JPS6335657B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a composition comprising a cationically polymerizable substance and an aryloxysulfoxonium salt. The present invention also provides for polymerization of such compositions by actinic radiation and optionally further crosslinking by heat in the presence of a thermosetting agent of the photopolymerized product thus obtained, It concerns the polymerization of materials by the action of heat alone and the use of such compositions as surface coatings and as adhesives in printing plates, printed circuits and reinforced composite materials. It is desirable to induce polymerization of organic materials with actinic radiation for a number of reasons. The use of photopolymerization procedures can, for example, avoid the use of organic solvents and the costs of solvent recovery, which are associated with toxicity, flammability and pollution risks. Photopolymerization makes it possible to insolubilize the resin composition in a confined or irradiated area, thus making it possible to produce printed circuits and printing plates, or to limit the adhesion of substrates to desired zones. possible. Furthermore, in manufacturing processes, irradiation procedures are often more rapid than methods involving heating and consequent cooling steps. Certain aromatic diazonium salts undergo decomposition upon irradiation with actinic radiation, and when this salt is mixed with cationically polymerizable substances, the Lewis acid generated by the irradiation can induce polymerization. It has been known for a long time to do this (e.g. British patent no.
(see specification). However, this diazonium salt was not completely satisfactory:
The pot life of mixtures of diazonium salts and cationically polymerizable substances is too short, especially in sunlight, and secondly, nitrogen is evolved during the liberation of the Lewis acid catalyst, and the evolution of this gas is limit the range of ways in which it can be used successfully. Therefore, while liberating the acid catalyst by irradiation,
Many proposals have been made to replace these diazonium salts with other compounds that do not generate nitrogen; in particular, onium and iodonium salts of sulfur have been intensively studied. Thus, in UK Patent No. 1,516,511 and corresponding US Pat. No. 4,058,401,
When mono-1,2-epoxides, epoxide resins (i.e. materials containing an average of more than one 1,2-epoxide group), or mixtures thereof, are exposed to radiant energy, by desorption of a Brønsted acid catalyst, Oxygen, sulfur, present in an amount capable of polymerizing or curing the epoxide (or polyepoxide);
It has recently been disclosed that selenium or tellurium can be polymerized or cured by radiation-sensitive aromatic onium salts. Such salts are described in the specification as follows: [(R) _a (R ¹ ) _b (R ² ) _c X] ⁺ _d [MQ _e ] ^(ef)- () (Formula In the formula, R represents a monovalent aromatic group, R ¹ represents an alkyl group, cycloalkyl group, or substituted alkyl group, and R ² represents a polyvalent aliphatic or aromatic group forming a heterocyclic or condensed ring structure. represents a group group, X represents an oxygen atom, a sulfur atom, selenium or tellurium, and M represents a metal atom or metalloid atom, such as antimony, iron, tin, bismuth,
aluminum, gallium, indium, titanium,
represents zirconium, scandium, vanadium, chromium, manganese, phosphine, phosphorus or arsenic;
Q represents a halogen group, a represents 0, 1, 2 or 3, b represents 0, 1 or 2, c represents 0 or 1, the sum of a + b + c represents 3 or the valence of X, d represents (e-f), f is the valence of M and represents an integer from 2 to 7, and e represents an integer up to 8 that is greater than f. ). In the immediately following British Patent No. 1,518,141 and the corresponding US Pat. No. 4,058,400, the same patentee claims that vinyl monomers, vinyl prepolymers, cyclic ethers, cyclic esters, cyclic sulfides, cyclic amines and organic The cationically polymerizable organic material, which is a monomer or prepolymer not containing 1,2-epoxide groups selected from silicon cyclic compounds, is also subjected to radiant energy in the presence of an effective amount of the radiation-sensitive onium salt of the Group A element. It is disclosed that it can be polymerized by exposure. Similarly, only onium salts of the above formula are described. More recently, in U.S. Pat. No. 4,102,687, the same patentee describes the curing of urea-formaldehyde resins, melamine formaldehyde resins, and phenol formaldehyde resins by ultraviolet irradiation in the presence of Group A onium salts. and start it.
It is disclosed that curing can be completed by heating. Again only onium salts of the formula are described. This patentee's disclosure regarding onium salts of sulfur was subsequently limited to sulfonium salts. In this way, British Patent No. 1535492 specifies:
Arylsulfonic acids, haloarylsulfonic acids, alkylsulfonic acids and haloalkylsulfones for the cationic polymerization of epoxide resins, vinyl monomers and prepolymers, cyclic organic ethers, cyclic organic esters, cyclic organic sulfides, cyclic amines and cyclic organosilicon compounds. The use of radiation-sensitive sulfonium salts of acids has been described. US Pat. No. 4,139,385 discloses the use of sulfonium and other salts in the curing of polyolefins with polythiols. Polyesterically unsaturated compounds such as diallyl phthalate, diallyl maleate or triallyl cyanurate are combined with trimethylolpropane-trithioglycolate or pentaerythrittetra(3
-mercaptopropionate) and for example triphenylsulfonium hexafluoroarzenate or tetrafluoroborate and then irradiated with UV light. The salt used as a catalyst has the following formula: [(R) _a (R ¹ ) _b ] ⁺ [MX _k ] ^(km)- () or: [(R) _c (R ² ) _e S] ⁺ [MX _k ] ^(km)- () or: [(R) _f (R ⁴ ) _g (R ⁵ ) _h Z] ⁺ [MX _k ] ^(km)- () (wherein, R represents a monovalent aromatic group; , R ¹ represents a divalent aromatic group, R ² represents a polyvalent aliphatic or aromatic group forming a heterocyclic or condensed ring structure, and R ⁴ represents an alkyl group, an alkoxy group, a cycloalkyl group, or represents a substituted alkyl group, R ⁵ represents an aromatic, heterocyclic, or polyvalent group forming a condensed ring structure, M represents a metal atom or metalloid atom, X represents a halogen group, and Z represents Represents a nitrogen, phosphorus, arsenic, bismuth or antimony atom, a represents 0 or 2, b or 1, but represents a + b = 2 or the valence of iodine, c represents 0 or 3, d represents 0 or 2, e represents 0 or 1, but (c+d+e)=3
or represents the valence of sulfur, f represents an integer from 0 to 4, g represents 0, 1 or 2, h represents 0, 1 or 2, (f + g + h) =
represents the valence of 4 or Z, j represents (k-m), m represents the valence of M and represents 2 to 7,
k represents an integer greater than 1 and less than or equal to 8. ) All compounds represented by West German Published Patent No. 2833648 describes the following formula: The triarylsulfonium salt represented by
2-Aliphatic unsaturated composition containing epoxide groups or epoxide resin and methyl methacrylate,
It is disclosed that it can be used to initiate the curing of polyesters or mixtures with aliphatic unsaturated materials such as styrene. In the formula, R
represents an optionally substituted aromatic hydrocarbon or heterocyclic group having 6 to 13 carbon atoms,
R ¹ represents an optionally substituted divalent aromatic hydrocarbon or heterocyclic group, a represents 1 or 3, b represents 0 or 1, S has a valence of 3, This valence may be satisfied by R alone or in combination with R and R ¹ , M represents a metal or metalloid atom, Q represents a halogen group, and d represents 4, 5 or 6. represent US Pat. No. 4,136,102 describes various sulfonium salts containing hexafluorophosphate, hexafluoroarsenate or hexafluoroantimonate anions and the use of these compounds for curing epoxide resins. They are also described as being useful in the polymerization of various unspecified cyclic organic and cyclic organosilicon compounds. DE 2730725 A1 discloses the photocuring of epoxide resin compositions also containing polyvinyl acetal with aromatic onium salts. The onium salts of sulfur described herein are only the compounds represented by the formula. U.S. Pat. No. 4,081,276 describes a method for forming photoresist images, particularly printed circuits, in which a layer of photoinitiator is exposed to radiant energy and then contacted with a cationically polymerizable material, such as an epoxide resin. Again, the onium salts of sulfur described herein are compounds of the formula above. Other patent holders, in Belgian Patent No. 845,746, disclose per molecule
The photopolymerization of a mixture consisting of a compound with an epoxide functionality of 1.5 epoxy groups or more and a compound with a hydroxy functionality of at least 1 is described. In U.S. Patent No. 4,090,936, this second
The patentee of (a) an organic compound having an average epoxide functionality in the range of about 1 to 1.3; (b) compatible with (a) and having a glass transition temperature of about -20°C to 105°C;
(a) of the organic polymer which is a polymer derived from at least one acrylate or methacrylate monomer, or a copolymer of styrene and allyl alcohol, or a polyvinyl butyral polymer, within the range of °C. about 3 to 50
% by weight and (c) an aromatic complex salt photopolymerization initiator which is an onium salt or halonium salt of a Group A or Group A element. Other disclosures of this second patentee's U.S. Pat. No. 4,069,054 are that cationically polymerizable monomers,
The present invention relates to a photopolymerizable composition containing an aromatic sulfonium compound and an aromatic tertiary amine, an aromatic tertiary diamine, or an aromatic polycyclic compound as a sensitizer. Aromatic sulfonium salts, triphenylsulfonium hexafluorophosphate, have been used commercially for the photopolymerization of epoxide resins. The inventors have surprisingly found that cationically polymerizable substances can be photopolymerized by aryloxysulfoxonium salts. The use of these salts as catalysts generally results in faster photopolymerization than the use of prior art sulfonium or iodonium salts. Additionally, U.S. Patent No.
Contrary to what would be expected from the teachings of '4102,687, we have discovered that urea-formaldehyde resins can be cured either by radiation or by the application of heat. A further advantage of aryloxysulfoxonium salts is that compositions containing them, unlike those containing conventional sulfonium salts as catalysts, do not produce unpleasant mercaptan odors upon irradiation. The invention therefore comprises a) a 1,2-epoxide, a vinyl monomer or prepolymer, an aminoplast or a phenoplast, and b) a compound of the formula: (in the formula, R ⁶ and R ⁷ are each) a C 1 -C 6 alkyl group which may be substituted with a halogen atom and whose chain may be interrupted by an ether oxygen atom or a sulfonyl group;
) an aryl group having 6 to 15 carbon atoms, or) an aryloxy group having 6 to 15 carbon atoms, or R ⁶ and R ⁷ together with the sulfur atom in the above formula form a heterocyclic group; represents a divalent group having 4 to 10 carbon atoms, R ⁸
represents an aryl group having 6 to 15 carbon atoms, M represents a metal atom or metalloid atom, X represents a halogen atom, preferably a fluorine atom or a chlorine atom, n is 4, 5 or 6, and the valence of M is Represents a number 1 greater than. ) An object of the present invention is to provide a composition comprising an effective amount of an aryloxysulfoxonium salt represented by: Another object of the invention is a method for converting a compound or a mixture of compounds capable of being converted into a high molecular weight substance under the action of a cationic catalyst into a high molecular weight substance, which comprises irradiating said composition of the invention with actinic radiation. The goal is to provide the following. The inventors have discovered that cationically polymerizable materials can also be polymerized by heating the compositions of the invention. A third object of the invention is therefore a method for converting a compound or a mixture of compounds convertible into a high molecular weight substance under the action of a cationic catalyst into a high molecular weight substance, which comprises heating said composition of the invention. The goal is to provide the following. Preferably, when R ⁶ and R ⁷ independently represent a group, each represents an aryl group or an aryloxy group having 6 to 11 carbon atoms, or R ⁶ and R ⁷
represents a monocyclic chain consisting only of carbon atoms and hydrogen atoms formed by joining together. More preferably, each R ⁶ has 1 or 2 carbon atoms.
represents a phenyl group or a naphthyl group which may optionally be substituted with 1 to 4 alkyl groups or with 1 or 2 fluorine atoms, chlorine atoms or bromine atoms. More preferably
R ⁷ also unsubstituted or substituted with 1 or 2 C1 -C4 alkyl groups, or with 1 or 2 fluorine, chlorine or bromine atoms; , represents a phenoxy group, a naphthyl group or a naphthyloxy group. When R ⁶ and R ⁷ together represent a divalent group, R ⁶ and R ⁷ are more preferably a group (—CH ₂ )— ₄
represents. R ⁸ is more preferably unsubstituted or by 1 or 2 alkyl or alkoxy groups each having 1 to 4 carbon atoms, by 1 or 2 nitro groups or by 1 or 2 free radicals. Represents a phenyl group or naphthyl group substituted with an elementary atom, a chlorine atom, or a bromine atom. M preferably represents phosmine, phosphorus, arsenic, antimony or bismuth, especially boron or phosphorus. The anion MX ^- _o can be, for example, hexachlorobismuthate, but preferably represents hexafluoroantimonate, hexafluoroarsenate, hexafluorophosphate or tetrafluoroborate. Suitable sulfoxonium salts include, for example, the following compounds: diphenyl phenoxy sulfoxonium hexafluorophosphate, phenyl diphenoxy sulfoxonium, hexafluorophosphate, methyldiphenoxy sulfoxonium hexafluorophosphate. ate, p-tolylphenoxy-p-tolyloxysulfoxonium hexafluorophosphate, ethyl(ethylsulfonylmethyl)-p-tolyloxy-sulfoxonium hexafluorophosphate, o-chlorophenoxy-p-tolyl-p-ph Enoxysulfoxonium hexafluorophosphate, 1
-Phenoxy-1-oxide-tetrahydrothiophenium hexafluorophosphate, 1-phenoxy-1-oxide-tetrahydrothiophenium tetrafluoroborate and 1-phenoxy-1-oxide-tetrahydrothiophenium hexafluoroantimonate. The salts represented by the formula are generally known [Chakey, Snodin, Stevens and Whiting, Journal of Chemical Society, (C), 1970] , 682-6] and a suitable sulfone or the following formula: Aryl esters of alkanesulfonic acids or arenesulfonic acids (for example, dimethylsulfone, tetrahydrothiophene- ^{1,1 -} dioxide, phenylmethanesulfonate or phenylbenzenesulfonate) of the following formula: R ⁸ N ₂ ⁺ MX ⁻ _o ( ) in which R ⁸ , M, X and n have the meanings given above. Obtained by decomposition of arene diazonium salts. The amount of b) used is sufficient to expose the composition to actinic radiation or heat the composition to induce polymerization. Usually from 0.1 to 7.5 parts by weight, especially from 0.5 to 6 parts by weight of component b) are used per 100 parts by weight of component a). Component a) is a 1,2-epoxide, vinyl monomer or prepolymer, aminoplast or phenoplast. Mono-1,2 such as epichlorohydrin, propylene oxide
- It can be an epoxide or a glycidyl ether of a monohydric alcohol or a phenol, such as n-butyl glycidyl ether or phenyl glycidyl ether; it can also be a glycidyl ester, such as for example glycidyl acrylate or methacrylate. Preferably an epoxide resin, especially one with directly bonded oxygen atoms, has the following formula: (In the formula, R ⁹ and R ¹¹ each represent a hydrogen atom when R ¹⁰ represents a hydrogen atom or a methyl group, and when R ¹⁰ represents a hydrogen atom, R ⁹ and R ¹¹
together represent -CH ₂ CH ₂ -. ) is an epoxide resin containing at least one group represented by: Such resins include, for example, compounds containing two or more carboxylic acid groups per molecule and shrimp chlorohydrin, glycerol dichlorohydrin, or β-methyl shrimp chlorohydrin reacted in the presence of an alkali. Mention may be made, in particular, of polyglycidyl and poly(β-methylglycidyl) esters obtained. Such polyglycidyl esters include, for example, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid,
From aliphatic polycarboxylic acids such as azelaic acid, sebacic acid or dimerized or trimerized linoleic acid; tetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, hexahydrophthalic acid and 4-
It can be derived from cycloaliphatic polycarboxylic acids such as methylhexahydrophthalic acid; and from aromatic polycarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid. Other suitable polyglycidyl esters are obtained by vinyl polymerization of glycidyl esters of vinylic acid, especially glycidyl acrylate and glycidyl methacrylate. Furthermore, for example, a compound containing at least two free alcoholic hydroxyl groups and/or phenolic hydroxyl groups per molecule can be reacted with a suitable shrimp chlorohydrin under alkaline conditions or in the presence of an acidic catalyst, followed by an alkaline reaction. Examples include polyglycidyl and poly(β-methylglycidyl) ether obtained by treatment with
These ethers include ethylene glycol, diethylene glycol and higher poly(oxyethylene) glycols, propane-1,2-diol and poly(oxypropylene) glycol, propane-1,
3-diol, poly(oxytetramethylene) glycol, pentane 1,5-diol, hexane 2,4,6-triol, glycerol, 1,
From acyclic alcohols such as 1,1-trimethylolpropane, pentaerythritol, sorbitol and poly(ebichlorohydrin); resorcitol, quinitol, bis(4-hydroxycyclohexyl)methane, 2,2-bis(4 - from cycloaliphatic alcohols such as -hydroxycyclohexyl)propane and 1,1-bis(hydroxymethyl)cyclohex-3-ene; and from N,N-bis(2-hydroxyethyl)aniline and p,p'-
It can be produced from an alcohol having an aromatic ring such as bis(2-hydroxyethylamino)diphenylmethane. or from monocyclic phenols such as resorcinol and hydroquinone and bis(4-hydroxyphenyl)methane, 4,4'-dihydroxydiphenyl, bis(4-hydroxyphenyl)
-Hydroxyphenyl)sulfone, 1,1,2,
2-tetrakis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane (also known as bisphenol A), 2,2-bis(3,5-dibromo-4 ―
Hydroxyphenyl)propane and aldehydes such as formaldehyde, acetaldehyde, chloral and furfuraldehyde, and phenol itself or ring has a chlorine atom or each has 9 carbon atoms.
Phenols substituted by alkyl groups containing up to (e.g. 4-chlorophenol, 2-methylphenol and 4-tert-butylphenol)
It can be made from polycyclic phenols such as novolaks formed from. Poly(N-glycidyl) compounds include, for example, N-glycidyl derivatives of amines such as aniline, n-butylamine, bis(4-amino-phenyl)methane and bis(4-methylaminophenyl)methane; triglycidyl isocyanate; Nurate;
It is also possible to use N,N'-diglycidyl derivatives of cyclic alkylene ureas such as ethylene urea and 1,3-propylene urea and N,N'-diglycidyl derivatives of hydantoins such as 5,5-dimethylhydantoin. However, these are generally not preferred. Di-(s-glycidyl) derivatives of dithiols such as ethane-1,2-dithiol and bis(4-mercaptomethylphenyl) ether can also be used as poly(s-glycidyl compounds), but these is also not preferred. Examples of the epoxide resin having a group in which R ⁹ and R ¹¹ taken together represent a -CH ₂ -CH ₂ - group include bis(2,3-epoxy-cyclopentyl) ether, 2,3-epoxy Examples include cyclopentyl glycidyl ether and 1,2-bis(2,3-epoxycyclopentyloxy)ethane. As epoxide resins having 1,2-epoxide groups bonded to different types of heteroatoms, it is possible to use, for example, glycidyl ether-glycidyl ester of lytic acid. Epoxide resins in which some or all of the epoxide groups are not terminal include, for example, vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, 4-oxatetracyclo[6.2.1.0 ^2,7 . 0 ^3,5 ] undec-9-ylglycidyl ether, 1,2-bis(4-oxatetracyclo[6.2.1.0 ^2,7 .0 ^3,5 ] undec-9-yloxy]ethane, 3,4-epoxy Cyclohexylmethyl 3',4'-epoxycyclohexanecarboxylate and its 6,6'-dimethyl derivative, ethylene glycol bis(3,4-epoxycyclohexane-carboxylate), 3-(3,4-epoxycyclohexyl)-8, 9-Epoxy-
It is also possible to use 2,4-dioxaspiro-[5,5]-undecane and epoxidized butadiene or copolymers of butadiene and ethylene-based compounds (eg styrene and vinyl acetate). Mixtures of epoxide resins can be used if desired. Particularly preferred epoxide resins for use in the present invention are dihydric phenols such as 2,2-bis(4-hydroxyphenyl)propane and bis(4-hydroxy-phenyl)methane and butane-1,4- It is a diglycidyl ether which may be a precursor of a dihydric alcohol such as a diol. If desired, the epoxide resin may be cured with polyhydric alcohols, ie compounds having at least two alcoholic, preferably primary hydroxyl groups per molecule. Preferably, the polyhydric alcohol is
Sufficient amounts are present to provide 0.5 to 1.5, especially 0.75 to 1.25, alcoholic hydroxyl groups. Polyhydric alcohols preferably contain, in addition to alcoholic hydroxyl groups consisting exclusively of carbon and hydrogen atoms, oxygen atoms and halogen atoms, which are optionally present as ether oxygen atoms, acetals or carbonyloxy groups. It is further preferred that the polyhydric alcohol has a molecular weight of at least 100 and especially 1000 or more. Suitable polyhydric alcohols include, for example, poly(oxyethylene) glycol, poly(oxypropylene) glycol, poly(oxytetramethylene) glycol, polyevichlorohydrin, ethylene oxide, propylene oxide or glycerol of tetrahydrofuran or 1,1,1 Poly(oxyethylene)-, poly(oxypropylene)- and poly(oxytetramethylene) triols obtained by polymerization in the presence of trimethylolpropane, hydroxyl-terminated polycaprolactones, co-compounds of styrene and allyl alcohol. Examples include polymers, polyvinyl alcohol, hydroxypropyl cellulose, hydroxyl-containing polyvinyl acetals and partial esters of cellulose such as cellulose acetate butyrate. Polymerizable vinyl monomers and prepolymers include styrene, α-methylstyrene, allylbenzene, divinylbenzene, vinylcyclohexane, 4-vinylcyclohex-1-ene, N-
Vinylpyrrolidin-2-one, N-vinylcarbazole, acrolein, isoprene, butadiene, piperylene, vinyl acetate, and vinyl ethers such as isobutyl ether, methyl vinyl ether, trimethylolpropane trivinyl ether, glycerol trivinyl ether, ethylene glycol and poly(oxy) ethylene glycol) and cyclic vinyl ethers having at least two cyclic vinyl ether groups each forming part of a 3,4-dihydro-2H-pyran ring, such as 3,4-dihydro-2H-pyran-2 -ylmethyl 3,4-dihydro-2H-pyran-2-carboxylate and its prepolymers. Preferably the vinyl compound is a vinyl ether of an aliphatic monohydric alcohol and a 3,4
-dihydro-2H-pyran-2-ylmethyl 3,
4-dihydro-2H-pyran-2-carboxylate and its prepolymer. Preferred aminoplasts as component a) have the following formula: -CH ₂ OR ¹² , directly bonded to one or more amide or thioamide nitrogen atoms per molecule, where R ¹² is a hydrogen atom and has 1 to 4 carbon atoms. represents an alkyl group or an acetyl group). Such aminoplasts include, for example, the following amides and amide-like substances such as N-hydroxymethyl, N-
Methoxymethyl, N-butoxymethyl and N-acetoxymethyl derivatives may be mentioned. Urea, thiourea and the following formula X: [In the formula, R ¹³ represents an oxygen atom or a sulfur atom, and R ₁₄ represents the following formula XI: (wherein R ¹³ represents the above meaning) or a methyl group, a methoxy group or a hydroxyl group, and -CO-, -O- or -N (R ¹⁵ )
- (in the formula, R ¹⁵ represents an alkyl or hydroxyalkyl group having up to 4 carbon atoms) represents a divalent group optionally interrupted with a methyl or methoxy substituent or -CO- or -N(R ¹⁵ )-contains 2 to 4 carbon atoms in addition to the interrupting group. ] Cyclic urea. Examples of such cyclic ureas include ethylene urea (imidazolidin-2-one), dihydroxyethylene urea (4,5-dihydroxyimidazolidin-2-one), hydantoin, and uron (tetrahydro-oxadiazin-4-one). , 1,2-propylene urea (4-methylimidazolidin-2-one), 1,3-propylene urea (hexahydro-2H-pyrimido-2-
), hydroxypropylene urea (5-hydroxyhexahydro-2H-pyrimid-2-one), dimethylpropylene urea (5,5-dimethylhexahydro-2H-pyrimid-2-one), dimethylhydroxypropylene urea and dimethylmethoxy Propylene urea (4-hydroxy- and 4-methoxy-5,5-dimethylhexahydro-2H-pyrimid-2-one), 5-
Mention may be made of ethyltriazin-2-one and 5-(2-hydroxyethyl)-triazin-2-one. Carbarmates and dicarbamates of aliphatic monohydric and dihydric alcohols containing up to 4 carbon atoms, such as methyl, ethyl, isopropyl, 2-hydroxyethyl, 2-methoxyethyl, 2-hydroxy-n-propyl and 3- Hydroxy-n-propylcarbamate, ethylene and 1,4-butylene dicarbamate. Melamine and other polyamino-1,3-triazines such as acetoguanamine, benzoguanamine and adipoguanamine. If desired, aminoplasts containing both N-hydroxymethyl and N-alkoxymethyl groups or both N-hydroxymethyl and N-acetoxymethyl groups can be used (e.g. 1 to 3 (hexamethylolmelamine) in which the hydroxyl groups are etherified with methyl groups. Preferred aminoplasts include urea, uron,
Condensation products of hydantoin or melamine with formaldehyde and partially or fully etherified products of such condensation products with aliphatic monohydric alcohols having 1 to 4 carbon atoms. Preferred phenoplasts are resols made from phenols and aldehydes. Suitable phenols include phenol itself, nosorcinol, 2,2-bis(p-hydroxyphenyl)propane, p-chlorophenol,
Phenols each substituted with 1 or 2 alkyl groups having 1 to 9 carbon atoms, such as o
-, m- and p-cresol, xylenol,
Mention may be made of p-tert-butylphenol, p-nonylphenol and phenols substituted with phenyl groups, especially p-phenylphenol. As the aldehyde to be condensed with the phenol, formaldehyde is preferred, but other aldehydes such as acetaldehyde and furfuraldehyde can also be used. Mixtures of such curable phenolic aldehyde resins can be used if desired. Preferred resols include phenol, p-chlorophenol, resorcinol or o-, m
- or a condensation product of p-cresol and formaldehyde. Preferably, the composition of the invention also contains a sensitizer if it is to be photopolymerized. By incorporating suitable sensitizers, we have found that the curing rate is further increased, thus allowing the application of shorter irradiation times and/or less intense irradiation sources. Furthermore, sensitivity to visible light is also increased. Sensitizers other than dyes, especially aromatic polycyclic compounds having at least three fused benzene rings and having an ionization energy of 7.5 ev or less, have been found to be more effective. Suitable such sensitizers are those described in US Pat. No. 4,069,054, including anthracene, rubrene, perylene, phenanthrene, fluoranthene, and pyrene. Based on the weight of a), the sensitizer content is preferably from 0.1 to 2, in particular from 0.25 to 0.75% by weight. Preferably, actinic radiation with a wavelength of 200 to 600 nm is used in the photopolymerization process. Suitable sources of actinic radiation include carbon arcs, mercury arcs, phosphorous fluorescent lamps emitting ultraviolet radiation, argon and xenon glow lamps, tungsten lamps and photographic flood lamps. Of these, mercury arcs, especially solar lamps, fluorescent solar lamps and metal halide lamps are most suitable. The time required for irradiation depends on a variety of factors, including, for example, the particular polymerizable substrate used, the type of light source, and the distance from the irradiation material. Appropriate times can be readily determined by those skilled in the photopolymerization arts. If, as in the method described below, the photopolymerized product is mixed and must be able to be cured by heating with a thermosetting agent, the irradiation must, of course, be carried out by the thermosetting agent. The photopolymerization is carried out at a temperature below which substantial thermal curing of the photopolymerized product occurs. If the compositions of the invention are to be polymerized substantially solely by heat, preferably from 100°C to 175°C.
Preferably for 3 to 20 minutes. The composition of the invention can be used as a surface coating. The compositions of the invention can be applied to substrates such as steel, aluminum, copper, cadmium, zinc, paper or wood, preferably as a liquid, and irradiated or heated. By irradiating through a mask, parts of the coating can be photopolymerized, and the parts not irradiated can be washed with a solvent to remove the unpolymerized parts while leaving the photopolymerized insoluble parts in the correct position. . The compositions of the invention can thus be used in the production of printing plates and printed circuits. Methods for producing printing plates and printed circuits from photopolymerizable compositions are well known (see, for example, GB 1495746). The composition of the invention can also be used as an adhesive. When applying photopolymerization, a layer of the composition of the invention is sandwiched between the surfaces of two objects, at least one of which is transparent to the compound line, such as glass, and the assembly is then heated or Irradiation and optionally heating can complete the polymerization. The compositions of the invention are also used in the production of fiber-reinforced composite materials, including sheet molding compounds. The compositions of the present invention are suitable for use in reinforcing fibers (including strands, filaments and whiskers) which may be in the form of woven or non-woven fabrics, unidirectional lengths or chopped strands, particularly glass, boron, stainless steel, tungsten, etc. , alumina, silicon carbide, asbestos, potassium titanate whiskers, poly(m-phenylene isophthalamide),
It can be applied directly in liquid form to aromatic polyamides such as poly(p-phenylene terephthalamide) or poly(p-benzamide), polyethylene, polypropylene or carbon. The fiber-reinforced composite material is advantageously placed under slight tension on a film of the photopolymerizable composition, such a film then optionally placed on top, and the assembly then heated. It can also be produced by a batch method in which pressure is applied at the same time. produced continuously by contacting the fiber-reinforced material with a film of the photopolymerizable composition and then optionally placing a second such film on the opposite side of the fiber-reinforced material and applying heat and pressure. You can also. More conveniently, two such films, preferably supported on opposite sides by belts or peelable sheets, are applied simultaneously to the fiber-reinforced material so as to contact each irradiated surface. When two such films are used, the films may be the same or different. Multilayer composites can be produced by heating and pressing films and layers interposed between one or more fiber reinforced materials.
When using unidirectional fibers as reinforcing material,
These successive layers can be oriented to form a crosslinked structure. Along with the fiber reinforced material, other types of reinforcements such as metal foils (e.g. aluminium, steel or titanium) or sheets of plastic materials (e.g. aromatic or aliphatic polyamides, polyimides, polysulfones or polycarbonates) or rubber (e.g. neoprene or acrylonitrile rubber)
sheets can be used. Alternatively, a mixture of reinforcing fibers and the composition of the present invention,
Heat directly to form composite material. In the production of sheet molding compounds, the composition of the present invention is irradiated or heated into layers through a support sheet along with the tip strand reinforcement and other ingredients. The polymerizable composition preferably contains a total of 20
The composition is applied in such a way that it contains from 80% to 80% by weight of the reinforcement, thus from 80 to 20% by weight of the reinforcement. More preferably a total of 30 to 50% by weight of the composition is used. The compositions of the invention are useful in making putties and fillers. The compositions of the present invention can be applied by dip coating, in which the article to be coated is dipped into a liquid composition, withdrawn, the deposited coating is photopolymerized (where it hardens) by heating or irradiation, and then optionally heated. It can be used as We have found that epoxide resins and phenoplasts can be cured in two steps using aryloxysulfoxonium salts; The partially cured composition is converted to a partially cured B-stage by irradiation with actinic radiation in the presence of a heat-activated crosslinker, and in a second step the partially cured composition is cured by a heat-activated crosslinker. Heat until complete.
A liquid or semi-liquid composition can be produced in this way, which can then be shaped with irradiation to solidify or used to impregnate a substrate; the solidified material can then be used to form the desired The resin is then heated to complete curing. Therefore, another embodiment of the invention is to form a B-stage product by combining an epoxide resin or phenoplast with an effective amount of an aryloxysulfoxonium salt having the formula for the polymerization of the epoxide resin or phenoplast. The curing of the composition is completed by irradiation and optionally heating in the presence of a curing amount of the latent heat curing agent of the epoxide resin or phenoplast. Further embodiments of the invention include an epoxide resin or phenoplast, an aryloxysulfoxonium salt of the formula and an epoxide in an effective amount to polymerize the epoxide resin or phenoplast by exposing the composition to actinic radiation. It consists of a composition containing a curing amount of a latent heat curing agent of a resin or phenoplast. Suitable heat-activated crosslinking agents for epoxide resin compositions include polycarboxylic anhydrides, complexes of amines, especially primary or tertiary aliphatic amines such as ethylamine, trimethylamine and n-octyldimethylamine, and boron trifluoride or trifluoride. Included are complexes with boron chloride and latent boron difluoride chelates. Aromatic polyamines and imidazoles are undesirable due to poor results, possibly due to reaction of the generated acid catalyst with the amine. In the case of relatively coarse particles, dicyandiamide can be advantageously used. Suitable heat-activated crosslinking agents for resols include hexamethylenetetramine and paraform. The heating temperature and time required for thermal curing after photopolymerization and the proportion of thermally active curing agent are easily found by routine experimentation and are already well known for thermal curing of epoxide resins and phenol-aldehyde resols. It can be easily derived from something. Compositions containing resins with epoxide groups or phenolic hydroxyl groups that can be thermally cured after photopolymerization are particularly useful in the production of multilayer printed circuits. Usually multilayer printed circuits are manufactured from several copper double-sided printed circuit boards laminated together and usually B-
They are separated from each other by insulating sheets of glass fiber impregnated with a step epoxide resin or phenol-formaldehyde resin. If the thermosetting agent is not mixed into the photopolymerizable resin layer in the circuit board, it is mixed into the insulating layer (conveniently an epoxy resin or phenol-formaldehyde resin prepreg) that alternates with the plate. If the prepreg is not too thick, a sufficient amount of thermosetting agent contained in the prepreg will migrate to induce a crosslinking reaction of the photopolymerized epoxide resin or phenol-formaldehyde resin. The laminate is heated and compressed to bond the layers together. However, conventional photopolymerizable materials do not form strong bonds with either copper or resin-impregnated glass fiber sheets. Laminates bonded with a photopolymer still covering the copper are therefore inherently weak and can delaminate in use. It is therefore common practice to remove the remaining photopolymer after the etching step by strong solvents or by mechanical methods, for example with a brush. Since such stripping processes can damage the surface of printed circuit copper or laminates on circuit resists, there is a need for a method that avoids the need to remove photopolymerized material before bonding the boards together. It was hot. The presence of residual crosslinking groups in the compositions of the present invention ensures that crosslinking occurs when the boards are bonded, so that good adhesion to copper and resin-impregnated glass fiber substrates is obtained, avoiding the above-mentioned need. and products with high glass transition temperatures are obtained. Another application involving thermal curing after photopolymerization of the compositions of the invention is in filament winding. A continuous tow of fiber reinforcement is thus impregnated with a composition containing a latent heat curing agent and then spread around a mandrel or former while the winding is irradiated with actinic radiation. Such filament windings still have a degree of flexibility that allows for easier removal of the mandrel or former than when rigid windings are formed in one step. If necessary, the winding is heated to crosslink the composition. Additionally, in such applications, a layer of the composition in liquid form is irradiated until solidified, placed between and in contact with the two surfaces to be bonded together to produce a film adhesive layer, and the assembly is bonded. to completely crosslink the composition. The film may be provided on one side with a cellulosic paper sheet having a peelable backing, such as a coating of polyolefin, polyester or silicone mold release agent. Handling of the assembly is often easier if the film has a sticky surface. Such films are produced by applying to the film a substance that is tacky at room temperature but crosslinks to a hard, insoluble, infusible resin under heated conditions applied to complete crosslinking of the composition. be able to. However, especially if the composition does not undergo excessive polymerization, it will have adequate tackiness without further treatment. Suitable adherends include metals such as iron, zinc, copper, nickel and aluminum, ceramics, glass and rubber. Next, the present invention will be explained with reference to examples. Unless otherwise specified, "parts" represent "parts by weight." The aryloxysulfoxonium salts used in these examples were prepared as described in Chalkley et al., supra. Example 1 50 parts of 2,2-bis(4-glycidyloxyphenyl)propane, 30 parts of 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, 20 parts of 1,4-bis(glycidyloxy)butane and phenoxy-p-tolyl-
A curable composition was prepared by forming a mixture of two parts of p-tolyloxysulfoxonium hexafluorophosphate. of this composition
A 10 μm thick film was applied onto a tin plate, and a “Mini-cure” device (Primarc Ltd.) containing two medium-pressure mercury arc lamps (80 W/cm) was placed on a belt. Exposure to ultraviolet light was performed in one pass at an operating speed of 30 m/min. The resin cured into a hard, solvent-resistant film (ie, withstood more than 20 rubs with an acetone-absorbed cotton swab) in less than 3 seconds. Example 2 A part of the curable film produced in Example 1 was
It was applied to a thickness of 10 μm on a mm-thick glass plate. Another glass plate was placed on top of this and the assembly was irradiated from a Primark 80 W/cm medium pressure mercury arc lamp at a distance of 8 cm. After 5 seconds of irradiation, the glass plates were permanently bonded together. Example 3 Add 2 parts of phenoxy-p-tolyloxy-sulfoxonium hexafluorophosphate to 100 parts of 3,4-dihydro-2H-pyran-2-ylmethyl 3,4-dihydro-2H-pyran-2-carboxylate. Ta. After mixing the ingredients thoroughly,
The mixture was applied to a tin plate as a 10 μm thick film. A hard, tack-free coating was obtained by irradiation for 5 seconds from an 80 W/cm medium pressure mercury arc lamp at a distance of 8 cm. Example 4 100 parts of commercially available phenol formaldehyde resol with a P:F ratio of 1:1.6 was mixed with
Tolyl-p-tolyloxy-sulfoxonium
Two parts of hexafluorophosphate were added.
The mixture as a 10 μm film was irradiated under the conditions described in Example 3 and a hard clear film was obtained after 5 seconds. Example 5 Phenoxy-p-tolyl-p-tolyloxy- was added to 100 parts of a highly condensed commercially available urea-formaldehyde resin with a urea:formaldehyde ratio of 1:1.4.
Two parts of sulfoxonium hexafluorophosphate were added. The mixture as a 10 μm thick film was irradiated under the conditions described in Example 3, giving a tack-free coating after 5 seconds. When the sulfoxonium salt was omitted, the resin remained sticky upon irradiation but could be easily removed by wiping or water. Example 6 Phenoxy-p-tolyl-p-tolyloxysulfoxonium hexafluorophosphate 2
and 100 parts of 2,2-bis(4-glycidyloxyphenyl)propane,
It was applied as a 10 μm film on a tin plate. This layer was irradiated from a 400 W high pressure metal halide quartz lamp (with radiation primarily in the 365 mμ band) at a distance of 22 cm. After 5 minutes of irradiation, a slightly tacky film was obtained which became tack-free after standing for an additional 5 minutes. Another portion of the above mixture was added to pyrene 0.5%. This mixture was irradiated as a 10 μm film under the same irradiation conditions as the mixture without pyrene, resulting in a tack-free coating after 45 seconds of irradiation. This film could not be removed with acetone. Example 7 1-Phenoxy as a 10 μm thick film
2 parts of 1-oxide tetrahydrothiophenium hexaphorophosphate and 2,2-bis(4-
A mixture of 100 parts of glycidyloxyphenyl)propane was irradiated under the conditions described in Example 2 to give a tack-free coating after 20 seconds of irradiation. Example 8 The procedure of Example 7 was repeated using 2 g of 1-phenoxy-1-oxidetetrahydrolothiophenium tetrafluoroborate in place of hexafluorophosphate. A tack-free coating was obtained after 1 minute of irradiation. Example 9 3,4-epoxycyclohexylmethyl 3,4
-Epoxy cyclohexane carboxylate 100
1 part of p-chlorophenoxy-p-tolylphenoxy-sulfoxonium hexafluorophosphate was added. The mixture was made into a 10 μm film and irradiated under the conditions described in Example 2 to yield a hard, solvent-resistant coating after irradiation for less than 1 second. Example 10 One part of phenyldiphenoxysulfoxonium hexafluorophosphate and 2,2-bis(4
A mixture of 100 parts of -glycidyloxyphenyl)propane was irradiated as a 10 μm film under the conditions described in Example 2 to form a hard,
A solvent-resistant coating film was obtained. Example 11 1 part of methyldiphenoxysulfoxonium hexafluorophosphate was added to 100 parts of 2,2-bis(4-glycidyloxyphenyl)-propane. Following the procedure of Example 2, a sufficiently cured coating film was obtained after 5 seconds of irradiation. Example 12 The procedure of Example 11 was repeated using 1 part of diphenyl-phenoxysulfoxonium hexafluorophosphate in place of the methyldiphenoxy analog. A hard, cured adhesive film was formed after 10 seconds of irradiation. Example 13 1-Phenoxy-1-oxide tetrahydrothiophenium hexafluoroantimonate 2
The procedure of Example 2 was carried out using a 10 μm thick coating of a mixture of 100 parts of 2,2-bis(4-glycidyloxyphenyl)propane and 100 parts of 2,2-bis(4-glycidyloxyphenyl)propane. A tack-free coating was obtained after irradiation for 10 seconds. Example 14 The procedure of Example 1 was repeated except that the "Mini-Cure" device was operated at a belt speed of 90 m/min. The resin cured into a hard, solvent-resistant coating within 19 seconds. 0.5% pyrene was added to another portion of the above composition.
This mixture was irradiated under the same irradiation conditions and a tack-free coating was obtained after only 10 seconds. Example 15 75 parts of 2,2-bis(4-glycidyloxyphenyl)propane, phenol-formaldehyde with epoxide content of 5.6 equivalents/Kg, 25 parts of polyglycidyl ether of Novorac, 4 parts of boron trichloride complex of n-octyldimethylamine A liquid composition was prepared by forming a mixture of 2 parts of p-chlorophenoxy-p-tolylphenoxy-sulfoxonium hexafluorophosphate. This curable composition was used to make prepregs by impregnating glass cloth (plain weave) and then both sides were irradiated for 5 seconds from an 80 W/cm medium pressure mercury arc lamp at a distance of 8 cm. Six sheets of 10 cm ² prepreg were pressed at 120° C. for 1 hour at a pressure of 2.1 MN/m ² to produce a 6-layer glass fabric laminate. glass
This laminate consisting of 58% has an interlaminar shear strength of
It was 448MN/ ^m2 . Example 16 Diglycidyl ether of 2,2-bis(p-hydroxyphenyl)propane (epoxide content 5.3
equivalent weight/Kg) 1g, 1,1,2,2-tetra(p-
4 g of tetraglycidyl ether (epoxide content 5.2 equivalents/Kg) of hydroxyphenyl)ethane, 2,2-bis(p-hydroxyphenyl ) A solution was prepared by dissolving 5 g of diglycidyl ether of propane and 0.1 g of p-chlorophenoxy-p-tolylphenoxysulfoxonium hexafluorophosphate in 10 g of cyclohexanone. A copper deposited laminate was coated with this composition and the solvent was evaporated to a film approximately 10 μm thick. Using a 500W medium pressure mercury lamp at a distance of 22cm,
This film was exposed through a negative for 10 minutes. After irradiation, the image was developed with toluene and the unirradiated areas were washed away leaving a good relief image on the copper. The uncoated copper area was then heated to 35°C with a ferric chloride aqueous solution (41%).
wt/wt FeCl ₃ ) and the coated areas were left intact. Example 17 This example illustrates the co-curing of a polyhydric alcohol and an epoxide resin by radiation. 3,4-epoxycyclohexylmethyl 3,4
-Epoxy cyclohexane carboxylate 100
100 parts of a commercially available styrene-allylic alcohol copolymer (“RJ100” from Monsanto Chemical Company) with a hydroxyl content of 3.56 equivalents/Kg and 2 parts of p-chlorophenoxy-p-tolylphenoxysulfoxonium hexafluorophosphate. A 10 μm thick film of the composition was applied onto a tin plate and irradiated with a medium pressure mercury arc lamp (80 W/cm). A tack-free, flexible coating was formed in 2 seconds. Example 18 In this example, the catalyst of the present invention was compared with prior art catalysts for efficacy in inducing photopolymerization. From 2 parts of catalyst, 50 parts of 2,2-bis(4-glycidyloxyphenyl)propane, 30 parts of 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate and 20 parts of 1,4-diglycidyloxybutane. A composition was prepared. A "Minicure" device (described in Example 1) was applied with a 10 μm thick film on a tin plate and operated at a belt speed of 60 m/min.
UV rays were irradiated by passing the sample twice. The irradiation time required for the coating to become tack-free is listed in the following table.

【table】

TABLE As mentioned above, triphenylsulfonium hexafluorophosphate is used commercially in the photopolymerization of epoxide resins. The iodonium salt 3,3'-dinitrodiphenyliodonium hexafluorophosphate, which is proposed in the above patent document as being suitable for the photopolymerization of epoxide resins, is one of the more active salts in unpublished experiments conducted by the present inventor. It has been shown that The superiority of the sulfoxonium salts used in the compositions a and b over those of the prior art is clearly demonstrated. Example 19 This and the following example illustrate thermal curing of compositions of the present invention. Two parts of 1-phenoxy-1-oxide tetrahydrothiophenium hexafluorophosphate were kneaded with 98 parts of 2,2-bis(4-glycidyloxyphenyl)-propane. Mixture sample 15
Although still fluid, it did not gel after heating at 60°C for 24 hours; 15g samples were heated at 110°C and 150°C and cured for 17 and 6 minutes, respectively.
The compositions have been shown to be latent (ie, have a long shelf life in the uncured state at about room temperature, but harden rapidly when heated at elevated temperatures). Example 20 A composition consisting of 2 parts of phenyldiphenoxysulfoxonium hexafluorophosphate and 98 parts of 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate was applied as a 10 μm thick film on a tin plate. and heated at 120°C for 15 minutes. A hard, tack-free coating was obtained. Example 21 A mixture of 2 parts of 1-phenoxy-1-oxide tetrahydrothiophenium hexafluorophosphate and 98 parts of the phenol-formaldehyde resol used in Example 4 was placed on a tin plate.
A 10 μm thick layer was heated at 110° C. for 15 minutes. A hard coating film resistant to acetone was obtained.

Claims (1)

[Scope of Claims] 1 a) 1,2-epoxide, vinyl monomer or prepolymer, aminoplast or phenoplast, and b) the following formula: (in the formula, R ⁶ and R ⁷ are each) a C 1 -C 6 alkyl group which may be substituted with a halogen atom and whose chain may be interrupted by an ether oxygen atom or a sulfonyl group;
) an aryl group having 6 to 15 carbon atoms, or) an aryloxy group having 6 to 15 carbon atoms, or R ⁶ and R ⁷ together with the sulfur atom in the above formula form a heterocyclic group; represents a divalent group having 4 to 10 carbon atoms, R ⁸
represents an aryl group having 6 to 15 carbon atoms, M represents a metal atom or metalloid atom, X represents a halogen atom, and n represents 4,5
Or 6 represents a number 1 greater than the valence of M. ) A photopolymerizable and thermally polymerizable composition comprising an effective amount of an aryloxysulfoxonium salt represented by: 2. A composition according to claim 1, wherein in the formula R ⁶ and R ⁷ each represents an aryl or aryloxy group having 6 to 11 carbon atoms. 3. The composition according to claim 1, wherein in the formula R ⁶ and R ⁷ represent a monocyclic chain consisting only of carbon atoms and hydrogen atoms formed together. 4 In the formula, R ⁸ is unsubstituted or each has 1 to 4 carbon atoms.
1 or 2 alkyl or alkoxy groups
by one or two nitro groups or by one fluorine, chlorine or bromine atom
2. A composition according to claim 1, which represents a phenyl or naphthyl group substituted by one or two. 5. The composition according to claim 1, wherein in the formula, M represents boron, phosphorus, arsenic, antimony or bismuth, and X represents a fluorine atom or a chlorine atom. 6 b) is diphenyl phenoxysulfoxonium hexafluorophosphate, diphenyldiphenoxysulfoxonium hexafluorophosphate, methyldiphenoxysulfoxonium hexafluorophosphate, p-tolylphenoxy-p-tolyloxysulfoxonium Hexafluorophosphate, ethyl(ethylsulfonylmethyl)-p-tolyloxysulfoxonium hexafluorophosphate, p-chlorophenoxy-p-tolylphenoxysulfoxonium hexafluorophosphate, 1-phenoxy-1-
Claim 1 which is oxidetetrahydrothiophenium hexafluorophosphate, 1-phenoxy-1-oxidetetrahydrothiophenium tetrafluoroborate, or 1-phenoxy-1-oxidetetrahydrothiophenium hexafluoroantimonate Composition of. 7. A composition according to claim 1, wherein a) is a resol resin made from a 1,2-epoxide or a phenol and an aldehyde. 8. A composition according to claim 1, containing from 0.1 to 7.5 parts by weight of b) per 100 parts by weight of a). 9. The composition according to claim 7, further comprising a curing amount of a latent heat curing agent of 1,2-epoxide or resol resin.