesion of side 1 and side 2 of each sheet was measured in accordance with Example 1. The results are set forth in the following Table 2.
~LZ985~
~.~Pl054 Table_2 __ _ _ __ _ _ S_~e~e Sid_ Adhesion t_me=0 lOsec 30sec 60sec 120sec 180sec _ __ _ ___ ___ _ _ 2 mm 1 4.5 4.3 3.7 1.~ l.0 0,5 2 4.5 4.2 4.4 4.7 4.8 4.3 ___ _ __ _~
3 mm 1 4.4 3.7 3.5 2.7 1.5 0.8 2 4.7 4.3 5.0 5.2 5.7 5.3 _ _ __ 4 mm l 4.4 3.4 1.4 1.2 1.0 0.08 2 4.7 4.3 4.2 4.7 ~.5 4.3 E mple 3 In this example, the same organopolysiloxane fluid was used as in Example 1 except ~ 0.5% by weight benzophenone was mixed with the fluid before it was cured to the cone penetration and ultimat~ elongation values set forth in Example l. A 3 mm thick sheet of the crosslinked material was exposed to the same W
light source used in Examples 1 and 2 for the time periods indi-cated in the following table up to 180 seconds. After the UV
light exposure the surface tackiness or adhesion of each side of the sheet was measured in accordance with Example 1. The results are set forth in the following Table 3.
~2~3S6~
S~2le Side Adhesion _ _ _ time=0lOsec 30sec 60s__ 120sec 180sec __.__ ___ _ __ _ _ __ 3 mm 1 9.4 8.6 4.8 ~.8 2.1 1.8 _ 2 5.1 5.7 5.3 5.9 5.3 _ _ Exa~ ple 4 In this example, an organopolysiloxane fluid ~hich is a mix-ture of trimethyl terminated poly dimethylsiloxane with 5% by weight divinyl terminated dimethylpolysiloxane and 0.5~ benzoyl peroxide was heat cured under nitrogen at a temperature of 150C
to a cone penetration of 260 and ultimate elongation of 850~.
The material was crosslink~d in a sheet 3 ~m thick. No additives were applied to the surface of the sheet in this example. Side 1 of the sheet was exposed to the same ultraviolet light source as in the above examples for the periods of time indicated in the following table. After the UV light exposure the surface tacki-ness or adhesion was measured in accordance with Example l and the results are set forth below in Table 4.
s~
Table 4 _ ___ _ _ _ __ Time of UV ~ _ _ _ _ Exposure:
(Seconds) 0 10 30 60 120 180 __ __ __ __ ____._ _ _ _ _____ ADHESION
No additives Side 1 2.5 2.8 2.8 2.9 3.2 3.6 __. _~ _ _ _ _ _ _ _ Side 2 3.1 2.9 2.7 2.8 2.9 2.7 ___ _ _ ___ __ _ _ ___ Ratlo tSide 1/2) 0.81 0.96 0.97 1.04 1.10 1.33 Example 5 The same organopolysiloxane fluid of Example 4 was cured to the same cone penetration and ultimate elongation values as Example 4 and a sheet 3 mm thick. A 3% solution oE benzophenone and 2-propanol was applied to side 1 of the sheet then side 1 was exposed to the same ultraviolet light source as in the previous examples. After exposure to the UV light the surface tackiness or adhesion was measured in accordance with Example 1 and the results are set forth in the following Table 5.
~29~
Table 5 __ __ __ ___ ___ __ __ _ Time of UV _ _ _ _ _ _ Exposure:
(Seconds) 0 10 30 60 120 180 . ___ . _ _ _ __ _ _ __ ___ ADHE-SION
Benzophenone or Side 1 3.0 1.9 0.8 0.4 0.2 0.1 _ __ _ _ _ _ ___ Side 2 2.8 2.5 2.7 206 2~8 2~8 _ ____ _ ___ Ratio (Side 1/2) 1.07 0.76 0.30 0.15 0.07 0.03 Exam e~ 6 In this example, the same organopolysiloxana fluid as in Example 4 was used with 0.5~ benzophenone mixed in the fluid then cured to the above cone penetration and ultimate elongation values in Example 4. Side 1 of the sheet, which is 3 mm thick, was exposed to the same ultraviolet light source as indicated above for the periods of time set forth below. The surface tackiness or adhesion was then measured on both sides of the sheet and the results are set forth below in Table 6.
~85~5 MP1~54 Table 6 Time of W _ Exposure:
(Seconds) 0 10 30 60 120 180 _ _ _ ADHESION
Benzophenone ir Side 1 3.22.2 1.3 0.6 0.3 0.1 _ _ Side 2 3.83.8 3.6 3.4 3.6 3.7 _ _ ___ .
Ratlo ~ Sida 1/2 ) 0.840.5B 0.36 0.18 0.08 0.05
Claims (20)
1. A method of reducing the surface tack of crosslinked organo-polysiloxane materials having cone penetration between about 100 and about 350 (10-1mm) and ultimate elongation at least about 100% which comprises:
applying to the surface of said material an effective amount of an organic peroxide or a photoinitiator; and irradiating the surface with ultraviolet light to effect a further crosslinking of the surface of said material to reduce the surface tack thereof without effecting significant further crosslinking of said material below said surface.
applying to the surface of said material an effective amount of an organic peroxide or a photoinitiator; and irradiating the surface with ultraviolet light to effect a further crosslinking of the surface of said material to reduce the surface tack thereof without effecting significant further crosslinking of said material below said surface.
2. A method according to claim 1 wherein the organlc peroxide comprises benzoyl peroxide.
3. A method according to claim 1 wherein the photoinitiator comprises benzophenone.
4. A method according to claim 1 wherein the peroxide comprises tert-butyl peroxy benzoate.
5. A method according to claim 1 wherein the photoinitiator comprises a substituted acetophenone.
6. A method o producing a crosslinked organopolysiloxane material having cone penetration between about 100 and about 350 (10-1mm) and ultimate elongation of at least about 100% and having reduced surface tack which comprises:
mixing in an organopolysiloxane fluid an effective amount of a photoinitiator;
thermally crosslinking said organopolysiloxane fluid to a cone penetration between about 100 and about 350 (10-1mm) and an ultimate elongation of at least about 100%, and irradiating a surface of said material with ultra-violet light to effect a further crosslinking of the surface of said material to reduce the surface tack thereof without effecting significant further crosslinking of said material below said surface.
mixing in an organopolysiloxane fluid an effective amount of a photoinitiator;
thermally crosslinking said organopolysiloxane fluid to a cone penetration between about 100 and about 350 (10-1mm) and an ultimate elongation of at least about 100%, and irradiating a surface of said material with ultra-violet light to effect a further crosslinking of the surface of said material to reduce the surface tack thereof without effecting significant further crosslinking of said material below said surface.
7. A method according to claim 6 wherein the photo-initiator comprises benzophenone.
8. A method according to claim 6 wherein the photo-initiator comprises a substituted acetophenone.
9. A method according to claim 6 wherein the photo-initiator comprises anthraquinone.
10. A method according to claim 6 wherein the photo-initiator comprises triphenylamine.
11. A method of producing a crosslinked organopoly-siloxane material having cone penetration between about 100 and 350 (10-1mm) and ultimate elongation of at least about 100% and having reduced surface tack which comprises:
mixing in an organopolysiloxane fluid an effective amount of a photoinitiator;
crosslinking said organopolysiloxane fluid to a material having cone penetration between about 100 and about 350 (10-1mm) and an ultimate elongation of at least about 100% by irradiating said fluid with ultraviolet light; and irradiating a surface of said material with ultra-violet light to effect a further crosslinking of the surface of said material to reduce the surface tack thereof without effecting significant further cross-linking of said material below said surface.
mixing in an organopolysiloxane fluid an effective amount of a photoinitiator;
crosslinking said organopolysiloxane fluid to a material having cone penetration between about 100 and about 350 (10-1mm) and an ultimate elongation of at least about 100% by irradiating said fluid with ultraviolet light; and irradiating a surface of said material with ultra-violet light to effect a further crosslinking of the surface of said material to reduce the surface tack thereof without effecting significant further cross-linking of said material below said surface.
12. A method according to claim 11 wherein the organo-polysiloxane further contains an organic peroxide in mixture therewith.
13. A method according to claim 11 wherein the photo-initiator comprises benzophenone.
14. A method according to claim 11 wherein the crosslinking of the organopolysiloxane fluid is effected simultaneously with the crosslinking of the surface by irradiating the fluid from two directions with different intensity ultraviolet light.
15. An organopolysiloxane material having cone penetration between about 100 and about 350 (10-1mm) and ultimate elongation of at least 100% and having reduced surface tack formed by:
applying to the surface of said material an effective amount of an organic peroxide or a photoinitiator; and irradiating a surface of said material with ultra-violet light to effect a further crosslinking of the surface of said material to reduce the surface tack thereof without effecting significant further cross-linking of said material below said surface.
applying to the surface of said material an effective amount of an organic peroxide or a photoinitiator; and irradiating a surface of said material with ultra-violet light to effect a further crosslinking of the surface of said material to reduce the surface tack thereof without effecting significant further cross-linking of said material below said surface.
16. An organopolysiloxane material having cone penetration between about 100 and about 350 (10-1mm) and ultimate elongation of at least 100% and having reduced surface tack formed by:
mixing in an organopolysiloxane fluid an effective amount of a photoinitiator;
thermally crosslinking said organopolysiloxane fluid to a cone penetration between about 100 and about 350 (10-1mm) and an ultimate elongation of at least about 100%; and irradiating a surface of said material with ultra-violet light to effect a further crosslinking of the surface of said material to reduce the surface tack thereof without effecting significant further cross-linking of said material below said surface.
mixing in an organopolysiloxane fluid an effective amount of a photoinitiator;
thermally crosslinking said organopolysiloxane fluid to a cone penetration between about 100 and about 350 (10-1mm) and an ultimate elongation of at least about 100%; and irradiating a surface of said material with ultra-violet light to effect a further crosslinking of the surface of said material to reduce the surface tack thereof without effecting significant further cross-linking of said material below said surface.
17. An organopolysiloxane material having cone penetration between about 100 and about 350 (10-1mm) and ultimate elongation of at least 100% and having reduced surface tack formed by:
mixing in an organopolysiloxane fluid an effective amount of a photoinitiator;
crosslinking said organopolysiloxane fluid to a material having cone penetration between about 100 and about 350 (10-1mm) and an ultimate elongation of at least about 100% by irradiating said fluid with ultraviolet light; and irradiating a surface of said material with ultra-violet light to effect a further crosslinking of the surface of said material to reduce the surface tack thereof without effecting significant further crosslinking of said material below said surface.
mixing in an organopolysiloxane fluid an effective amount of a photoinitiator;
crosslinking said organopolysiloxane fluid to a material having cone penetration between about 100 and about 350 (10-1mm) and an ultimate elongation of at least about 100% by irradiating said fluid with ultraviolet light; and irradiating a surface of said material with ultra-violet light to effect a further crosslinking of the surface of said material to reduce the surface tack thereof without effecting significant further crosslinking of said material below said surface.
18. A substrate having disposed thereon a material according to claim 15.
19. A substrate having disposed thereon a material according to claim 16.
20. A substrate having disposed thereon a material according to claim 17.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US730,692 | 1985-05-02 | ||
| US06/730,692 US4595635A (en) | 1985-05-02 | 1985-05-02 | Organopolysiloxane materials having decreased surface tack |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1298565C true CA1298565C (en) | 1992-04-07 |
Family
ID=24936417
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000508126A Expired - Lifetime CA1298565C (en) | 1985-05-02 | 1986-05-01 | Organopolysiloxane materials having decreased surface tack |
Country Status (17)
| Country | Link |
|---|---|
| US (1) | US4595635A (en) |
| EP (1) | EP0204427B1 (en) |
| JP (1) | JP2537795B2 (en) |
| KR (1) | KR860009062A (en) |
| AT (1) | ATE85269T1 (en) |
| AU (1) | AU5705186A (en) |
| BR (1) | BR8601930A (en) |
| CA (1) | CA1298565C (en) |
| DE (1) | DE3687670T2 (en) |
| DK (1) | DK200186A (en) |
| ES (1) | ES8801843A1 (en) |
| FI (1) | FI861831A (en) |
| IL (1) | IL78583A0 (en) |
| MX (1) | MX165071B (en) |
| NO (1) | NO861721L (en) |
| NZ (1) | NZ215913A (en) |
| ZA (1) | ZA863319B (en) |
Families Citing this family (64)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4728709A (en) * | 1983-06-30 | 1988-03-01 | Loctite Corporation | Terminal cluster vinyl silicones and acrylate cluster silicones therefrom |
| JPS62187848A (en) * | 1986-02-10 | 1987-08-17 | Fuotopori Ouka Kk | Method for preventing tacky adhesion on surface of photosensitive resin |
| US4741940A (en) * | 1986-05-19 | 1988-05-03 | Raychem Corporation | Articles and methods for protecting substrates |
| US4750962A (en) * | 1987-01-07 | 1988-06-14 | Raychem Corporation | Method of picking up and placing gel material |
| AR246820A1 (en) * | 1987-07-07 | 1994-09-30 | Raychem Corp | Terminal block and adaptor |
| US5069636A (en) * | 1987-07-07 | 1991-12-03 | Raychem Corporation | Terminal block and adapter |
| US5286516A (en) * | 1987-12-01 | 1994-02-15 | Raychem Corporation | Environmental sealing |
| US5229058A (en) * | 1987-12-01 | 1993-07-20 | Raychem Corporation | Environmental sealing |
| JPH07108746B2 (en) * | 1988-01-19 | 1995-11-22 | 株式会社明治ゴム化成 | Roller surface modification method |
| US4966922A (en) * | 1988-06-09 | 1990-10-30 | General Electric Company | Dual curable silicone compositions |
| JP2931859B2 (en) * | 1988-10-24 | 1999-08-09 | ニチバン株式会社 | Surface treatment method for adhesive composition |
| US5008301A (en) * | 1989-02-21 | 1991-04-16 | Dow Corning Corporation | Ultraviolet curing conformal coating with dual shadow cure |
| WO1990010035A1 (en) * | 1989-03-01 | 1990-09-07 | Raychem Corporation | Method of curing organopolysiloxane compositions and compositions and articles therefrom |
| US5204126A (en) * | 1990-02-06 | 1993-04-20 | Nanofilm Corporation | Mold surfaces with ultra thin release films |
| US5088734A (en) * | 1990-07-09 | 1992-02-18 | Glava Gary L | Attenuating handle for recreational and work implements |
| US5246383A (en) * | 1990-09-17 | 1993-09-21 | Raychem Corporation | Gel filled electrical connector |
| US5376019A (en) * | 1990-09-17 | 1994-12-27 | Raychem Corporation | Gel filled modular electrical connecting block |
| US5226837A (en) * | 1990-11-16 | 1993-07-13 | Raychem Corporation | Environmentally protected connection |
| US5587244A (en) * | 1990-12-11 | 1996-12-24 | Flinchbaugh; David E. | Low pressure medical silicone gasket |
| JPH06508258A (en) * | 1991-06-07 | 1994-09-14 | レイケム・コーポレイション | Hinged gel-filled safety and environmental protection device |
| US5354210A (en) * | 1991-08-23 | 1994-10-11 | The Whitaker Corporation | Sealant compositions and sealed electrical connectors |
| US5360350A (en) * | 1991-08-23 | 1994-11-01 | The Whitaker Corporation | Sealant compositions and sealed electrical connectors |
| US5844021A (en) * | 1991-08-23 | 1998-12-01 | The Whitaker Corporation | Sealant compositions and sealed electrical connectors |
| US5525073A (en) * | 1994-06-01 | 1996-06-11 | Raychem Corporation | Environmental protection device with manually operated latch mechanism |
| KR970706356A (en) * | 1994-09-30 | 1997-11-03 | 허버트 지. 버카드 | Silicone Sealing Material Exhibiting High Stress Relaxation Rate (High Stress Relaxation) |
| JP3436435B2 (en) * | 1995-02-22 | 2003-08-11 | 東レ・ダウコーニング・シリコーン株式会社 | Method of curing ultraviolet-curable silicone composition |
| US5601756A (en) * | 1995-08-23 | 1997-02-11 | Swearengin; John V. | Liquid ultraviolet stabilizer and method |
| US5929138A (en) * | 1996-11-05 | 1999-07-27 | Raychem Corporation | Highly thermally conductive yet highly comformable alumina filled composition and method of making the same |
| US6377383B1 (en) | 1997-09-04 | 2002-04-23 | The University Of British Columbia | Optical switching by controllable frustration of total internal reflection |
| US5999307A (en) * | 1997-09-04 | 1999-12-07 | The University Of British Columbia | Method and apparatus for controllable frustration of total internal reflection |
| TW396187B (en) | 1997-09-23 | 2000-07-01 | Novartis Ag | Method of hydrogel surface treatment and article formed therefrom |
| US6038119A (en) * | 1998-09-21 | 2000-03-14 | Atkins; Ian Paul | Overvoltage protection device including wafer of varistor material |
| US6430020B1 (en) | 1998-09-21 | 2002-08-06 | Tyco Electronics Corporation | Overvoltage protection device including wafer of varistor material |
| US6906292B2 (en) * | 1998-10-29 | 2005-06-14 | Applera Corporation | Sample tray heater module |
| US6316099B1 (en) | 1999-03-31 | 2001-11-13 | 3M Innovative Properties Company | Multi-layered sealant |
| US6162663A (en) * | 1999-04-20 | 2000-12-19 | Schoenstein; Paul G. | Dissipation of heat from a circuit board having bare silicon chips mounted thereon |
| US6531771B1 (en) | 1999-04-20 | 2003-03-11 | Tyco Electronics Corporation | Dissipation of heat from a circuit board having bare silicon chips mounted thereon |
| US6494464B1 (en) | 2000-04-20 | 2002-12-17 | Tyco Electronics Corporation | Gel sealant enclosure with visual seal indication |
| US6384979B1 (en) | 2000-11-30 | 2002-05-07 | The University Of British Columbia | Color filtering and absorbing total internal reflection image display |
| US6866529B2 (en) | 2000-12-21 | 2005-03-15 | Tyco Electronics Corporation | Adjustable sealable connector |
| US6437921B1 (en) | 2001-08-14 | 2002-08-20 | The University Of British Columbia | Total internal reflection prismatically interleaved reflective film display screen |
| US6452734B1 (en) | 2001-11-30 | 2002-09-17 | The University Of British Columbia | Composite electrophoretically-switchable retro-reflective image display |
| US6891658B2 (en) | 2002-03-04 | 2005-05-10 | The University Of British Columbia | Wide viewing angle reflective display |
| US6865011B2 (en) | 2002-07-30 | 2005-03-08 | The University Of British Columbia | Self-stabilized electrophoretically frustrated total internal reflection display |
| US6854996B2 (en) * | 2002-12-20 | 2005-02-15 | Tyco Electronics Corporation | Electrical connectors and methods for using the same |
| WO2004075359A1 (en) * | 2003-02-18 | 2004-09-02 | Homac Mfg. Company | Connector and insulating boot for different sized conductors and associated methods |
| US6971897B1 (en) | 2003-10-29 | 2005-12-06 | Tyco Electronics Corporation | Gel-filled telephone jack |
| US7164536B2 (en) | 2005-03-16 | 2007-01-16 | The University Of British Columbia | Optically coupled toroidal lens:hemi-bead brightness enhancer for total internal reflection modulated image displays |
| US7433169B2 (en) * | 2005-12-15 | 2008-10-07 | Raycap Corporation | Overvoltage protection devices including wafer of varistor material |
| US7201596B1 (en) | 2006-01-06 | 2007-04-10 | Tyco Electronics Corporation | Electrical connector systems, plug systems and methods for using the same |
| US7736187B2 (en) * | 2007-03-20 | 2010-06-15 | Tyco Electronics Corporation | Electrical connector assemblies and joint assemblies and methods for using the same |
| US7736165B2 (en) * | 2007-07-16 | 2010-06-15 | Tyco Electronics Corporation | Electrical connector assemblies and methods for forming and using the same |
| CN101805419B (en) * | 2010-04-09 | 2012-08-29 | 北京化工大学 | Fluorine-containing photoinitiator and application thereof |
| US8743525B2 (en) | 2012-06-19 | 2014-06-03 | Raycap Intellectual Property, Ltd | Overvoltage protection devices including wafer of varistor material |
| US9906017B2 (en) | 2014-06-03 | 2018-02-27 | Ripd Research And Ip Development Ltd. | Modular overvoltage protection units |
| US10319545B2 (en) | 2016-11-30 | 2019-06-11 | Iskra Za{hacek over (s)}{hacek over (c)}ite d.o.o. | Surge protective device modules and DIN rail device systems including same |
| US10707678B2 (en) | 2016-12-23 | 2020-07-07 | Ripd Research And Ip Development Ltd. | Overvoltage protection device including multiple varistor wafers |
| US10447026B2 (en) | 2016-12-23 | 2019-10-15 | Ripd Ip Development Ltd | Devices for active overvoltage protection |
| US10340110B2 (en) | 2017-05-12 | 2019-07-02 | Raycap IP Development Ltd | Surge protective device modules including integral thermal disconnect mechanisms and methods including same |
| US10685767B2 (en) | 2017-09-14 | 2020-06-16 | Raycap IP Development Ltd | Surge protective device modules and systems including same |
| US11223200B2 (en) | 2018-07-26 | 2022-01-11 | Ripd Ip Development Ltd | Surge protective devices, circuits, modules and systems including same |
| US11791597B2 (en) * | 2021-02-05 | 2023-10-17 | Aptiv Technologies (2) S.À R.L. | Flexible electrical bus bar and method of manufacturing the same |
| US11862967B2 (en) | 2021-09-13 | 2024-01-02 | Raycap, S.A. | Surge protective device assembly modules |
| US11723145B2 (en) | 2021-09-20 | 2023-08-08 | Raycap IP Development Ltd | PCB-mountable surge protective device modules and SPD circuit systems and methods including same |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1226687A (en) * | 1969-07-28 | 1971-03-31 | ||
| CA1019693A (en) * | 1973-09-28 | 1977-10-25 | George A.L. Gant | Release characteristics of substrates |
| JPS53143669A (en) * | 1977-05-23 | 1978-12-14 | Asahi Chem Ind Co Ltd | Elimination of surface tuckiness of radically-polymerizable resin cured product |
| US4163082A (en) * | 1978-10-23 | 1979-07-31 | Dow Corning Corporation | U.V.-radiation method for decreasing surface tack of disposed organopolysiloxane greases and gels |
| JPS6034988B2 (en) * | 1979-03-19 | 1985-08-12 | 信越化学工業株式会社 | How to cure organopolysiloxane |
| US4364809A (en) * | 1979-03-19 | 1982-12-21 | Shin-Etsu Chemical Co., Ltd. | Method for preparing cured rubbery products of organopoly-siloxanes |
| DE2922089C2 (en) * | 1979-05-31 | 1984-05-30 | Dynamit Nobel Ag, 5210 Troisdorf | Process for the production of partially cross-linked foils from an EPDM or EPM plastic |
| JPS6011762B2 (en) * | 1979-07-27 | 1985-03-28 | ダイキン工業株式会社 | combustion device |
| JPS59109573A (en) * | 1982-12-15 | 1984-06-25 | Toshiba Silicone Co Ltd | Silicone sealant composition |
-
1985
- 1985-05-02 US US06/730,692 patent/US4595635A/en not_active Expired - Lifetime
-
1986
- 1986-04-22 IL IL78583A patent/IL78583A0/en unknown
- 1986-04-22 NZ NZ215913A patent/NZ215913A/en unknown
- 1986-04-29 ES ES554513A patent/ES8801843A1/en not_active Expired
- 1986-04-30 NO NO861721A patent/NO861721L/en unknown
- 1986-04-30 BR BR8601930A patent/BR8601930A/en not_active IP Right Cessation
- 1986-04-30 FI FI861831A patent/FI861831A/en not_active Application Discontinuation
- 1986-05-01 DE DE8686303345T patent/DE3687670T2/en not_active Expired - Fee Related
- 1986-05-01 CA CA000508126A patent/CA1298565C/en not_active Expired - Lifetime
- 1986-05-01 EP EP86303345A patent/EP0204427B1/en not_active Expired - Lifetime
- 1986-05-01 AT AT86303345T patent/ATE85269T1/en not_active IP Right Cessation
- 1986-05-01 DK DK200186A patent/DK200186A/en not_active Application Discontinuation
- 1986-05-02 AU AU57051/86A patent/AU5705186A/en not_active Abandoned
- 1986-05-02 ZA ZA863319A patent/ZA863319B/en unknown
- 1986-05-02 KR KR1019860003442A patent/KR860009062A/en not_active Application Discontinuation
- 1986-05-02 JP JP61102962A patent/JP2537795B2/en not_active Expired - Lifetime
- 1986-05-02 MX MX2379A patent/MX165071B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DE3687670T2 (en) | 1993-08-26 |
| EP0204427A3 (en) | 1988-09-21 |
| ATE85269T1 (en) | 1993-02-15 |
| MX165071B (en) | 1992-10-21 |
| ES8801843A1 (en) | 1988-02-16 |
| AU5705186A (en) | 1986-11-06 |
| DK200186D0 (en) | 1986-05-01 |
| US4595635A (en) | 1986-06-17 |
| FI861831A (en) | 1986-11-03 |
| BR8601930A (en) | 1987-01-06 |
| IL78583A0 (en) | 1986-08-31 |
| FI861831A0 (en) | 1986-04-30 |
| ZA863319B (en) | 1988-01-27 |
| NZ215913A (en) | 1989-01-06 |
| EP0204427A2 (en) | 1986-12-10 |
| DK200186A (en) | 1986-11-03 |
| JPS61261328A (en) | 1986-11-19 |
| NO861721L (en) | 1986-11-03 |
| JP2537795B2 (en) | 1996-09-25 |
| EP0204427B1 (en) | 1993-02-03 |
| KR860009062A (en) | 1986-12-19 |
| ES554513A0 (en) | 1988-02-16 |
| DE3687670D1 (en) | 1993-03-18 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKLA | Lapsed |