CA1120181A - Triarylsulfonium hexa-fluoro phosphate and arsenate photoinitiators - Google Patents
Triarylsulfonium hexa-fluoro phosphate and arsenate photoinitiatorsInfo
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- CA1120181A CA1120181A CA000361443A CA361443A CA1120181A CA 1120181 A CA1120181 A CA 1120181A CA 000361443 A CA000361443 A CA 000361443A CA 361443 A CA361443 A CA 361443A CA 1120181 A CA1120181 A CA 1120181A
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- Prior art keywords
- divalent
- equal
- monovalent
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C381/00—Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
- C07C381/12—Sulfonium compounds
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G85/00—General processes for preparing compounds provided for in this subclass
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- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Epoxy Resins (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Polymerisation Methods In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Triarylsulfonium salts are provided having chemically combined sulfur or oxygen containing monovalent polyaryl radicals. The triarylsulfonium salts can be used as cationic photoinitiators to effect the deep section cure of a variety of organic resin compositions.
Triarylsulfonium salts are provided having chemically combined sulfur or oxygen containing monovalent polyaryl radicals. The triarylsulfonium salts can be used as cationic photoinitiators to effect the deep section cure of a variety of organic resin compositions.
Description
~ 181 RD 11,717 The present invention relates to certain triarylsulfonium salts having chemically combined sulfur or oxygen containing monovalent polyaryl radicals and photocurable compositions containing such triarylsulfonium salts.
Prior to the present invention, as shown by Crivello in U.S. Patent No. 4,058,401 issued November 15, 1977, U.S. Patent No. 4,069,055 issued January 17, 1978 and U.S. Patent No. 4,161,478 issued July 17, 1979, epoxy resins and other cationically polymerizable organic materials were rapidly cured under ultraviolet light with various aryl sulfonium salts. Although valuable results were achieved by the use of such photocurable compositions and photoinitiators, the cure of the cationically poly-merizable organic material to a tack-free state was generally effective only to a thickness of up to about 10-15 mils within a period of up to about 60 seconds.
Experience has shown that in certain applications, such as for use in encapsulation of electronic components, or for use in protective coatings, deep section curing of various cationically polymerizable organic materials, that is, a cure of at least 20 mils, is often required. As a result, the use of triarylsulfonium salt photoinitiators has been somewhat restricted.
The present invention is based on the discovery that photoinitiators having the formula ~k .
112~181 RD 11, 717 (1) [(R)a (Rl)b (R )C S] [Y]
have been found effective for the deep section cure of a wide variety of cationically polymerizable organic materials, such as epoxy resins, phenolformaldehyde resins, vinyl ethers, episulfides, cyclic amines, etc., under either ultraviolet light or visible light when used in combination with certain organic sensitizers as described hereinafter, where R in formula (1) is a monovalent organic radical having the formula R3 (X)~ 4 -\ ( Z ~ /
Rl is a monovalent C(6 13) aromatic radical, R is a divalent C(6 20) aromatic radical, R3 is a monovalent or divalent C(6 13 aromatic radical, R4 is a divalent or trivalent C(6 13) aromatic radical, X is -S- or -0-, Y is a non-nucleophilic anion defined more particularly below, Z is a divalent radical selected from R " " e -N-, -0-, -S-, -S-, -S- and --~CH2 ~ , and R iS a C(1-13) organic radical, a is an integer equal to 1 to 3 inclusive, b is an integer equal to 0 to 2 inclusive, c is an integer equal to 0 or 1, and the sum of a + b + 2c is equal to 3, d i8 equal to 0 when R3 is monovalent and R4 is divalent, and d is equal to 1 when R3 is divalent and R4 is trivalent, and e is an integer equal to 1 to 4 inclusive. In addition, it has been found that the cure of the aforementioned cationically polymerizable organic materials is substantially faster when utilizing the l~Z0~8~ RD 11,717 photoinitiators of formula (1) as compared to the photoinitiators of the prior art.
Some of the non-nucleophilic anions shown by Y
of formula (1) are, for example, MQn, where M is a metal or metalloid, Q is a halogen radical and n has a value of 4-6 inclusive, where MQn is preferably MF6, such as PF6 , SbF6-and AsF6 . In addition, Y also can include perchlorate, CF3SO3 , C6H4SO3 , Cl , Br , F , I , nitrate, phosphate, CF3CO2 , FPO4 , etc.
There is provided by the present invention photocurable compositions comprising (A) a cationically polymerizable organic material and (B) an effective amount of photoinitiator of formula (1).
Radicals included by R of formula (1) are, for example, <~S~ , ~0~, ~ O~ , etc-, derivatives of such radicals, substituted with 1-4, C(l 8) alkyl, or alkoxy radicals, such as the corresponding methyl, methoxy, ethyl, propyl, butoxy, etc., halogen radicals, for example, chlorine, bromine or fluorine, etc. Radicals included within R are more particularly phenyl, tolyl, xylyl, naphthyl, anthryl. Radicals included by R are, for example, l~ZO18~ RD 11,717 ~Z~
where Z is as previously defined.
Included by the triarylsulfonium salts of formula (1), are compounds having the formula, _ __ _ , 112~181 RD 11, 717 .+~ ~ +~ _ ' PF6, 5 5 A5F6 S AsF6 , ~52~ S AsF6 SbF6 ' ~5{~5~5 ~> _ ' +~) <~5~ 5l?6~- ~5 SbF6 ~; ~'$
O----~ S AsF6 ~ (~ ~ 5 PF6 RD 11,717 ~ PF6 , etc-The triarylsulfonium salts of formula (1) can be made by procedures related to methods shown in our U.S.
Patent No. 4,238,619 issued December 9, 1980 and assigned to the same assignee as the present invention. A diaryl-thioether can be reacted with a diaryliodonium salt in the presence of a copper (II) catalyst as shown by the following R S R + [(R )2 I ] [MQn ] ( )> [(R)2 R S ] [MQn ]
where R, Rl, M, Q and n are as previously defined. An additional method is based on the use of AlC13. U.S.
Patent No. 2,807,648 issued September 24, 1957 to Pitt shows a direct Friedel Crafts condensation of an aromatic hydrocarbon using AlC13. A method which can be used to make some of the photoinitiators of formula (1) is based on the use of sulfur monochloride and chlorine as follows:
4 ~ + 2S2C12 + 2C1 3~ ~ ~ - ~ Cl + 5HCl.
~OJ
The above triarylsulfonium salt can be converted t~~'the preferred photoinitiators of formula (1) where Y is MQ or MF6 by a metathesis using an alkali metal MQn or MF6 salts ` l~Z0~81 RD 11,717 such as KMQn, KMF6~ NaMF6~ etc.
Organic polymerizable materials which can be utiliæed in the photocurable compositions of the present invention include epoxy resins such as monomeric, dimeric or oligomeric of polymeric epoxy materials containing one or a plurality of epoxy functional groups. For example, those resins which result from the reaction of bisphenol-A
t4,4'-isopropylidenediphenol) and epichlorohydrin, or by the reaction of low molecular weight phenolformaldehyde resin (Novolak resin) with epichlorohydrin, can be used alone or in combination with an epoxy containing compound as a reactive diluent. Such diluents as phenyl glycidyl ether, 4-vinylcyclohexene dioxide, limonene dioxide, 1,2-cyclohexene oxide, glycidyl acrylate, glycidyl methacrylate, styrene oxide, allyl glycidyl ether, etc., may be added as viscosity modifying agents.
In addition, the range of these compounds can be extended to include polymeric materials containing terminal or pendant epoxy groups. Examples of these compounds are vinyl copolymers containing glycidyl acrylate or methacrylate as one of the comonomers. Other classes of epoxy containing polymers amenable to cure using the above catalysts are epoxysiloxane resins, epoxy-polyurethanes and epoxy-polyesters.
Such polymers usually have epoxy functional groups at the ends of their chains. Epoxysiloxane resins and method for making are more particularly shown by E. P. Plueddemann and G. Fanger, J. Am. Chem~ Soc. 80 632-5 (1959). As described in the Literature, epoxy resins can also be modified in a number of standard ways such as reaction with amines, carboxylic acids, thiols, phenols, alcohols, etc., as shown in U.S. PatenLs Nos.
Prior to the present invention, as shown by Crivello in U.S. Patent No. 4,058,401 issued November 15, 1977, U.S. Patent No. 4,069,055 issued January 17, 1978 and U.S. Patent No. 4,161,478 issued July 17, 1979, epoxy resins and other cationically polymerizable organic materials were rapidly cured under ultraviolet light with various aryl sulfonium salts. Although valuable results were achieved by the use of such photocurable compositions and photoinitiators, the cure of the cationically poly-merizable organic material to a tack-free state was generally effective only to a thickness of up to about 10-15 mils within a period of up to about 60 seconds.
Experience has shown that in certain applications, such as for use in encapsulation of electronic components, or for use in protective coatings, deep section curing of various cationically polymerizable organic materials, that is, a cure of at least 20 mils, is often required. As a result, the use of triarylsulfonium salt photoinitiators has been somewhat restricted.
The present invention is based on the discovery that photoinitiators having the formula ~k .
112~181 RD 11, 717 (1) [(R)a (Rl)b (R )C S] [Y]
have been found effective for the deep section cure of a wide variety of cationically polymerizable organic materials, such as epoxy resins, phenolformaldehyde resins, vinyl ethers, episulfides, cyclic amines, etc., under either ultraviolet light or visible light when used in combination with certain organic sensitizers as described hereinafter, where R in formula (1) is a monovalent organic radical having the formula R3 (X)~ 4 -\ ( Z ~ /
Rl is a monovalent C(6 13) aromatic radical, R is a divalent C(6 20) aromatic radical, R3 is a monovalent or divalent C(6 13 aromatic radical, R4 is a divalent or trivalent C(6 13) aromatic radical, X is -S- or -0-, Y is a non-nucleophilic anion defined more particularly below, Z is a divalent radical selected from R " " e -N-, -0-, -S-, -S-, -S- and --~CH2 ~ , and R iS a C(1-13) organic radical, a is an integer equal to 1 to 3 inclusive, b is an integer equal to 0 to 2 inclusive, c is an integer equal to 0 or 1, and the sum of a + b + 2c is equal to 3, d i8 equal to 0 when R3 is monovalent and R4 is divalent, and d is equal to 1 when R3 is divalent and R4 is trivalent, and e is an integer equal to 1 to 4 inclusive. In addition, it has been found that the cure of the aforementioned cationically polymerizable organic materials is substantially faster when utilizing the l~Z0~8~ RD 11,717 photoinitiators of formula (1) as compared to the photoinitiators of the prior art.
Some of the non-nucleophilic anions shown by Y
of formula (1) are, for example, MQn, where M is a metal or metalloid, Q is a halogen radical and n has a value of 4-6 inclusive, where MQn is preferably MF6, such as PF6 , SbF6-and AsF6 . In addition, Y also can include perchlorate, CF3SO3 , C6H4SO3 , Cl , Br , F , I , nitrate, phosphate, CF3CO2 , FPO4 , etc.
There is provided by the present invention photocurable compositions comprising (A) a cationically polymerizable organic material and (B) an effective amount of photoinitiator of formula (1).
Radicals included by R of formula (1) are, for example, <~S~ , ~0~, ~ O~ , etc-, derivatives of such radicals, substituted with 1-4, C(l 8) alkyl, or alkoxy radicals, such as the corresponding methyl, methoxy, ethyl, propyl, butoxy, etc., halogen radicals, for example, chlorine, bromine or fluorine, etc. Radicals included within R are more particularly phenyl, tolyl, xylyl, naphthyl, anthryl. Radicals included by R are, for example, l~ZO18~ RD 11,717 ~Z~
where Z is as previously defined.
Included by the triarylsulfonium salts of formula (1), are compounds having the formula, _ __ _ , 112~181 RD 11, 717 .+~ ~ +~ _ ' PF6, 5 5 A5F6 S AsF6 , ~52~ S AsF6 SbF6 ' ~5{~5~5 ~> _ ' +~) <~5~ 5l?6~- ~5 SbF6 ~; ~'$
O----~ S AsF6 ~ (~ ~ 5 PF6 RD 11,717 ~ PF6 , etc-The triarylsulfonium salts of formula (1) can be made by procedures related to methods shown in our U.S.
Patent No. 4,238,619 issued December 9, 1980 and assigned to the same assignee as the present invention. A diaryl-thioether can be reacted with a diaryliodonium salt in the presence of a copper (II) catalyst as shown by the following R S R + [(R )2 I ] [MQn ] ( )> [(R)2 R S ] [MQn ]
where R, Rl, M, Q and n are as previously defined. An additional method is based on the use of AlC13. U.S.
Patent No. 2,807,648 issued September 24, 1957 to Pitt shows a direct Friedel Crafts condensation of an aromatic hydrocarbon using AlC13. A method which can be used to make some of the photoinitiators of formula (1) is based on the use of sulfur monochloride and chlorine as follows:
4 ~ + 2S2C12 + 2C1 3~ ~ ~ - ~ Cl + 5HCl.
~OJ
The above triarylsulfonium salt can be converted t~~'the preferred photoinitiators of formula (1) where Y is MQ or MF6 by a metathesis using an alkali metal MQn or MF6 salts ` l~Z0~81 RD 11,717 such as KMQn, KMF6~ NaMF6~ etc.
Organic polymerizable materials which can be utiliæed in the photocurable compositions of the present invention include epoxy resins such as monomeric, dimeric or oligomeric of polymeric epoxy materials containing one or a plurality of epoxy functional groups. For example, those resins which result from the reaction of bisphenol-A
t4,4'-isopropylidenediphenol) and epichlorohydrin, or by the reaction of low molecular weight phenolformaldehyde resin (Novolak resin) with epichlorohydrin, can be used alone or in combination with an epoxy containing compound as a reactive diluent. Such diluents as phenyl glycidyl ether, 4-vinylcyclohexene dioxide, limonene dioxide, 1,2-cyclohexene oxide, glycidyl acrylate, glycidyl methacrylate, styrene oxide, allyl glycidyl ether, etc., may be added as viscosity modifying agents.
In addition, the range of these compounds can be extended to include polymeric materials containing terminal or pendant epoxy groups. Examples of these compounds are vinyl copolymers containing glycidyl acrylate or methacrylate as one of the comonomers. Other classes of epoxy containing polymers amenable to cure using the above catalysts are epoxysiloxane resins, epoxy-polyurethanes and epoxy-polyesters.
Such polymers usually have epoxy functional groups at the ends of their chains. Epoxysiloxane resins and method for making are more particularly shown by E. P. Plueddemann and G. Fanger, J. Am. Chem~ Soc. 80 632-5 (1959). As described in the Literature, epoxy resins can also be modified in a number of standard ways such as reaction with amines, carboxylic acids, thiols, phenols, alcohols, etc., as shown in U.S. PatenLs Nos.
2,935,488 - issued May 3, 1960 - Phillips et al; 3,235,620 -issued February 15, 1966 - Phillips et al; 3,369,055 - issued llZ0181 RD 11,717 February 13, 1968 - Salyer et al; 3,379,653 - issued April 23, 1968 - Ernst et al; 3,398,211 - issued August 20, 1968 - Ramos; 3,403,199 - issued September 24, 1968 - Ramos;
3,563,840 - issued February 16, 1971 - Stine; 3,567,797 -issued March 2, 1971 - Mango et al; 3,677,995 - issued July 18, 1972 - Earing; etc. Further coreactants which can be used with epoxy resins are hydroxy terminated flexibilizers such as hydroxy terminated polyesters, shown in the Encyclopedia of Polymer Science and Technology, Vol. 6, 1967, Interscience Publishers, New York, pp. 209-271 and particularly p. 238.
Included by the thermosetting organic condensation resins of formaldehyde which can be used in the practice of the present invention are, for example, urea type resins, phenol-formaldehyde type resins, etc.
In addition, there can be used melamine thiourea resins, melamine, or urea aldehyde resins, cresol-formaldehyde resins and combinations with other carboxy, hydroxyl, amino and mercapto containing resins, such as polyesters, alkyds and polysulfides.
Some of the vinyl organic prepolymers which can be used to make the polymerizable compositions of the present invention are, for example, CH2=CH-O-(CH2-CH2O)n,-CH=CH2, where n' is a positive integer having a value up to about lOOQ or higher, multi-functional vinylethers, such as 1,2,3-propane trivinylether, trimethylolpropane trivinylether, prepolymers having the formula, ~ CH~ , and n CH=CH 2 11~181 RD 11,717 low molecular weight polybutadiene having a viscosity of from 200 to lO,nO0 centipoises at 25C, etc. Products resulting from the cure of such compositions can be used as printing inks and other applications typical of thermosetting resins.
A further category of the organic materials which can be used to make the polymerizable compositions are cyclic ethers which are convertible to thermoplastics.
Included by such cyclic ethers are, for example, oxetanes such as 3,3 bis~chloromethyloxetane, alkoxyoxetanes as shown by U.S. Patent No. 3,673,216 - issued June 27, 1972 - Schroeter, assigned to the same assignee as the present invention;
oxolanes such as tetrahydrofuran, oxepanes, oxygen containing spiro compounds, trioxane, dioxolane, etc.
In addition to cyclic ethers, there are also included cyclic esters such as - lactones, for example, propiolactone, cyclic amines, such as 1, 3, 3-trimethyl-azetidine and A organosilicon~cyclics, for example, materials included by the formula,
Included by the thermosetting organic condensation resins of formaldehyde which can be used in the practice of the present invention are, for example, urea type resins, phenol-formaldehyde type resins, etc.
In addition, there can be used melamine thiourea resins, melamine, or urea aldehyde resins, cresol-formaldehyde resins and combinations with other carboxy, hydroxyl, amino and mercapto containing resins, such as polyesters, alkyds and polysulfides.
Some of the vinyl organic prepolymers which can be used to make the polymerizable compositions of the present invention are, for example, CH2=CH-O-(CH2-CH2O)n,-CH=CH2, where n' is a positive integer having a value up to about lOOQ or higher, multi-functional vinylethers, such as 1,2,3-propane trivinylether, trimethylolpropane trivinylether, prepolymers having the formula, ~ CH~ , and n CH=CH 2 11~181 RD 11,717 low molecular weight polybutadiene having a viscosity of from 200 to lO,nO0 centipoises at 25C, etc. Products resulting from the cure of such compositions can be used as printing inks and other applications typical of thermosetting resins.
A further category of the organic materials which can be used to make the polymerizable compositions are cyclic ethers which are convertible to thermoplastics.
Included by such cyclic ethers are, for example, oxetanes such as 3,3 bis~chloromethyloxetane, alkoxyoxetanes as shown by U.S. Patent No. 3,673,216 - issued June 27, 1972 - Schroeter, assigned to the same assignee as the present invention;
oxolanes such as tetrahydrofuran, oxepanes, oxygen containing spiro compounds, trioxane, dioxolane, etc.
In addition to cyclic ethers, there are also included cyclic esters such as - lactones, for example, propiolactone, cyclic amines, such as 1, 3, 3-trimethyl-azetidine and A organosilicon~cyclics, for example, materials included by the formula,
4 R"Si m where R" can be the same or different monovalent organic radical such as methyl or phenyl and m is an integer equal to 3 to 8 inclusive. An example of an organosilicone cyclic is hexamethyl trisiloxane, octamethyl tetrasiloxane, etc. The products made in accordance with the present invention are high molecular weight oils and gums.
The photocurable compositions of the present invention can be made by blending the cationically polymerizable organic material with an effective amount such as from 0.1%
to 15~ by weight of the photocurable composition of the triarylsulfonium salt of formula (1~.
~12018~
RV 11,717 In certain instances, an organic solvent, such as acetone, nitromethane and acetonitrile can be used to facilitate the mixing of various ingredients. The diaryliodonium salts can be formed in situ if desired. In addition, the curable compositions may contain inactive ingredients, such as silica, talc, clay, glass fibers, extenders, hydrated alumina, carbon fibers, process aids, etc., in amounts of up to 500 parts of filler per 100 parts of cationically polymerizable organic material. The curable compositions can be applied to such substrates as metal, rubber, plastic, molded parts of films, paper, wood, glass, cloth, concrete, ceramic, etc.
Some of the applications in which the curable compositions of the present invention can be used are, for example, protective, decorative and insulating coatings, potting compounds, printing inks, sealants, adhesives, molding compounds, wire insulations, textile coatings, laminates, impregnated tapes, varnishes, etc.
In order that those skilled in the art will be better able to practice the invention, the following examples are given by way of illustration and not by way of limitation.
All parts are by weight.
A mixture of 19.6 parts of 86% potassium hydroxide, 33 parts of thiophenol and about 120 parts of dimethylacetamide was heated at a temperature of 120C with stirring to effect the removal of water. After about 6.5 parts of water was collected, there was added to the resulting mixture 26.3 parts of para-dibromobenzene and the mixture was heated to reflux. After 6 hours at reflux the reaction mixture was allowed to cool and 300 parts of water was added.
There was obtained a tan colored solid which was filtered ~ 81 RD 11,717 and washed with water several times. The product wa~ then dried. There was obtained 34.7 parts of 1, 4-dithiophenoxybenzene based on method of preparation.
A mixture of 7.35 parts of the above disulfide, 11.75 parts of diphenyliodonium hexafluoroarsenate and 0.2 part of copper benzoate was heated for 3 hours at 120C.
The resulting reaction mixture was washed several times with about 50 part portions of diethylether and the remaining solid was recrystalized from 95% ethanol. There was obtained a 45%
yield of a very light tan crystalline product having a melting point of 69-75 and the following elemental analysis:
Calculated %C, 51.3; %H, 3.50; %S, 11.43. Found %C, 51.21;
%H, 3.59; %S, 11.37. Based on method of preparation there was obtained a triarylsulfonium salt having the formula, ~S~S AsF6 A 3~ solution of the above photoinitiator was prepared in 4-vinylcyclohexene dioxide. A similar solution was prepared for triphenylsulfonium hexafluoroarsenate.
The respective solutions were then measured for tack-free time using a GE H3T7 mercury arc lamp at a distance of 6 inches from the substrate which consisted of the respective epoxy formulas applied as a 1 mil film onto a glass slide. The photoinitiator of the present invention had a tack-free time of less than 1 second while the triphenylsulfonium hexafluoroarsenate mixture had a tack-free time of about
The photocurable compositions of the present invention can be made by blending the cationically polymerizable organic material with an effective amount such as from 0.1%
to 15~ by weight of the photocurable composition of the triarylsulfonium salt of formula (1~.
~12018~
RV 11,717 In certain instances, an organic solvent, such as acetone, nitromethane and acetonitrile can be used to facilitate the mixing of various ingredients. The diaryliodonium salts can be formed in situ if desired. In addition, the curable compositions may contain inactive ingredients, such as silica, talc, clay, glass fibers, extenders, hydrated alumina, carbon fibers, process aids, etc., in amounts of up to 500 parts of filler per 100 parts of cationically polymerizable organic material. The curable compositions can be applied to such substrates as metal, rubber, plastic, molded parts of films, paper, wood, glass, cloth, concrete, ceramic, etc.
Some of the applications in which the curable compositions of the present invention can be used are, for example, protective, decorative and insulating coatings, potting compounds, printing inks, sealants, adhesives, molding compounds, wire insulations, textile coatings, laminates, impregnated tapes, varnishes, etc.
In order that those skilled in the art will be better able to practice the invention, the following examples are given by way of illustration and not by way of limitation.
All parts are by weight.
A mixture of 19.6 parts of 86% potassium hydroxide, 33 parts of thiophenol and about 120 parts of dimethylacetamide was heated at a temperature of 120C with stirring to effect the removal of water. After about 6.5 parts of water was collected, there was added to the resulting mixture 26.3 parts of para-dibromobenzene and the mixture was heated to reflux. After 6 hours at reflux the reaction mixture was allowed to cool and 300 parts of water was added.
There was obtained a tan colored solid which was filtered ~ 81 RD 11,717 and washed with water several times. The product wa~ then dried. There was obtained 34.7 parts of 1, 4-dithiophenoxybenzene based on method of preparation.
A mixture of 7.35 parts of the above disulfide, 11.75 parts of diphenyliodonium hexafluoroarsenate and 0.2 part of copper benzoate was heated for 3 hours at 120C.
The resulting reaction mixture was washed several times with about 50 part portions of diethylether and the remaining solid was recrystalized from 95% ethanol. There was obtained a 45%
yield of a very light tan crystalline product having a melting point of 69-75 and the following elemental analysis:
Calculated %C, 51.3; %H, 3.50; %S, 11.43. Found %C, 51.21;
%H, 3.59; %S, 11.37. Based on method of preparation there was obtained a triarylsulfonium salt having the formula, ~S~S AsF6 A 3~ solution of the above photoinitiator was prepared in 4-vinylcyclohexene dioxide. A similar solution was prepared for triphenylsulfonium hexafluoroarsenate.
The respective solutions were then measured for tack-free time using a GE H3T7 mercury arc lamp at a distance of 6 inches from the substrate which consisted of the respective epoxy formulas applied as a 1 mil film onto a glass slide. The photoinitiator of the present invention had a tack-free time of less than 1 second while the triphenylsulfonium hexafluoroarsenate mixture had a tack-free time of about
5 seconds.
Chlorine was introduced into a mixture of 37.2 ~ RD 11,717 parts of dipllenylsulfide and 13.34 parts of aluminum chloride to a total of 9.5 parts of chlorine was added with stirring. The reaction mixture was poured onto 500 parts of ice to effect the decomposition of the aluminum chloride complex. There was obtained a white semi-solid which was washed twice with 200 part portions of hot water. There was then added to the resulting washed residue, 27.8 parts of potassium hexafluoroarsenate and 500 parts of hot water and the mixture was stirred at a temperature of 30C for 1 hour.
There was obtained an orange oil which separated and which was recovered by decanting the aqueous solution. It was purified by washing with water several times and finally with anhydrous ethyl ether. The resulting product was then dried under reduced pressure at 60C for 16 hours. The product was then recrystallized from 95% ethanol. There was obtained a 31% yield of a triarylsulfonium salt having a melting point of 77-87C. Based on method of preparation, the salt had the following formula:
~ S ~}-St' AsF6 EXAMpLE 3 -Three percent solutions were prepared consisting of 3, 4-epoxycyclohexylmethyl-3', 4'-epoxycyclohexanecarboxylate and triphenylsulfonium hexafluoroarsenate (Prior art~ and the photoinitiator of the present invention as shown by Example 2.
Films of increasing thickness were drawn onto glass plates and cured for one minute using a G.E. H3T7 medium pressure mercury arc lamp at a distance of 6 inches from the films.
The thickest film which could be cured down to the glass to a ~ 181 RD 11,717 non-tacky state using the aforementioned photoinitiators is shown as follows:
Photoinitiator Max. Thickness Prior Art 10-15 mils Example 2 50 mils The above results show that the photocurable compositions of the present invention containing a photo-initiator within the scope of formula (1) cured to a thickness more than 4 times that of the photocurable composition of the prior art.
Additional photocurable compositions were prepared utilizing the photoinitiators of Example 2 and cyclohexene oxide as a cationic polymerizable organic material. The solution contained 0.021 mols of photoinitiator per liter of cyclohexene oxide. Aliquots of these photocurable mixtures (3 ml) were irradiated under sealed conditions using a Hano~ia 450 medium pressure mercury arc lamp. The aliquots were withdrawn periodically, quenched at various times and the polymer isolated by precipitation in methanol. The resulting photocured products were recovered by filtering and drying the polymer overnight at 60 C in vacuo. The polymer was weighed to determine the percent conversion. The following table shows the results obtained, where the values are expressed in percent conversion:
- TABLE II
Irradiation Photoinit. Photoinit.
Time (prior art) (Example 2) 0.5 8 32 30 1 min. 14 41 2 min. 18 49 4 min. 34 64 ~1~0~8~ RD 11,717 table II cont'd.
Chlorine was introduced into a mixture of 37.2 ~ RD 11,717 parts of dipllenylsulfide and 13.34 parts of aluminum chloride to a total of 9.5 parts of chlorine was added with stirring. The reaction mixture was poured onto 500 parts of ice to effect the decomposition of the aluminum chloride complex. There was obtained a white semi-solid which was washed twice with 200 part portions of hot water. There was then added to the resulting washed residue, 27.8 parts of potassium hexafluoroarsenate and 500 parts of hot water and the mixture was stirred at a temperature of 30C for 1 hour.
There was obtained an orange oil which separated and which was recovered by decanting the aqueous solution. It was purified by washing with water several times and finally with anhydrous ethyl ether. The resulting product was then dried under reduced pressure at 60C for 16 hours. The product was then recrystallized from 95% ethanol. There was obtained a 31% yield of a triarylsulfonium salt having a melting point of 77-87C. Based on method of preparation, the salt had the following formula:
~ S ~}-St' AsF6 EXAMpLE 3 -Three percent solutions were prepared consisting of 3, 4-epoxycyclohexylmethyl-3', 4'-epoxycyclohexanecarboxylate and triphenylsulfonium hexafluoroarsenate (Prior art~ and the photoinitiator of the present invention as shown by Example 2.
Films of increasing thickness were drawn onto glass plates and cured for one minute using a G.E. H3T7 medium pressure mercury arc lamp at a distance of 6 inches from the films.
The thickest film which could be cured down to the glass to a ~ 181 RD 11,717 non-tacky state using the aforementioned photoinitiators is shown as follows:
Photoinitiator Max. Thickness Prior Art 10-15 mils Example 2 50 mils The above results show that the photocurable compositions of the present invention containing a photo-initiator within the scope of formula (1) cured to a thickness more than 4 times that of the photocurable composition of the prior art.
Additional photocurable compositions were prepared utilizing the photoinitiators of Example 2 and cyclohexene oxide as a cationic polymerizable organic material. The solution contained 0.021 mols of photoinitiator per liter of cyclohexene oxide. Aliquots of these photocurable mixtures (3 ml) were irradiated under sealed conditions using a Hano~ia 450 medium pressure mercury arc lamp. The aliquots were withdrawn periodically, quenched at various times and the polymer isolated by precipitation in methanol. The resulting photocured products were recovered by filtering and drying the polymer overnight at 60 C in vacuo. The polymer was weighed to determine the percent conversion. The following table shows the results obtained, where the values are expressed in percent conversion:
- TABLE II
Irradiation Photoinit. Photoinit.
Time (prior art) (Example 2) 0.5 8 32 30 1 min. 14 41 2 min. 18 49 4 min. 34 64 ~1~0~8~ RD 11,717 table II cont'd.
6 min. 49 69 8 min. 55 77 The procedure of example 4 was repeated except that in place of the cyclohexene oxide there was utilized 2-chloroethylvinylether. Four ml aliquots of the mixture were irradiated in accordance with the procedure of Example 4 to provide the following percent conversion values:
TABLE III
Irradiation Photoinit. Photoinit.
Time (prior art) (Example 2 15 sec. 0 17 30 sec. 0 43 60 sec. 0 87 300 sec. 0 87 2100 sec. 2 87 The above results sho~ that the photoinitiators of the present invention are superior to the photoinitiator of the prior art.
The procedure of Example 4 was repeated except that in the place of the cyclohexene oxide there was utilized trioxane and methylene chloride. Solutions were prepared containing 1.386 x lO lmol of trioxane and 1.386 x 10 4mol of photoin~tiator. The mixtures were then irradiated in accordance with the procedure of Example 5 resulting in the following percent conversion values.
1~8~ RD 11,717 TABLE IV
Irradiation Photoinit. Photoinit.
Time (prior art) (Example 2) 30 sec. 9 60 sec. 0 86 120 sec. 0 78 240 sec. 60 85 One percent solutions were prepared consisting of diethyleneglycol divinyl ether and triphenylsulfonium hexafluoroarsenate and the photoinitiator of the present invention as shown by Example 2. Ten grams of each of the above mixtures were poured into identical 2 in. diameter cups and irradiated for 5 seconds at a distance of 23 cm from a GE H3T7 medium pressure mercury arc lamp. The solid polymer was remoyed from the cups, washed with acetone to remove unreacted divinyl ether and then dried. The respective weights of the dry polymers were proportional to the thickness of cure in the samples.
Photoinitiator Weight (grams~
Prior Art 0.89 Example 2 2.33 The above results show that the photocurable compositions of the present invention containing a photoinitiator within the scope of formula (l) cured to a thickness of more than 2.6 times that of the prior art. On a molar basis, the compounds of the present invention were 3.2 times more efficient than the prior art.
Two percent solutions were prepared consisting of Methylon 75201, a phenol-formaldehyde resol of the formula, ~lZ0~8~
RD 11,717 O-CH2-CH=CH O-CH -CH=CH2 HOH2C ~ CH2 ~CH20H
and triphenylsulfonium hexafluoroarsenate (prior art) and the photoinitiator of the present invention as shown by Example 2. The two solutions were spread as 3 mil films onto glass plates and exposed to W light at a distance of 6 inches from a GE H3T7 mercury arc lamp. The resin film containing the photoinitiator of the present invention re~uired 1.5 minutes to become tack-free whereas the film containing the photoinitiator of the prior art requixed 5.5 minutes irradiation under the same conditions.
The previous example was repeated except the phenolformaldehyde was replaced with a silicone resin having the following formula, (CH30)3Si-CH2-CH ~
After 10 seconds irradiation, the sample containing the photoinitiator of Example 2 was tack-free and could not be removed by rubbing with acetone. On the other hand, the sample containing the triphenylsulfonium salt was soft and readily removed by acetone.
The above example was repeated in which the resin employed had the following molecular structure: (A-187 Union Carbide Corp.) /\
CH2-cH-cH2-o-cH2-cH2-cH2-si(OcH3)3 `` ~120181 RD 11,717 Seventy-five seconds irradiation were necessary to produce a tack-free 3 mil film using the photoinitiator of the prior art, while only 30 seconds were required to give a tack-free film with the photoinitiator of the present invention.
Three percent solutions in cycloaliphatic epoxy resin ERL 4221 of photoinitiators of the formulas, ~ 6 5~3 PF6- and ~ S ~ S+ pF6 were applied onto glass substrates and cured in accordance with Example 7. After washing the resulting cured films with acetone and allowing them to dry the films were weighed.
The photoinitiator of the present invention was found to provide a film twice as thick as that of the prior art.
A three percent solution of the photoinitiator of Example 2 in 3, 4-epoxycyclohexylmethyl-3', 4'-epoxycyclohexane carboxylate was prepared. The sample was divided into equal portions and Q.5% by weight perylene was added to one of the solutions. The samples were exposed to visible light from a GE H3T7 lamp fitted with a filter to remove all ultraviolet light at wavelengths below 390 nm.
The sample containing the perylene dye sensitizer cured within 30 seconds, while the sample free of dye remained uncured even after 5 minutes irradiation. This example demonstrates the use of dye sensitizers in combination with the photoinitiators of the present invention to provide visible light curable compositions.
- ~lZ0~8~
RD 11,717 A mixture was stirred for 18 hours at room temperature consisting of 11.2 parts (0.02 mole) of diphenyl-4-thiophenoxyphenyl sulfonium hexafluoroarsenate, 20 parts o glacial acetic acid, and about 4 parts of 30% hydrogen peroxide. The mixture was then poured into 200 parts of distilled water. A crude product was obtained which was washed with water and then with anhydrous ethyl ether.
Based on elemental analysis, spectroscopic analysis and method of preparation, the product had the following structure:
~ SO~ S AsF6 A three percent solution of the above photoinitiator in 4-vinylcyclohexene dioxide cured to a tack-free film when irradiated with a GE H3T7 lamp at a distance of 10 inches.
There was added 11.2 parts (0.02 mole~ of the sulfonium salt of Example 2 in about 15 parts of acetone.
There was then added, 2 parts of 30% hydrogen peroxide, slowly with cooling. The solution was allowed to stir overnight and then poured into 200 parts of water. An oil was obtained which solidified on washing with water followed by anhydrous ethyl ether. The product which was obtained after drying overnight in vacuo had a melting point of 70-74F
and by elemental analysis, and spectroscopic analysis as well as by method of preparation had the following structure:
~ ~Oifl~ RD 11,717 ~ 3--SO ~ S+ AsF6 ~>
A three percent solution of the above photoinitiator in 4-vinyl-cyclohexene dioxide cured as a film as described in the previous example had a tack-free time of seconds.
Although the above examples are directed to only a few of the very many variables which can be used in the practice of the present invention, it should be understood that the present invention is broadly directed to W curable compositions, certain triarylsulfonium salts included within formula (1) and methods or making such materials. As utilized in the definition of the present invention, the expression "effective amount" when applied to the triarylsulfonium salt is that amount required for cure of the organic material. It has been found 0~1% to 15% by weight of triarylsulfonium salt, based on the weight of photocurable composition can be used.
TABLE III
Irradiation Photoinit. Photoinit.
Time (prior art) (Example 2 15 sec. 0 17 30 sec. 0 43 60 sec. 0 87 300 sec. 0 87 2100 sec. 2 87 The above results sho~ that the photoinitiators of the present invention are superior to the photoinitiator of the prior art.
The procedure of Example 4 was repeated except that in the place of the cyclohexene oxide there was utilized trioxane and methylene chloride. Solutions were prepared containing 1.386 x lO lmol of trioxane and 1.386 x 10 4mol of photoin~tiator. The mixtures were then irradiated in accordance with the procedure of Example 5 resulting in the following percent conversion values.
1~8~ RD 11,717 TABLE IV
Irradiation Photoinit. Photoinit.
Time (prior art) (Example 2) 30 sec. 9 60 sec. 0 86 120 sec. 0 78 240 sec. 60 85 One percent solutions were prepared consisting of diethyleneglycol divinyl ether and triphenylsulfonium hexafluoroarsenate and the photoinitiator of the present invention as shown by Example 2. Ten grams of each of the above mixtures were poured into identical 2 in. diameter cups and irradiated for 5 seconds at a distance of 23 cm from a GE H3T7 medium pressure mercury arc lamp. The solid polymer was remoyed from the cups, washed with acetone to remove unreacted divinyl ether and then dried. The respective weights of the dry polymers were proportional to the thickness of cure in the samples.
Photoinitiator Weight (grams~
Prior Art 0.89 Example 2 2.33 The above results show that the photocurable compositions of the present invention containing a photoinitiator within the scope of formula (l) cured to a thickness of more than 2.6 times that of the prior art. On a molar basis, the compounds of the present invention were 3.2 times more efficient than the prior art.
Two percent solutions were prepared consisting of Methylon 75201, a phenol-formaldehyde resol of the formula, ~lZ0~8~
RD 11,717 O-CH2-CH=CH O-CH -CH=CH2 HOH2C ~ CH2 ~CH20H
and triphenylsulfonium hexafluoroarsenate (prior art) and the photoinitiator of the present invention as shown by Example 2. The two solutions were spread as 3 mil films onto glass plates and exposed to W light at a distance of 6 inches from a GE H3T7 mercury arc lamp. The resin film containing the photoinitiator of the present invention re~uired 1.5 minutes to become tack-free whereas the film containing the photoinitiator of the prior art requixed 5.5 minutes irradiation under the same conditions.
The previous example was repeated except the phenolformaldehyde was replaced with a silicone resin having the following formula, (CH30)3Si-CH2-CH ~
After 10 seconds irradiation, the sample containing the photoinitiator of Example 2 was tack-free and could not be removed by rubbing with acetone. On the other hand, the sample containing the triphenylsulfonium salt was soft and readily removed by acetone.
The above example was repeated in which the resin employed had the following molecular structure: (A-187 Union Carbide Corp.) /\
CH2-cH-cH2-o-cH2-cH2-cH2-si(OcH3)3 `` ~120181 RD 11,717 Seventy-five seconds irradiation were necessary to produce a tack-free 3 mil film using the photoinitiator of the prior art, while only 30 seconds were required to give a tack-free film with the photoinitiator of the present invention.
Three percent solutions in cycloaliphatic epoxy resin ERL 4221 of photoinitiators of the formulas, ~ 6 5~3 PF6- and ~ S ~ S+ pF6 were applied onto glass substrates and cured in accordance with Example 7. After washing the resulting cured films with acetone and allowing them to dry the films were weighed.
The photoinitiator of the present invention was found to provide a film twice as thick as that of the prior art.
A three percent solution of the photoinitiator of Example 2 in 3, 4-epoxycyclohexylmethyl-3', 4'-epoxycyclohexane carboxylate was prepared. The sample was divided into equal portions and Q.5% by weight perylene was added to one of the solutions. The samples were exposed to visible light from a GE H3T7 lamp fitted with a filter to remove all ultraviolet light at wavelengths below 390 nm.
The sample containing the perylene dye sensitizer cured within 30 seconds, while the sample free of dye remained uncured even after 5 minutes irradiation. This example demonstrates the use of dye sensitizers in combination with the photoinitiators of the present invention to provide visible light curable compositions.
- ~lZ0~8~
RD 11,717 A mixture was stirred for 18 hours at room temperature consisting of 11.2 parts (0.02 mole) of diphenyl-4-thiophenoxyphenyl sulfonium hexafluoroarsenate, 20 parts o glacial acetic acid, and about 4 parts of 30% hydrogen peroxide. The mixture was then poured into 200 parts of distilled water. A crude product was obtained which was washed with water and then with anhydrous ethyl ether.
Based on elemental analysis, spectroscopic analysis and method of preparation, the product had the following structure:
~ SO~ S AsF6 A three percent solution of the above photoinitiator in 4-vinylcyclohexene dioxide cured to a tack-free film when irradiated with a GE H3T7 lamp at a distance of 10 inches.
There was added 11.2 parts (0.02 mole~ of the sulfonium salt of Example 2 in about 15 parts of acetone.
There was then added, 2 parts of 30% hydrogen peroxide, slowly with cooling. The solution was allowed to stir overnight and then poured into 200 parts of water. An oil was obtained which solidified on washing with water followed by anhydrous ethyl ether. The product which was obtained after drying overnight in vacuo had a melting point of 70-74F
and by elemental analysis, and spectroscopic analysis as well as by method of preparation had the following structure:
~ ~Oifl~ RD 11,717 ~ 3--SO ~ S+ AsF6 ~>
A three percent solution of the above photoinitiator in 4-vinyl-cyclohexene dioxide cured as a film as described in the previous example had a tack-free time of seconds.
Although the above examples are directed to only a few of the very many variables which can be used in the practice of the present invention, it should be understood that the present invention is broadly directed to W curable compositions, certain triarylsulfonium salts included within formula (1) and methods or making such materials. As utilized in the definition of the present invention, the expression "effective amount" when applied to the triarylsulfonium salt is that amount required for cure of the organic material. It has been found 0~1% to 15% by weight of triarylsulfonium salt, based on the weight of photocurable composition can be used.
Claims (8)
1. A photocurable composition comprising:
(A) a cationically polymerizable organic material selected from the class consisting of condensation resins of formaldehyde, vinyl organic prepolymers, cyclic ethers, cyclic esters, cyclic lactones and organosilicone cyclics, and (B) an effective amount of a triarylsulfonium salt of the formula [(R)a (R1)b (R2)c S]+ [MF6]-where R is a monovalent organic radical having the formula R1 is a monovalent C(6-13) aromatic radical, R2 is a divalent C(6-20) aromatic radical, R3 is a monovalent or divalent C(6-13) aromatic radical, R4 is a divalent or trivalent C(6-13) aromatic radical, X is -S- or -O-, M is an element selected from the class consisting of arsenic and phosphorus, Z is a divalent radical selected from and a is an integer equal to 1 to 3 inclusive, b is an integer equal to 0 to 2 inclusive, c is an integer equal to 0 or 1, and the sum of a + b + 2c is equal to 3, d is equal to 0 when R3 is monovalent and R4 is divalent, and d is equal to 1 when R3 is divalent and R4 is trivalent, and e is an integer equal to 1 to 4 inclusive.
RD-11,717
(A) a cationically polymerizable organic material selected from the class consisting of condensation resins of formaldehyde, vinyl organic prepolymers, cyclic ethers, cyclic esters, cyclic lactones and organosilicone cyclics, and (B) an effective amount of a triarylsulfonium salt of the formula [(R)a (R1)b (R2)c S]+ [MF6]-where R is a monovalent organic radical having the formula R1 is a monovalent C(6-13) aromatic radical, R2 is a divalent C(6-20) aromatic radical, R3 is a monovalent or divalent C(6-13) aromatic radical, R4 is a divalent or trivalent C(6-13) aromatic radical, X is -S- or -O-, M is an element selected from the class consisting of arsenic and phosphorus, Z is a divalent radical selected from and a is an integer equal to 1 to 3 inclusive, b is an integer equal to 0 to 2 inclusive, c is an integer equal to 0 or 1, and the sum of a + b + 2c is equal to 3, d is equal to 0 when R3 is monovalent and R4 is divalent, and d is equal to 1 when R3 is divalent and R4 is trivalent, and e is an integer equal to 1 to 4 inclusive.
RD-11,717
2. The photocurable composition of claim 1, where the cationically polymerizable organic material is a phenol-formaldehyde.
3. The photocurable composition of claim 1, where the cationically polymerizable organic material is a vinyl ether.
4. A triarylsulfonium salt of the formula [(R)a (R1)b (R2)c S]+ [MF6]-where R is a monovalent organic radical having the formula R1 is a monovalent C(6-13) aromatic radical, R2 is a divalent C(6-20) aromatic radical, R3 is a monovalent or divalent C(6-13) aromatic radical, R4 is a divalent or trivalent C(6-13) aromatic radical, X is -S- or -0-, M is an element selected from the class consisting of arsenic and phosphorus, Z is a divalent radical selected from -0-, -S-, , and a is an integer equal to 1 to 3 inclusive, b is an integer equal to 0 to 2 inclusive, c is an integer equal to 0 or 1, and the sum of a + b + 2c is equal to 3, d is equal to 0 when R3 is monovalent and R4 is divalent, and d is equal to 1 when R3 is divalent and R4 is trivalent, and e is an integer equal to 1 to 4 inclusive.
5. The compound AsF6-.
RD 11, 717
RD 11, 717
6. The compound PF6-.
7. The compound AsF6-.
8. The compound AsF6-.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US7969279A | 1979-09-28 | 1979-09-28 | |
| US79,692 | 1979-09-28 |
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| Publication Number | Publication Date |
|---|---|
| CA1120181A true CA1120181A (en) | 1982-03-16 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000361443A Expired CA1120181A (en) | 1979-09-28 | 1980-09-25 | Triarylsulfonium hexa-fluoro phosphate and arsenate photoinitiators |
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| Country | Link |
|---|---|
| JP (1) | JPS5655420A (en) |
| KR (1) | KR840001676B1 (en) |
| AU (1) | AU539699B2 (en) |
| BR (1) | BR8006335A (en) |
| CA (1) | CA1120181A (en) |
| DE (1) | DE3035807A1 (en) |
| ES (1) | ES8200089A1 (en) |
| FR (1) | FR2466457A1 (en) |
| GB (1) | GB2061280B (en) |
| ZA (1) | ZA805273B (en) |
Families Citing this family (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2069486B (en) * | 1980-02-19 | 1984-09-26 | Gen Electric | Method for making triarylsulphonium salts |
| GB8330692D0 (en) * | 1983-11-17 | 1983-12-29 | Sericol Group Ltd | Preparation of photoinitiators |
| JPS61190524A (en) * | 1985-01-25 | 1986-08-25 | Asahi Denka Kogyo Kk | Energy ray-curable composition |
| DE3909688A1 (en) * | 1989-03-23 | 1990-09-27 | Espe Stiftung | METHOD FOR GLUING OR POOLING SUBSTRATES AND DEVICE FOR CARRYING OUT ITSELF |
| US5166125A (en) * | 1992-02-19 | 1992-11-24 | Eastman Kodak Company | Method of forming color filter array element with patternable overcoat layer |
| US5166126A (en) * | 1992-02-19 | 1992-11-24 | Eastman Kodak Company | Color filter array element with protective overcoat layer and method of forming same |
| WO1995017755A1 (en) * | 1993-12-22 | 1995-06-29 | Abb Patent Gmbh | Process for producing an insulation system |
| JPH1041633A (en) | 1996-07-25 | 1998-02-13 | Hitachi Ltd | Multi layer wiring board and photosensitive resin compd. therefor |
| JP3765896B2 (en) | 1996-12-13 | 2006-04-12 | Ｊｓｒ株式会社 | Photocurable resin composition for optical three-dimensional modeling |
| JP2003073481A (en) | 2001-09-06 | 2003-03-12 | Brother Ind Ltd | Active energy ray-curable composition, ink containing the same and printer using the ink |
| JP2003105077A (en) | 2001-09-28 | 2003-04-09 | Brother Ind Ltd | Active energy ray-curable composition, ink containing the same, and printer using the ink |
| JP4947021B2 (en) * | 2002-12-25 | 2012-06-06 | Ｊｓｒ株式会社 | Onium salt compound, radiation-sensitive acid generator, and positive-type radiation-sensitive resin composition |
| US7365104B2 (en) | 2005-03-31 | 2008-04-29 | Eastman Kodak Company | Light curable articles containing azinium salts |
| DE602006015319D1 (en) | 2005-07-01 | 2010-08-19 | Basf Se | sulfonium salt |
| KR101389057B1 (en) | 2006-04-13 | 2014-05-13 | 시바 홀딩 인크 | Sulphonium salt initiators |
| CN101522613B (en) | 2006-10-04 | 2013-03-06 | 西巴控股有限公司 | Sulphonium salt photoinitiators |
| TW200838967A (en) | 2007-02-02 | 2008-10-01 | Jsr Corp | Composition for radiation-curable adhesive, composite, and method for producing the composite |
| JP5473921B2 (en) | 2007-10-10 | 2014-04-16 | ビーエーエスエフ ソシエタス・ヨーロピア | Sulfonium salt initiator |
| WO2009047152A1 (en) | 2007-10-10 | 2009-04-16 | Basf Se | Sulphonium salt initiators |
| CN101952269B (en) | 2007-10-10 | 2014-06-25 | 巴斯夫欧洲公司 | Sulphonium salt initiators |
| JP5622564B2 (en) | 2010-06-30 | 2014-11-12 | 富士フイルム株式会社 | Photosensitive composition, pattern forming material, and photosensitive film using the same, pattern forming method, pattern film, low refractive index film, optical device, and solid-state imaging device |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4161478A (en) * | 1974-05-02 | 1979-07-17 | General Electric Company | Photoinitiators |
| US4173476A (en) * | 1978-02-08 | 1979-11-06 | Minnesota Mining And Manufacturing Company | Complex salt photoinitiator |
-
1980
- 1980-08-26 ZA ZA00805273A patent/ZA805273B/en unknown
- 1980-09-09 GB GB8029024A patent/GB2061280B/en not_active Expired
- 1980-09-23 DE DE19803035807 patent/DE3035807A1/en active Granted
- 1980-09-25 CA CA000361443A patent/CA1120181A/en not_active Expired
- 1980-09-26 FR FR8020689A patent/FR2466457A1/en active Granted
- 1980-09-26 ES ES495420A patent/ES8200089A1/en not_active Expired
- 1980-09-26 JP JP13310380A patent/JPS5655420A/en active Granted
- 1980-09-27 KR KR1019800003761A patent/KR840001676B1/en active IP Right Grant
- 1980-09-29 AU AU62780/80A patent/AU539699B2/en not_active Ceased
- 1980-09-29 BR BR8006335A patent/BR8006335A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| GB2061280A (en) | 1981-05-13 |
| ZA805273B (en) | 1981-11-25 |
| ES495420A0 (en) | 1981-10-16 |
| AU6278080A (en) | 1981-04-09 |
| BR8006335A (en) | 1981-04-14 |
| FR2466457B1 (en) | 1985-03-08 |
| GB2061280B (en) | 1984-05-16 |
| JPS5655420A (en) | 1981-05-16 |
| ES8200089A1 (en) | 1981-10-16 |
| KR830003526A (en) | 1983-06-21 |
| AU539699B2 (en) | 1984-10-11 |
| DE3035807C2 (en) | 1993-04-01 |
| FR2466457A1 (en) | 1981-04-10 |
| DE3035807A1 (en) | 1981-04-09 |
| KR840001676B1 (en) | 1984-10-13 |
| JPS6336332B2 (en) | 1988-07-20 |
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