JPH0350771B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides at least two mercaptans (-
A composition consisting of a polymercaptan having SH) groups, a compound having at least 2, preferably at least 3 ethylenically unsaturated double bonds and another ethylenically unsaturated compound having at least one free carboxyl group. It is about things. The invention also relates to a process for the polymerization of said compositions with actinic radiation and/or thermally activated free radical catalysts and to the use of the polymerization products as surface coatings, as adhesives and in reinforced composite materials, especially printed circuits. be. In European Patent Application No. 0031305, the inventors disclosed the following polymerizable composition. This polymerizable composition has (1) at least one group selected from acryloyloxy and methacryloyloxy groups in the molecule.
Allyl, methallyl and 1- bonded to a carbon atom forming part of the aromatic nucleus directly or via a linear atom or an oxycarbonyl group (-OOC-) bonded directly to the above carbon atom in order.
(2) a compound containing at least one mercaptan group directly bonded to an aliphatic carbon atom per molecule; providing at least 0.8 of the above mercaptan groups per group selected from allyl, methallyl and 1-propenyl groups in (), but acryloyl, methacryloyl, allyl, methallyl and 1-propenyl groups in component (1); The composition contains less than 1.0 of the above mercaptan groups per group selected from the following. By exposing the composition to actinic radiation or under the influence of a free radical catalyst, the composition is polymerized. In the so-called negative resist method for producing printed circuits by photopolymerization, a support is coated with a photopolymerizable composition and the coated support is passed through a negative to substantially transparent and substantially opaque. It is conventional practice to expose the coating to actinic radiation within a range such that polymerization occurs in the areas of the coating that were exposed to the actinic radiation. Alternatively, the exposure can be performed using computer-controlled laser light instead of the negative. The image is then developed by eluting with a suitable solvent the areas in which no polymerization has occurred, ie, the areas not exposed to actinic radiation. Thereafter, the support, usually a copper support, can be exposed to an etching solution so that the areas not protected by the layer of photopolymerized composition are etched. In other processes, for example in the production of multilayer boards, layers of photopolymerized compositions can also be generally removed by mechanical means. Disadvantages of currently practiced methods are that organic solvents, which have the combined hazards of toxicity and flammability, are often used for development, and that mechanical treatments to remove photopolymerized compositions are difficult for printed circuits. This means that it can cause damage. The method of the invention consists in using a polymerizable composition which also contains carboxylic acid groups. Even if the exposure to actinic radiation is carried out through a substantially opaque area negative, the composition is removed from the unexposed areas by treatment with an aqueous alkaline solution to form a salt of a carboxylic acid. be able to. The use of organic solvents for this purpose, with their attendant drawbacks, is therefore avoided. Another advantage is that the polymerized composition can be removed later, if desired, by using a stronger alkaline aqueous solution. The object of the present invention is to (a) contain in the molecule at least one group selected from acryloyloxy and methacryloyloxy groups (), directly or via an oxygen atom or an oxycarbonyl group (-OCO-), an aromatic nucleus; At least one group selected from allyl, methallyl, and 1-propenyl group bonded to a carbon atom forming a part of
(b) a compound containing in the molecule at least 3 groups, preferably at least 3 groups () and (); (c) a compound containing at least two mercaptan groups per molecule directly bonded to an aliphatic carbon atom; , providing at least 0.8 said mercaptan groups per group selected from allyl, methallyl and 1-propenyl groups in component (a),
However, the polymerizable composition containing component (b) in a proportion that provides less than 1.0 mercaptan groups per one selected from acryloyl, methacryloyl, allyl, methallyl and 1-propenyl groups in component (a). It's about providing things. Other features of the invention provide a method of polymerizing the composition as described above, comprising exposing the composition to the action of actinic radiation or a thermally activated free radical catalyst, and the polymerization product obtained by the method. It is in. Preferably component (b) contains 0.75 groups selected from acryloyloxy and methacryloyloxy groups for each group selected from acryloyloxy and methacryloyloxy groups present in component (a).
present in sufficient quantities to give 1.25 to 1.25. British Patent No. 1474715 describes photopolymerizable acrylic esters containing free carboxylic acid groups, which are synthesized by reacting at least a dianhydride of a polycarboxylic acid with an alcohol containing at least two acrylic ester groups. There is. US Patent No.
Nos. 4079183, 4181807 and 4179577 include:
A free carboxylic acid group and some bonded to two aromatic rings obtained by reacting at least dianhydride of a polycarboxylic acid with an alcohol hydroxyl group of an alcohol containing at least one specific unsaturated group. Photopolymerizable compounds containing specific unsaturations are described. All of these publications describe the removal of unphotopolymerized materials by contacting them with aqueous alkaline solutions, but do not mention the photopolymerization of these materials in the presence of polymercaptans. In the compositions of the invention, component (a) preferably has no ethylenically unsaturated groups other than in the acryloyloxy, methacryloyloxy, allyl, methallyl and 1-propenyl groups. Component (a) preferably has a molecular weight of at most 5000. Preferably the acryloyloxy or methacryloyloxy group is directly or of the formula: Group or formula represented by: (In the formula, R represents a hydrogen atom or a methyl group,
and a represents an integer from 1 to 6. ) is bonded to the carbon atom of the aromatic nucleus via a group represented by Preferably component (a) contains at least 2 and at most 6 groups selected from acryloyloxy and methacryloyloxy groups per molecule, and preferably component (a) contains allyl, methallyl and 1-propenyl groups per molecule. Contains at least 2 and at most 15 selected from the group. A more preferred component (a) is one in which the total number of groups selected from acryloyloxy and methacryloyloxy groups per molecule is the same as the total number of groups selected from allyl, methallyl and 1-propenyl groups in the molecule. It is a certain compound. The aromatic nucleus in component (a) is preferably a benzene nucleus or a naphthalene nucleus. Further preferred component (a) is at least two phenolic hydroxyl groups esterified with an acryloyl or methacryloyl group, either directly or via the (terminal) ether oxygen atom of the formula or the group represented by the formula, and allyl, methallyl and 1-
It is a polyhydric phenol having a group selected from propenyl groups and at least two phenolic hydroxyl groups which are directly etherified. Also preferred component (a) is at least one carboxylic acid group bonded to the acryloyl or methacryloyl group via the (terminal) carbon atom of the formula or the group represented by the formula and allyl, methallyl and 1-propenyl groups. A polycarboxylic acid having at least one carboxylic acid group directly esterified with a selected group. Particularly preferred component (a) is at least two phenolic hydroxyl groups esterified with groups selected from acryloyl and methacryloyl groups, either directly or via the (terminal) ether oxygen atom of the group represented by the above formula or formula. polyhydric phenol having a carbon atom of the benzene or naphthalene nucleus directly substituted by at least two groups selected from allyl, methallyl and 1-propenyl groups, in particular when these substituents are It is a polyhydric phenol with an acryloyl or methacryloyl group in the ortho position. Examples of compounds suitable as component (a) are those of formulas XII below. (In formulas to R ² represents an allyl, methallyl or 1-propenyl group, R ³ represents a carbon atom-carbon atom bond, an alkylene or alkylidene group having at most 5 carbon atoms, an ether oxygen atom, a sulfur atom or the formula: -CO-,-
represents a group represented by SS-, -SO-, or -SO ₂ -, each R ⁴ represents a hydrogen atom, a chlorine atom or a bromine atom, or an alkyl group having 1 to 4 carbon atoms, and each R ⁵ represents a group represented by the formula : CH ₂ =C(R)COOR ¹ -, or at least one group is represented by the formula: CH ₂ =C(R)COOR ¹ -, and at least two are allyloxy , represents a methallyloxy or 1-propenyloxy group, represents an allyloxy, methallyloxy or 1-propenyloxy group;
It is provided that the CH ₂ - and R ² - groups are in the ortho or rose position of the CH ₂ =C(R)COOR ¹ - and R ⁵ groups. ) Specific examples of compounds suitable as component (a) are given below. 2,2-bis(3-allyl-4-(methacryloyloxy)phenyl)propane, bis(3-allyl-4-(methacryloyloxy)phenyl)
Methane, 2,2-bis(3-methallyl-4-(methacryloyloxy)phenyl)propane, bis(3-methallyl)-4-(methacryloyloxy)
phenyl)methane, 2,2-bis(3-(1-propenyl)-4-(methacryloyloxy)phenyl)propane, bis(3-(1-propenyl)-4
-(methacryloyloxy)phenyl)methane,
and their acryloyl analogs: 2,2-bis(3-allyl-4-(3-(methacryloyloxy)-2-hydroxypropoxy)
phenyl)propane, bis(3-allyl-4-
(3-(methacryloyloxy)-2-hydroxypropoxy)phenyl)methane, the corresponding bis(3-methallyl) and bis(3-(1-propenyl)) compounds, and their acryloyl analogues: 2,2-bis (3-allyl-4-(2-methacryloyloxy)ethoxy)phenyl)propane, bis(3-allyl-4-(2-methacryloyloxy)ethoxy)phenyl)methane, 2,2
-bis(3-methallyl-4-(2-(methacryloyloxy)ethoxy)phenyl)propane, the corresponding bis(3-methallyl) and bis(3-(1
-propenyl)) compounds and their acryloyl analogues: 2,2-bis(3-allyl-4-(2-(methacryloyloxy)-2-methylethoxy)phenyl)propane, bis(3-allyl-4- (2-(methacryloyloxy)-2-methylethoxy)phenyl)methane, corresponding bis(3-methallyl)
and (3-(1-propenyl)) compounds, and their acryloyl analogues: 2,6-diallylphenyl acrylate, 2,
6-dimethallylphenyl acrylate, 2,6-
Di(1-propenyl) phenyl acrylate and their methacrylates; 1,3-diallyl-2-(2-hydroxy-3
-(methacryloyloxy)propoxy)benzene and the corresponding 1,3-dimethallyl and 1,
3-di(1-propenyl) compound; 1-allyl-2-(2-methacryloyloxy)
ethoxy)benzene, 1-allyl-2-hydroxy-2-(methacryloyloxy)propoxy)
Benzene, 1-allyl-2-(2-methacryloyloxy)-2-methylethoxy)benzene, and the corresponding 1-methallyl compounds, and their acryloyl analogs; 1,3-diallyl-2-(2-methacryloyloxy) ) ethoxy) benzene, 1,3-dimethallyl-2-(2-methacryloyloxy)ethoxy)
Benzene, 1,3-di(1-propenyl)-2-
(2-methacryloyloxy)ethoxy)benzene, and their acryloyl analogues; 1,3-diallyl-2-(2-methacryloyloxy)-2-methylethoxy)benzene, 1,
3-dimethallyl-2-(2-(methacryloyloxy)-2-methyltoxy)benzene, 1,3-di(1-propenyl)-2-(2-(methacryloyloxy)-2-methylethoxy)benzene, and the like 2,2-bis(3,5-diallyl-4-(methacryloyloxy)phenyl)propane, bis(3,5-diallyl-4-(methacryloyloxy)phenyl)methane, the corresponding bis(3 ,5-
dimethallyl) and bis(3,5-di(1-propenyl)) compounds and their acryloyl analogs: 2,2-bis(3,5-diallyl-4-(3-
(methacryloyloxy)-2-hydroxypropoxy)-phenyl)propane, bis(3,5-diallyl-4-(3-(methacryloyloxy)-2
-Hydroxypropoxy)phenyl)methane, the corresponding bis(3,5-dimethallyl) and bis(3,5-di(1-propenyl) compounds and their acryloyl analogues. Others that can be used as component (a) The compound contains one or two acryloyloxy or methacryloyloxy groups per molecule and only one
Contains five allyl, methallyl or 1-propenyl groups. The latter group has the formula: or (wherein R has the meaning given in the formula, R ¹ and R ² have the meaning given in the formula to XII, and each R ⁶ represents the formula or a group represented by the formula. ) can be bonded to an oxycarbonyl group that is directly bonded in order to a carbon atom that forms a part of an aromatic nucleus represented by Specific examples of compounds represented by formulas are shown below. 1-(allyloxycarbonyl)-2,4-bis(3-(methacryloyloxy)-2-hydroxypropoxycarbonyl)benzene, 1-(allyloxycarbonyl)-2,5-bis(3-(methacryloyloxy)- 2-hydroxypropoxycarbonyl)benzene, 1-(allyloxycarbonyl)-2,4-bis(methacryloyloxycarbonyl)benzene, 1-(allyloxycarbonyl)-2,5-bis(methacryloyloxycarbonyl)benzene, corresponding 1-(methallyloxycarbonyl) compound, corresponding 1-(1-propenyloxycarbonyl) compound, 1-allyloxycarbonyl-2-(3-methacryloyloxy-2-hydroxypropoxycarbonyl)benzene, 1-(methallyloxycarbonyl) compound oxycarbonyl)-2-
(3-methacryloyloxy-2-hydroxypropoxycarbonyl)benzene and corresponding acryloyloxy compounds. Other compounds, i.e. compounds containing two or more acryloyloxy or methacryloyloxy groups and one or more allyl, methallyl or 1-propenyl groups per molecule, have the formula: (In the formula, each R ₁ ⁵ represents a CH ₂ =C(R)COOR ¹ - group or an allyloxy group, a methallyloxy group, or a 1-propenyloxy group, and at least two R ₁ ^5s have the formula: CH ₂ =C (R)COOR represents the above group represented by ¹ -, and at least one R ₁ ⁵ represents an allyloxy group, methallyloxy group or 1-propenyloxy group, in which case the -CH ₂ - group represents a substituent -R located in the ortho or para position of ₁ ⁵ , R and a have the meanings given in the formula,
R ¹ has the meaning given to it in formulas and formulas XII, and R ⁴ has the meaning given to it in formulas and. ). In addition, as component (a), 6 or more per molecule, for example,
Compounds containing 12 allyl, methallyl or 1-propenyl groups and obtainable by the pioneered process can be used. For example, allyl, methallyl or 1-
Diglycidyl ethers of dihydric phenols substituted with propenyl groups are divalent phenols, dihydric alcohols, dicarboxylic acids or hydantoin rings.
It can be pioneered using a hydantoin with 2 free -NH-. The precursor product is then reacted with the secondary hydroxyl groups formed with glycidyl (meth)acrylate or (meth)acryloyl chloride. Other pioneer products containing six or more allyl, methallyl or 1-propenyl groups are diglycidyl ethers of dihydric phenols, diglycidyl ethers of dihydric alcohols or di(N-glycidyl)hydantoins such as 1,3 - diglycidylhydantoin and 3,3'-diglycidyl-1,
The 1'-methylenebis(hydantoin) can be obtained by preceding it with a divalent phehal substituted on the aromatic nucleus with one or more allyl, methallyl or 1-propenyl groups, and then converting the resulting secondary hydroxyl group into a glycidyl group. React with (meth)acrylate or (meth)acryloyl chloride. In addition, as component (a), the formula: (wherein one of R ⁷ and R ⁸ and one of R ⁹ and R ¹⁰
have the same meaning and each represent an allyl or methallyl group, and the remaining groups of R ⁷ and R ⁸ and the remaining groups of R ⁹ and R ¹⁰ each represent an alcohol residue excluding the alcoholic hydroxy group. and the alcohol residue is a (meth)acryloyloxy group, especially a (meth)acryloyloxy group.
Contains an acryloyloxyalkyleneoxy or (meth)acryloyloxyhydroxyalkyleneoxy group. ) can be used. Preferably the remaining groups of R ⁷ and R ⁸ and R ⁹
and each of the remaining groups of R ¹⁰ has the formula: (wherein R has the meaning given to it in the formula and R ⁶ has the meaning given to it in the formula and). Materials that have long been known to polymerize by exposure to actinic radiation are used with photoinitiators such as benzoin and its alkyl ethers in order to shorten the exposure time required for polymerization. However, the use of initiators is often disadvantageous. That is, the initiator may change the electrical properties of the polymer. The initiator volatilizes upon heating, making it unsuitable for use in multilayer printed circuits. Therefore, during the manufacture of multilayer printed circuits, the polymer must be removed after the metal etching process. This removal adds to the cost of the laminate and may cause damage to the metal surface. The inventors have found that the use of additional photoinitiators can be avoided by using a compound of the formula as component (a). A specific example of a compound of the formula is diallylbis(3-methacryloyloxy)-benzophenone-3,4,3',4'-tetracarboxylic acid.
2-hydroxypropyl) tetraester. The method for preparing compounds suitable for use as component (a) is the same as that described in the European patent application mentioned above. Component (b) preferably has a molecular weight of at most 1000. Preferably, each of the acryloyloxy or methacryloyloxy groups is bonded directly to a hydrogen atom, or directly or via a carboxyl group-containing group to a carbon atom or part of a heterocyclic ring of an aliphatic, cycloaliphatic or aromatic group. The nitrogen atom, especially the formula: (In the formula, R ¹¹ represents an alkylene, arylene, or aralkylene group which may be substituted with one or more other carboxylic acid groups, and the alkylene group and the alkylene moiety of the aralkylene group have 2 to 10 carbon atoms. and the arylene moiety of the arylene group and aralkylene group has 6 to 10 carbon atoms. Preferably component (b) contains at most 6 groups selected from acryloyloxy and methacryloyloxy groups per molecule and at most 2 carboxyl groups per molecule. The aromatic group in component (b) is preferably a benzene or naphthalene nucleus. Further preferred component (b) is a polyhydric phenol having at least two phenolic hydroxyl groups which are esterified by acryloyl or methacryloyl groups via carboxyl-containing groups of the formula. Examples of compounds suitable as component (b) are those of the following formula. (wherein a and R have the meanings given in the formula, R ³
has the meaning given in formula and formula XII, and R ⁴
has the meaning given by the expression and the expression
R ¹² represents a carboxyl-containing group of the formula defined above and each R ¹³ represents a C 1 -C 8 alkyl group, in particular a methyl or ethyl group, a C 7 -9 aralkyl group or a C 7 -C 9 aralkyl group; Number of atoms: 6 to 8
represents an aryl group, or together with the two carbon atoms to which R ¹³ are attached, the cyclopentane ring represents or represents a cyclohexane ring, and in the formula, each - shown in the formula
_CH2 =C(R) ^COOR12O where the _CH2- group is shown in the formula
- provided that it is in the ortho or rose position of the group. ). Particular examples of compounds suitable as component (b) are succinic acid, maleic acid, geltaric acid, adipic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endomethylenetetrahydrophthalic acid,
Pyromellitic acid or trimellitic acid and the following alcohols: 2,2-bis(4-(3-(methacryloyloxy)-2-hydroxypropoxy)phenyl)propane, bis(4-(3-(methacryloyloxy)-2-hydroxy) propoxy)phenyl)methane, and their partial esters with acryloyl analogs. Other compounds that can be used as component (b) have the formula or: or (wherein R ¹² has the meaning given to it and R has the meaning defined in the formula) and two acryloyloxy or methacryloyloxy groups. Specific examples of compounds of the formula or are succinic acid, maleic acid, glutaric acid,
Adipic acid, phthalic acid, tetrahydrophthalic acid,
hexahydrophthalic acid, endomethylenetetrahydrophthalic acid, pyromellitic acid, or trimellitic acid and the following alcohol: 1,3-bis(3
-(methacryloyloxy)-2-hydroxypropoxycarbonyl)benzene, 1,4-bis(3
-(methacryloyloxy)-2-hydroxypropoxycarbonyl)benzene and its corresponding partial ester with an acryloyloxy compound. Other compounds suitable for use as component (b) are of the formula: [wherein R has the meaning defined in the formula, and R ¹⁴ has the following formula:

【formula】

【formula】

【formula】

【formula】 or

[Formula R ³ has the meaning as defined in Formula and Formula XII, and R ¹³ has the meaning as defined in Formula]]. Other compounds suitable for use as component (b) are acrylic acid, methacrylic acid, and compounds in which the acryloyloxy or methacryloyloxy group, respectively, is bonded directly to the carbon atom of the aliphatic group, especially those of the formula: (wherein R has the meaning given in the formula, R ¹⁵
is −CH ₂ CH ₂ − or

[Formula] and R ¹⁶ represents at least a dicarboxylic acid residue from which two carboxy groups have been removed. ) is a compound represented by Preferred substituents R ¹⁶ are the residues of maleic acid, succinic acid, glutaric acid, adipic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endomethylenetetrahydrophthalic acid, trimellitic acid or pyromellitic acid. Compounds represented by
It can be obtained by reacting with acrylic acid to open the ring and esterifying the resulting secondary alcohol hydroxyl group with an anhydride of a di- or polycarboxylic acid. Alternatively, these compounds can be obtained by reacting the corresponding phenols, alcohols, amines or amido-imides with glycidyl acrylate or glycidyl methacrylate and then esterifying them with di- or polycarboxylic acid anhydrides. The compound represented by the formula can be obtained by reacting a dicarboxylic anhydride or a polycarboxylic anhydride with 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate. A wide variety of polymercaptans are suitable for use as component (c) in the compositions of the present invention. Preferred mercaptans do not contain any allyl, methallyl, 1-propenyl, acryloyl or methacryloyl groups and preferably have a molecular weight of at most 3000. The polymercaptans used usually contain at most 6 mercaptan groups per molecule directly bonded to aliphatic carbon atoms. However, preferably the polymercaptan contains two or more of the above groups. The first class consists of esters of monomercaptan alkylene carboxylic acids and polyhydric alcohols or esters of aliphatic monomercaptan monoalcohols and polycarboxylic acids. More preferably, the above ester has the following formula: (wherein R ¹⁷ has from 2 to 60 carbon atoms, the chain optionally being interrupted by at most one ether oxygen atom)
represents an aliphatic or araliphatic hydrocarbon group, preferably having 1 to 4 carbon atoms, the chain ^of which may be interrupted by at most one carbonyloxy group; represents an aliphatic hydrocarbon group, b represents an integer from 2 to 6, and c is zero or (b+c) is at most 6 (the term c(d) is interpreted algebraically) and at most 3;
represents a positive integer, and a and e represent the number of zero or one, but are not the same number. ). Furthermore, preferred esters have the formula: R ¹⁹ (OCOR ²⁰ SH) _b () in which b has the meaning given in the formula and R ¹⁹ represents an aliphatic hydrocarbon radical having from 2 to 10 carbon atoms. and R ²⁰ is −(CH ₂ )−, −
(CH ₂ ) ₂ − or −CH(CH ₃ )−. ) is a polymercaptan represented by The second class includes esters of monomercaptanedicarboxylic acids, with the formula: R ²³ −[(O) _d −CO(O) _e −R ²¹ (O) _e −CO(R) _d −R ²² SH] _f (
) (wherein d and e have the meanings given in the formula, f represents an integer from 1 to 6, and R ²¹ represents -O- or -CO given in the formula via its carbon atom) - represents a divalent organic group bonded to the - unit, and R ²² is a divalent organic group bonded to the -SH group and -O- or -CO- unit provided in the formula through its carbon atom. and R ²³ is f bonded via its carbon atom to the adjacent -O- or -CO- unit given in the formula.
represents the number 1, at least one aliphatic -
It represents an organic group which necessarily contains an SH group, preferably at least one aliphatic -SH group when f represents the number 2. ) consists of mercaptan-containing esters, including esters of monomercaptan dicarboxylic acids represented by When d represents the number of zero, R ²¹ is preferably
saturated carbon atoms having from 2 to 20 carbon atoms, which may be substituted by one or more methyl groups and one or more mercaptan groups and interrupted by one or more ether oxygen atoms and one or more carbonyloxy groups; Represents an aliphatic unbranched hydrocarbon chain. When d represents the number 1, R ²¹ is preferably () a saturated aliphatic hydrocarbon group having 2 to 10 carbon atoms which may have a mercaptan group, () one or more ethylenically unsaturated double Represents a cyclic aliphatic-aliphatic hydrocarbon group having 5 to 34 carbon atoms, or () a mononuclear arylene hydrocarbon group having 6 to 12 carbon atoms, which may have a bond. R ²² is preferably when d represents the number of zero;
Number of carbon atoms that can have a carboxyl group: 1
It represents a saturated aliphatic hydrocarbon group having 2 to 3 carbon atoms, and when d represents the number 1, it represents a saturated aliphatic hydrocarbon group having 2 to 4 carbon atoms which may be substituted with a hydroxyl group or a chlorine atom. R ²³ is preferably () a C 2 -C 51 aliphatic or cycloaliphatic-aliphatic hydrocarbon group which can carry at least one aliphatic mercaptan group, or () C 6 -C 15 a mononuclear or dinuclear arylene hydrocarbon group, or () a chain of 4 to 20 carbon atoms, interrupted by at least one ether oxygen atom and optionally substituted with at least one aliphatic mercaptan group, or ( ) represents a chain of 6 to 50 carbon atoms, interrupted by at least one carbonyloxy group, optionally interrupted by at least one ether oxygen atom and optionally substituted by at least one aliphatic mercaptan group; . Class 3 is the following L: (In the formula, R ²⁴ represents a polyhydric alcohol group excluding (j+k) alcoholic hydroxyl groups, particularly an aliphatic hydrocarbon group having 2 to 10 carbon atoms, and each R ²⁵ represents the indicated consecutive oxygen atom. represents an alkylene radical containing chains with at least two at most 6 carbon atoms between them, R ²⁶ represents an aliphatic radical of 1 to 6 carbon atoms containing at least one mercaptan group, and g represents Preferably, it represents a positive integer such that the average molecular weight of the polymercaptan is at most 2000, h represents a number of 0 or 1, and j represents 0 or an integer such that the (j + k) value is at most 6. , and k represents an integer of 2 to 6, preferably 3 to 6). The substituents R ²⁵ in each poly(oxyalkylene) chain can be the same or different and may be substituted, for example with phenyl or chloromethyl groups. Preferably substituent R ²⁵ is -C ₂ H ₄ -
or −C ₃ H ₆ −. Preferred compounds among the compounds represented by formula L are: Ester represented by and formula L; It is an ether represented by . In formula L and formula L, R ¹⁹ has the meaning given in formula L, R ²⁵ , g, j and k have the meaning given in formula L, and m represents the number 1 or 2. The fourth class of polymercaptans suitable as component (b) are: (wherein each R ²⁷ represents an alkylene hydrocarbon group containing 2 to 4 carbon atoms, R ²⁸ represents a hydrogen atom or a methyl or ethyl group, and n is an integer having an average value of at least 1, preferably represents an integer such that the average molecular weight of sulfide is at most 1000, and either p represents the number of zeros when q and r each represent the number of zeros, or q represents the number of zero or one. and when r represents the number 1, p represents 1.) is a mercaptan-terminated sulfide. Preferred sulfides of formula L are:
In the formula, R ²⁸ represents a hydrogen atom, p and q each represent a number of 1, and n represents a number such that the molecular weight of the sulfide is from 500 to 800. A fifth class of polymercaptans suitable as component (b) have the formula L: [In the formula, each R has the meaning given in the formula, ^R29 is the formula: -CN, -COOH, _-CONH2 , -
represents a group represented by COOR ³⁰ , -C ₆ H ₅ or -OCOR ³⁰ (in the formula, R ³⁰ represents an alkyl group having 1 to 8 carbon atoms), t represents an integer of at least 1; , u represents zero or a positive integer, and s represents an integer of 1 or more, preferably an integer such that the average number molecular weight of the polymercaptan is at most 1000. ) consisting of mercaptan-terminated poly(butadiene). Class 6 of polymercaptans for use as component (b) have the formula L: (wherein a and each R have the meanings given in the formula). Class 7 is poly(thioglycolate) and poly(mercaptopropionate) of tris(2-hydroxyethyl)isocyanurate and tris(2-hydroxypropyl)isocyanurate,
and N,N'-bis(2-hydroxyethyl)
- and N,N'-bis(2-hydroxypropyl)-hydantoin, i.e. of the following formula: or (wherein each R has the meaning given in the formula and each
R ¹³ has the meaning given in the formula and each R ²⁰
has the meaning given in the expression, and
R ³¹ represents a -OCR ²⁰ SH group or a hydrogen atom. )
Poly(thioglycolate) of the compound represented by
and poly(mercaptopropionate). Specific examples of suitable polymercaptans (C) are pentaerythritol tetrathioglycolate, dipentaerythritol hexa(3-mercaptopropionate), trimethylolpropane trithioglycolate, ethylene glycol dithioglycolate, with an average molecular weight of 800. Tris (3-mercapto-2-hydroxypropyl ether) of polyoxypropylene triol, average formula L: HS (C ₂ H ₄ OCH ₂ OC ₂ H ₄ SS) ₆ C ₂ H ₄ OCH ₂ OC ₂ H ₄ SH
Polysulfide represented by (L), N,N′,N″-tris(3-(mercaptoacetyloxy)ethyl)
-1,3,5-triazine-2,4,6-trione and 1,3-bis(2-(mercaptoacetyloxy)ethyl)-5,5-dimethylhydantoin. In the photopolymerization of the composition of the present invention, the wavelength is 200~
Preference is given to using actinic radiation at 600 nm. Suitable sources of actinic radiation are carbon arcs, mercury arcs, fluorescent lamps with phosphorus that emit ultraviolet light, argon and xenon glow lamps, tungsten lamps and photographic floodlights. Among these, mercury arc especially solar lamp,
Fluorescent solar lamps and metal haloenide lamps are optimal. The time required to expose the photopolymerized composition depends on a variety of factors, including, for example, the particular compound used, the type of light source, and the distance from the irradiated composition. Suitable times can be readily determined by those familiar with photopolymerization technology. For photopolymerization, a composition (other than one containing a compound of the formula) is treated with an added photoinitiator, i.e., which provides an excited state during irradiation to form free radicals; It should contain a catalyst to initiate polymerization of the composition. Suitable photoinitiators are given in the European patent application cited above. Generally, 0.05 to 10% by weight of photoinitiator is mixed, preferably 0.5 to 5% by weight, based on the combined weight of components (a), (b) and (c). Free radical catalysts suitable for the polymerization of the compositions of the invention are thermally activated and exert fairly rapid polymerization action only at temperatures above room temperature. Such suitable catalysts are also given in the above-mentioned European patent applications. The amount of free radical catalyst, together with its promoter, is usually based on the total weight of components (a), (b) and (c):
0.05 to 5% by weight, preferably 0.1 to 1% by weight. Standard free radical catalyzed polymerization methods can be carried out. The compositions of the present invention are used as surface coatings for the production of printing plates and printed circuits, as adhesives for the production of fiber-reinforced composite materials, as compositions for dip coating, filament winding and sheet molding. It can be used using the methods described. The invention therefore provides articles having surface coatings consisting of polymerization products made by the process of the invention, and articles having surfaces bonded by polymerization products made by the process of the invention. Furthermore, the inventors have discovered that the composition of the invention can be cured in two stages. That is, compositions of the present invention containing a thermally activated free radical catalyst and optionally a photoinitiator cannot be partially polymerized by exposure to actinic radiation doses insufficient to cause complete polymerization. can.
This is then heated to activate the free radical catalyst and complete the cure. Other features of the invention therefore provide a composition comprising components (a), (b) and (c) as described above, optionally a photoinitiator and a thermally activated free radical catalyst, and exposing the composition to actinic radiation. A method of curing the composition comprises heating the composition to partially polymerize by exposing and then activating the thermally activated free radical catalyst. The above compositions can be used to form adhesive films, composites, dip coatings and to make sheet molding compositions, as described in US Pat. No. 4,220,513. The compositions of the invention may be marketed in two ingredient bags, one containing ingredients (a) and (c) and the other containing ingredient (b), or as a three ingredient bag. be able to. In addition, the compositions of the invention can be stored for short periods of time as a mixture, protected from actinic radiation and free radical sources. The present invention will be further explained with reference to Examples below. In the examples, "%" represents "% by weight". 2,2-bis(3-allyl-4-(3-(methacryloyloxy)-2-hydroxypropoxy)
Phenyl)propane was prepared as described in the above European patent application or as described below. 2,2-bis(3-allyl-4-hydroxyphenyl)propane (308g) was mixed with 2-methoxyethanol (10g) and epichlorohydrin (740g).
g) and heated to 60°C. Sodium hydroxide flakes (80 g) were added dropwise over 3 hours and the mixture was also stirred at 60° C. for a further 1/2 hour. The mixture was filtered, the residue was washed with toluene, and the filtrate was evaporated under reduced pressure to remove excess solvent and epichlorohydrin. The concentrated product was filtered again to give a 2,2-
Bis(3-allyl-4-(glycidyloxy)phenyl)propane was obtained. This diepoxide (100 g) and 2,6-di-tert-butyl-p-cresol (0.2 g) were mixed and heated to 100°C. Add 1 1/2 to this mixture
Over time, methacrylic acid (45 g), 5% chromium octoate solution (0.1 g) dissolved in diesel oil and 2,6-di-tert-butyl-p-cresol (0.4
g) mixture was added. The mixture was stirred at 100° C. until the epoxide content was negligible. 0.44 g of tetramethylammonium chloride and 0.3 g of 2,6-di-tert-butyl-p-cresol
Methylbicyclo[2.2.1]hept- containing g
2-ene-5,6-dicarboxylic anhydride (89g)
and 2-hydroxyethyl methacrylate (65
2-(methacryloyloxy)ethylmethyl-5-carboxybicyclo[2.2.1]hept-2-ene-6- by heating the mixture of g) to 90°C and stirring for a further 3 hours at that humidity. A carboxylate was produced. Methylbicyclo[2.2.1]hept-2-ene-5,
2-(methacryloyloxy)ethyl 5-carboxycyclohex-1-ene-4-carboxylate was produced in the same manner using 82 g of tetrahydrophthalic anhydride instead of 6-dicarboxylic anhydride. 1-allyloxycarbonyl-2-(3-methacryloyloxy-2-hydroxypropoxycarbonyl)benzene was produced as follows. Phthalic anhydride (74g), allyl alcohol (87g)
g) and tetramethylammonium chloride (0.16g) were mixed and stirred at 80°C for 1 1/4 hours.
The mixture was then cooled and excess allyl alcohol was removed under reduced pressure. The residue (103g) was mixed with tetramethylammonium chloride (0.17g) and 2,
Treated with 6-di-tert-butyl-4-methylphenol (0.35g) and heated at 80°C. At this temperature, glycidyl methacrylate (71 g) was added dropwise over 1/2 hour. Heat the mixture at 80°C for another 2 1/2
Stir for hours. The weight of the product with an epoxide content of 0.48 eq/Kg was 174 g. Dean and Stark
A mixture of 125.5 g of tris(2-hydroxyethyl)isocyanurate, 142.6 g of thioglycolic acid, 4.14 g of toluene-p-sulfonic acid and 250 ml of toluene (30 ml of water taken) was heated at reflux temperature in a Heat for 1/2 hour, then cool the toluene solution and dilute with 250 ml of water twice to 5%
Once with 250 ml of sodium bicarbonate solution and again with 250 ml of water.
ml, dried over magnesium sulfate, filtered and the toluene was distilled off to give N,N′,N″-
Tris(2-(mercaptoacetoxy)ethyl)-
1,3,5-triazine-2,4,6-trione was produced. Yield is 190g, thiol content is 5.9
Equivalent weight/Kg. 1,3-bis(2-(mercaptoacetyloxy)ethyl)-5,5-dimethylhydantoin,
1,3-bis(2-hydroxyethyl)-5,5
- Prepared in a similar manner from 113 g of dimethylhydantoin and 96.6 g of thioglycolic acid (20 ml of water taken). The yield was 138.5g, and the thiol content was
It was 5.3 equivalent/Kg. Example 1 2,2-bis(3-allyl-4-(3-(methacryloyloxy)-2-hydroxypropoxy)
phenyl)propane, 5 g of 2-(methacryloyloxy)ethylmethyl-5-carboxybicyclo[2.2.1]hept-2-ene-6-carboxylate, 3.8 g of pentaerythritol tetrathiocricholate (i.e. 1 per allyl group). thiol equivalent) and benzyl dimethyl ketal 0.56 g
The mixture was applied as a 10 μm thick film to a copper-coated laminate. 1 under a mercury arc lamp with a ratio of 80w/cm at a distance of 8cm
A tack-free film was created by irradiation for seconds. Further, the photo negative was irradiated for 15 minutes under a mercury arc lamp with a ratio of 30 W/cm at a distance of 22 cm, and then
% aqueous sodium hydroxide solution to form a good image. This image was then laminated
It could be removed by immersion in a 10% aqueous sodium hydroxide solution. Example 2 2-(methacryloyloxy)ethylmethyl-
5-carboxybicyclo[2.2.1]hept-2-
The procedure of Example 1 was repeated using 1.2 g of acrylic acid instead of ene-6-carboxylate.
A good image was formed by developing with 1% aqueous sodium hydroxide. Example 3 2-(methacryloyloxy) in place of 2-(methacryloyloxy)ethylmethyl-5-carboxybicyclo[2.2.1]hept-2-ene-6-carboxylate prepared as in Example 1.
Ethyl 5-carboxycyclohex-1-ene-
A mixture containing 10 g of 4-carboxylate and 0.71 g of benzyl dimethyl ketal was applied to the copper laminate and irradiated similarly except for a 2 second exposure to obtain the desired tack-free layer. The layer was further irradiated and developed with 1% aqueous sodium carbonate to form a good image. The image could then be removed by immersion in a 5% aqueous sodium hydroxide solution. Example 4 5.6 g of N,N',N''-tris(2-(mercaptoacetyloxy)ethyl)-1,3,5-triazine-2,4,6-trione instead of pentaerythol tetrathioglycolate and replaced 0.56g of benzyl methyl ketal with 0.63g
The method of Example 1 was repeated using: A good image was obtained by irradiating through the negative for the necessary 10 minutes and developing with a 1% aqueous sodium hydroxide solution. Example 5 Pentaerythritol tetrathioglycolate was replaced by 6.2 g of 1,3-bis(2-(mercaptoacetyloxy)ethyl)-5,5-dimethylhydantoin, and 0.56 g of benzyl dimethyl ketal was replaced by 0.65 g. Example 1 using g
The method was repeated. A good image was obtained by developing with 1% sodium hydroxide. Example 6 2,2-bis(3-allyl-4-(3-methacryloyloxy)-2-hydroxypropoxy)
10 g of phenyl)propane, 2-(methacryloyloxy)ethyl 5-carboxycyclohexe-1
-ene-4-carboxylate 5g, 1,3-bis(2-(mercaptoacetyloxy)ethyl)-
6.2 g of 5,5-dimethylhydantoin and 2.2'-
Azobis(2-methylpropionitrile) 0.65g
The composition consisting of the following was applied as a 10 μm thick film onto a tin plate and cured by heating at 120° C. for 10 minutes to obtain a solvent-resistant coating film. Example 7 1-allyloxycarbonyl-2-(3-methacryloyloxy-2-hydroxypropoxycarbonyl)benzene 7.0g, acrylic acid 1.4g,
A composition consisting of 2.2 g of ethylene glycol dithioglycolate and 0.2 g of benzyl dimethyl ketal was applied as a 10 μm thick film to a copper-coated laminate. 10 under a mercury arc lamp (80w/cm) at a distance of 8cm.
A tack-free film was produced by irradiating for seconds. The photographic negative was further irradiated for 20 minutes under a mercury arc lamp (30 W/cm) at a distance of 22 cm, and then developed with a 1% aqueous sodium carbonate solution to form a good image.

Claims (1)

[Claims] 1 (a) At least one group selected from acryloyloxy and methacryloyloxy groups (), directly or via an oxygen atom or an oxycarbonyl group (-OCO-) in the molecule, containing an aromatic At least one group selected from allyl, methallyl, and 1-propenyl group bonded to a carbon atom forming part of the nucleus
(b) containing in the molecule at least one group () selected from acryloyloxy and methacryloyloxy groups; at least one free carboxy group (); and (c) a compound containing at least two mercaptan groups per molecule directly bonded to aliphatic carbon atoms, with a group selected from allyl, methallyl and 1-propenyl groups in component (a). providing at least 0.8 mercaptan groups per mercaptan group,
However, 1.0 per group selected from acryloyl, methacryloyl, allyl, methallyl and 1-propenyl groups in component (a) to which component (b) has been added.
a polymerizable composition containing less than 2 mercaptan groups. 2 Component (a) as a whole is a group () and a group ()
The composition according to claim 1, which contains at least three of the following. 3 The acryloyloxy or methacryloyloxy group in component (a) is directly or formula: Group or formula represented by: (In the formula, R represents a hydrogen atom or a methyl group,
and a represents an integer from 1 to 6. ) The composition according to claim 1 or 2, wherein the composition is bonded to the carbon atom of the aromatic nucleus via a group represented by the following. 4 Component (a) directly or via the (terminal) ether oxygen atom of the formula or the group represented by the formula,
A polyhydric phenol having at least two phenolic hydroxyl groups esterified with an acryloyl or methacryloyl group and at least two phenolic hydroxyl groups directly etherified with a group selected from allyl, methallyl and 1-propenyl groups. The composition according to claim 3, which is 5. Component (a) has at least two phenolic hydroxyl groups which are esterified with a group selected from acryloyl and methacryloyl groups, either directly or via the (terminal) ether oxygen atom of the formula or the group represented by the formula. Claim 1, which is a polyhydric phenol, wherein the carbon atoms of the benzene or naphthalene nucleus are directly substituted by at least two groups selected from allyl, methallyl and 1-propenyl groups. 3
Compositions as described in Section. 6. Component (a) contains at least one carboxylic acid group bonded to the acryloyl or methacryloyl group via the (terminal) carbon atom of the formula or the group represented by the formula and allyl, methallyl and 1-
The composition according to claim 3, which is a polyhydric carboxylic acid having at least one carboxylic acid group directly esterified with a group selected from propenyl groups. 7 Each of the acryloyloxy or methacryloyloxy groups in component (b) is bonded directly to a hydrogen atom, or directly or via a carboxyl group-containing group to a carbon atom of an aliphatic, cycloaliphatic or aromatic group or a heterocyclic group. Claims 1 to 6 bonded to a nitrogen atom forming part of a ring
The composition according to any one of paragraphs. 8 The carboxyl group-containing group has the formula; (In the formula, R ¹¹ represents an alkylene, arylene, or aralkylene group which may be substituted with one or more other carboxylic acid groups, and the alkylene group and the alkylene moiety of the aralkylene group have 2 to 10 carbon atoms. 8. The composition of claim 7, wherein the arylene group and the arylene moiety of the aralkylene group have 6 to 10 carbon atoms. 9. A patent in which component (b) is present in an amount that provides 0.75 to 1.25 groups selected from acryloyloxy and methacryloyloxy groups for each group selected from acryloyloxy and methacryloyloxy groups in component (a) Claims 1 to 8
The composition according to any one of paragraphs. 10. Any one of claims 1 to 9, wherein component (c) is an ester of a monomercaptan alkylene carboxylic acid and a polyhydric alcohol or an ester of an aliphatic monomercaptan monohydric alcohol and a polycarboxylic acid. Composition according to item 1.