JPH107754A - Photopolymerizable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photopolymerizable resin compsn. which cures by exposure to light at a higher rate than a vinyl ether compd, and is excellent in flow properties, physical properties after curing, adhesion to a metal, etc., by compounding a compd. having properly ether groups with a cationic photopolymn. initiator. SOLUTION: This compsn, is prepd. by compounding a propenyl ether compd. having propenyl ether group represented by the formula: CH3 -CH=CH-O- and a number average mol.wt. of 500 or higher with a cationic photopolymn. initiator. pref. the compd. has at least five propenyl ether groups and a main chain selected from among polyether, polyvinyl, polyester, polyurethane, polyamide, polycarbonate, and novolak main chains. Pref. the initiator is an onium salt (e.g. triarylsulfonium salt).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition containing a compound having a propenyl ether group and having high-speed curability, and a cured product thereof. More specifically, the present invention relates to a resin composition that cures in a very short time by irradiation with ultraviolet light or an electron beam, and a cured product obtained by curing the resin composition.

[0002]

2. Description of the Related Art Photocurable resin compositions are used as resist materials for printed wiring boards, resists for liquid crystals, etc., hard coat agents, optical fiber coating agents, optical disk coating agents, paper coating agents, woodworking coating agents. Widely used as photosensitive resins such as paints, photosensitive printing plates, printing inks and adhesives. As such a photocurable resin composition, an acrylate resin represented by epoxy acrylate, urethane acrylate, or the like;
Alicyclic epoxy resins, vinyl ether resins and the like have been put to practical use.

[0003]

However, the acrylate resin is extremely poor in surface curability because polymerization is inhibited by oxygen at the time of curing, and it is difficult to cope with a high-speed UV curing process due to its high viscosity. is there. Although the alicyclic epoxy resin does not inhibit polymerization by oxygen, the curing speed is extremely low when cured by photocationic polymerization. As a photosensitive resin composition in which these points are improved, a vinyl ether resin can be cited, but the curing speed is not sufficient for applications requiring high-speed curability.

[0004] Crivello et al., Journal of Polymer Science.
of Polymer Science), Part A
(Part A), polymer chemistry (Polym
er Chemistry, Vol. 31, p. 1473 (1993), discloses a propenyl ether compound that cures by light irradiation at a higher speed than a vinyl ether compound. However, they are not sufficiently satisfactory for industrial use because of their high volatility and insufficient flow properties. Furthermore, a high-speed curable photosensitive resin composition which has insufficient hardness and adhesiveness to metal and is durable for industrial use is desired.

SUMMARY OF THE INVENTION In view of the above situation, an object of the present invention is to cure by irradiation with light at a higher speed than a vinyl ether compound, and to be excellent in flow characteristics, resin cured properties, adhesion to metal, and the like, and to be manufactured at a low cost. An object of the present invention is to provide a photocurable resin composition.

[0006]

The present invention provides a compound (A) having a propenyl ether group represented by the following formula (1) in the molecule and having a number average molecular weight of 500 or more: And a photocurable resin composition comprising a cationic photopolymerization initiator (B). CH ₃ —CH ＝ CH—O— (1) Hereinafter, the present invention will be described in detail.

The photocurable resin composition of the present invention comprises a compound having a propenyl ether group (A) and a cationic photopolymerization initiator (B). Hereinafter, the propenyl ether group-containing compound (A) will be described in detail. The propenyl ether group-containing compound (A) in the present invention (hereinafter referred to as “
This is referred to as “compound (A)”) having a propenyl ether group represented by the above formula (1) in the molecule. The compound (A) preferably has at least five propenyl ether groups in the molecule. If the number is less than 5, the curing speed is reduced. More preferably, it has at least ten.

The number average molecular weight of the compound (A) is 50
0 or more. If it is less than 500, the viscosity will be low, the fluidity will be high, and film formation will be difficult, so it will be limited to the above range. More preferably, it is 1000 or more.

The compound (A) is not particularly limited as long as it has the above propenyl ether group and has a number average molecular weight of 500 or more, but may be polyether, polyvinyl, polyester, polyurethane, polyamide,
Those having at least one main chain selected from the group consisting of polycarbonate and novolak are preferred. In this case, the compound (A) preferably has at least five propenyl ether groups in a side chain.

[0010] Among the above compounds (A), polyethers,
As those having at least one kind of main chain selected from the group consisting of polyvinyl, polyester, polyurethane, polyamide, polycarbonate and novolak, those having structures represented by the following general formulas (2) to (10), respectively Etc. are exemplified.

[0011]

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Hereinafter, these will be described in detail. Compound (A) having a structure represented by the above general formula (2)
Has a polyether main chain. In the general formula (2), a is an integer of 2 to 200. a is 200
If it exceeds, the viscosity will usually be high and it will be difficult to dissolve the cationic photopolymerization initiator (B). If it is less than 2, the viscosity will be low and the fluidity will be high, making film formation difficult.
Preferably it is 2-80, More preferably, it is 5-10. A ¹ represents an alkylene group substituted or unsubstituted with an —XZ group, an arylene group, an aralkylene group, a haloalkylene group, or a residue obtained by ring-opening polymerization of a glycidyl ether. In the present specification, -X-
The Z group represents a group represented by -XZ (wherein, X represents a divalent organic group; Z represents a propenyl ether group represented by the general formula (1)). A in the general formula (1)
Preferably, at least 5 of the A ¹ groups are groups substituted with a —XZ group.

In the general formula (2), a number of A
¹ may be the same or different, and the (A ¹ -O) a portion may be a random addition or a block addition.

Examples of X include, for example, one or more groups selected from the group consisting of ether groups, carbonate groups, ester groups, imino groups, amide groups, urethane groups, urea groups and sulfide groups. is exemplified also be a hydrocarbon group or the like have, as specific examples, eg, -CH _{2
-, - CH 2 CH 2 -} , - CH 2 OCH 2 CH 2 -, -
_{CHOC (= O) OCH 2 -} , - CH 2 NHCH 2 CH
_{2 -, - CH 2 NHC (} = O) NH (CH 2) 6 NHC
(= O) O -, - CH 2 S (CH 2) 2 C (= O) O
(CH ₂ ) _2- and the like.

Specific examples of A ^{1 in} the general formula (2) include methylene, ethylene, propylene, 1-
Butylene group, 2-butylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, tetramethylene group, methyltetramethylene group, pentamethylene group, pentylene group, isoamylene group, hexylene group, cyclohexene group, neohexene group, A group in which a hydrogen atom of an alkylene group exemplified by a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, a dodecylene group or the like is substituted by an -XZ group; a methylene group, an ethylene group, a propylene group, a 1- Butylene group, 2-butylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, tetramethylene group, methyltetramethylene group, pentamethylene group, pentylene group, isoamylene group, hexylene group, cyclohexene group, neohexene group, Heptylene, octylene, nonylene, deci Alkylene groups such as phenylene, undecylene and dodecylene groups; arylene groups such as phenylene, naphthylene, anthrylene and phenanthrylene; benzylene, 1-phenylene, 2-phenylene, 1-phenylpropylene and 2-phenylene Aralkylene groups such as phenylpropylene group and 3-phenylpropylene group; haloalkylene groups such as chloroethylene group, dichloroethylene group, bromoethylene group and chloromethylethylene group; butyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, 2- Ethylhexyl glycidyl ether, cresyl glycidyl ether, p-sec-butylphenyl glycidyl ether,
Glycidyl methacrylate, diglycidyl ether,
(Poly) ethylene glycol diglycidyl ether,
(Poly) propylene glycol diglycidyl ether,
Examples thereof include residues obtained by ring-opening polymerization of glycidyl ethers such as butanediol diglycidyl ether, diglycidylaniline, trimethylolpropane triglycidyl ether, and glycerin triglycidyl ether.
Of these, an alkylene group having 2 to 6 carbon atoms is preferable, and an ethylene group and a propylene group are more preferable. When the alkylene group is long, the solubility of the cationic photopolymerization initiator (B) becomes poor.

Specific examples of the compound (A) having the structure of the above general formula (2) include, for example, the following general formula (12): R ³ [—O— (A ¹ —O) a—R ⁴ ] m ₁ (12) (wherein, R ³ represents a residue obtained by removing m ₁ hydroxyl group from a polyhydric alcohol or polyhydric phenol. R ⁴ represents a propenyl group, a hydrogen atom, an alkyl group, an acyl group, ) .m ₁ representing at least two, propenyl of .m ₁ single R ⁴ representing an acryloyl group or an aryl group, 2
It is an integer of ~ 200. ) And the like.

The polyhydric alcohols include, for example, glycerin, polyglycerin (2 to 18-mer of glycerin, such as diglycerin, triglycerin, tetraglycerin, etc.);
Trimethylolalkane (trimethylolethane, trimethylolpropane, trimethylolbutane, etc.) and dimers and trimers thereof; monopentaerythritol, dipentaerythritol, 1,3,3
Polyhydric alcohols such as 5-pentaerythritol, sorbitol, sorbitan, sorbitan glycerin condensate, adonitol, arabitol, xylitol, mannitol; xylose, arabinose, ribose, rhamnose, glucose, fructose, galactose, mannose, sorbose, cellobiose, maltose Saccharides; and partially etherified products thereof (eg, methyl ether, ethyl ether), partially acetic acid esterified products, methyl glucoside; polyvinyl alcohol (polymer having a polymerization degree of 5 to 700), and polymer of 2-hydroxyethyl acrylate (Polymer having a polymerization degree of 5 to 700), polymer of 2-hydroxyethyl methacrylate (polymer having a polymerization degree of 5 to 700), and polymer of allyl alcohol (polymerization degree of 5 to 7) 0 polymer) and the like. Among them, glycerin, polyglycerin, trimethylolalkane and its dimer to trimer are particularly preferable.

Examples of the polyhydric phenol include cresol novolak resin and phenol novolak resin.

The compound (A) having the structure represented by the general formula (3) has a polyvinyl main chain.
In the general formula (3), b is an integer of 2 to 200.
When b exceeds 200, the viscosity usually increases and the dissolution of the cationic photopolymerization initiator (B) becomes difficult. When it is less than 2, the viscosity becomes low and the fluidity becomes high, so that film formation becomes difficult. Become. Preferably it is 3-100, More preferably, it is 3-20. Q ¹ represents a hydrogen atom, a hydroxyl group, an alkyl group, an aryl group, a haloalkyl group, a haloaryl group, an alkoxycarbonyl group, an acetoxy group, or-
Represents an XZ group. The b Q ¹ in the general formula (3) may be the same or different. Further, it is preferable that at least 5 of the b Q ^{1 in} the general formula (3) be a group substituted with a —XZ group.

Specific examples of Q ^{1 in} the general formula (3) include a hydrogen atom; a hydroxyl group; an alkyl group such as a methyl group and an ethyl group; an aryl group such as a phenyl group and a tolyl group; A haloalkyl group such as a chloromethylphenyl group, a chloroethylphenyl group,
Haloaryl groups such as 4,6-trichlorophenyl group and 2,4,6-tribromophenyl group; alkoxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group and butoxycarbonyl group; acetoxy group and -XZ group. No.

The compound (A) having the structure represented by the general formula (4) has a polyester main chain. In the general formula (4), c is an integer of 2 to 200. When c exceeds 200, the viscosity usually increases and it becomes difficult to dissolve the cationic photopolymerization initiator (B). When c is less than 2, the viscosity becomes low and the fluidity becomes high, so that film formation becomes difficult. Preferably 2-80, more preferably 2
-20. A ² is a residue of an alkylene diol substituted or unsubstituted with an -XZ group, -X-
Represents a residue of an arylene diol substituted or unsubstituted with a Z group, or a residue of a polyether diol substituted or unsubstituted with a -XZ group. A ³ is an alkylene group substituted or unsubstituted with an -XZ group, an arylene group substituted or unsubstituted with an -XZ group, an aralkylene group,
Or, it represents a haloalkylene group. In the general formula (4), c A ² and c A ³ may be the same or different. In addition, it is preferable that at least 5 of c A ² and c A ^{3 in} the general formula (4) be a group substituted with a —XZ group.

[0022] In the A ^2, specific examples of diols excluding the hydroxyl group corresponding to A ² is ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6 Alkylene diols such as hexanediol, 1,9-nonanediol, neopentyl glycol, 1,4-cyclohexanediol; catechol, bis (2-hydroxyphenyl)
Arylene diols such as methane, bis (4-hydroxyphenyl) methane, bisphenol A; poly (oxyethylene) diol, poly (oxypropylene) diol, poly (oxytetramethylene) diol, ethylene oxide adduct of bisphenol A, bisphenol A Polyether diols such as propylene oxide adducts, and those in which hydrogen atoms other than hydroxyl groups of these diols are substituted with -XZ groups. Of these, poly (oxyethylene) diol and poly (oxypropylene) diol are preferred. The degree of polymerization of the above polyether diol is usually 2 to 200, preferably 2 to 100, particularly preferably 3 to 20.

[0023] Specific examples of the A ³ in the general formula (4), a methylene group, an ethylene group, a propylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, undecylene group A hydrogen atom of an alkylene group such as a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, and a dodecylene group;
A group substituted with an XZ group; an arylene group such as a phenylene group, a naphthylene group, an anthrylene group, a phenanthrylene group; a phenylene group, a naphthylene group, an anthrylene group;
A hydrogen atom of an arylene group such as a phenanthrylene group is -X
A group substituted with a -Z group; an aralkylene group such as a benzylene group, a 1-phenylene group, a 2-phenylene group, a 1-phenylpropylene group, a 2-phenylpropylene group, or a 3-phenylpropylene group; a chloroethylene group, a dichloroethylene And haloalkylene groups such as a bromoethylene group and a chloromethylethylene group.

Specific examples of the compound (A) having the structure of the above general formula (4) include, for example, the following general formula (13)

[0025]

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(Wherein R ⁵ represents m ₂ from a polyvalent carboxylic acid)
Represents a residue excluding a number of carboxyl groups. R ⁶ represents a diol residue of any of polyether diol, polyurethane diol and polycarbonate diol. R ⁷ represents a propenyl group, a hydrogen atom, an alkyl group, an acyl group, a (meth) acryloyl group or an aryl group. At least two of m ₂ R ⁷ represent a propenyl group. m ₂ is an integer of 2 to 200. ) And the like.

Examples of the polycarboxylic acid include isophthalic acid, terephthalic acid, adipic acid and the like.

The compound (A) having the structure represented by the general formula (5) has a polyester main chain. In the general formula (5), d is an integer of 2 to 200. When d exceeds 200, the viscosity usually increases and it becomes difficult to dissolve the cationic photopolymerization initiator (B). When d is less than 2, the viscosity becomes low and the fluidity becomes high, so that film formation becomes difficult. Preferably 2-80, more preferably 2
Is an integer of up to 20. A ⁴ is, -X-Z substituted or unsubstituted alkylene group with a group, -X-Z substituted or unsubstituted arylene group with a group, aralkylene group, or a haloalkylene group. The d A ⁴ 's in the general formula (5) may be the same or different. Further, it is preferable that at least 5 of d A ^{4 in} the general formula (5) are a group substituted with a —XZ group.

[0029] Specific examples of the A ⁴ in the general formula (5), such as those exemplified as specific examples of the A ³ and the like.

The compound (A) having the structure represented by the general formula (6) has a polyurethane main chain. In the above general formula (6), e is an integer of 2 to 200. When e exceeds 200, the viscosity is usually high and the dissolution of the cationic photopolymerization initiator (B) is difficult. Preferably 2 to 50, more preferably 2
Is an integer of up to 20. A ⁵ represents a residue obtained by removing an isocyanate group from diisocyanate. A ⁶ is -XZ
A residue of an alkylene diol substituted or unsubstituted with a group, a residue of an arylene diol substituted or unsubstituted with a -XZ group, or a group substituted or unsubstituted with a -XZ group It represents the residue of a (poly) ether diol or the residue of a polyester diol substituted or unsubstituted with an -XZ group.
Formula (6) d pieces of A ⁵ and d pieces of A ⁶ in may each be the same or different. In addition, at least 5 of d A ⁵ and d A ^{6 in} the general formula (6) are preferably a group substituted with a —XZ group.

[0031] In the A ^5, specific examples of the diisocyanate to give A ⁵ Excluding the isocyanate groups,
Tolylene diisocyanate (TDI), p-phenylene diisocyanate, m-phenylene diisocyanate,
1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 4,4′-dicyclohexylmethane diisocyanate (Desmodur W), 4,
4'-diphenylmethane diisocyanate (MDI),
1,5-tetrahydronaphthalene diisocyanate, naphthalene-1,5-diisocyanate, bis (2-methyl-3-isocyanatophenyl) methane, 4,4'-diphenylpropane diisocyanate, tetramethylxylylene diisocyanate (TMXDI), isophorone diisocyanate (IPDI) and the like. Of these, tolylene diisocyanate (TD)
I), 4,4'-diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPD
I), tetramethyl xylene diisocyanate (TMX
DI), 4,4'-dicyclohexylmethane diisocyanate (Desmodur W) and 1,6-hexamethylene diisocyanate.

[0032] In the A ^6, specific examples of the diol giving A ⁶ except a hydroxyl group, ethylene glycol, propylene glycol, 1,3-butanediol,
1,4-butanediol, 1,6-hexanediol,
1,9-nonanediol, neopentyl glycol,
Alkylene diols such as 1,4-cyclohexanediol; arylene diols such as catechol, bis (2-hydroxyphenyl) methane, bis (4-hydroxyphenyl) methane, bisphenol A; poly (oxypropylene) diol, poly (oxytetramethylene) ) Polyether diols such as diols, ethylene oxide adducts of bisphenol A and propylene oxide adducts of bisphenol A; polyester diols such as poly (ethylene adipate) diol, poly (butylene isophthalate) diol, polycaprolactone diol; these diols In which a hydrogen atom other than a hydroxyl group of the formula (1) is substituted with an -XZ group. Of these, poly (oxyethylene) diol and poly (oxypropylene) diol are preferred.

[0033] Specific examples of the compound (A) having a structure of the general formula (6) is, for example, the following general formula ^{(14) R 8 (NHCOO-} R 9) m 3 (14) ( wherein, R ⁸ Represents a residue obtained by removing an isocyanate group from a polyvalent isocyanate, and R ⁹ represents — (Z ¹ O) n—C
H = CH-CH ₃ ^{group, - (Z 1 O) n} -CO-C
(R ¹⁰⁾ = CH ₂ group, - represents a (Z ¹ O) nH group, hydrogen or an alkylene group. At least one of the m ₃ pieces of R ⁹ - a ^{(Z 1 O) n-CH} = CH-CH 3 group, at least another ^{one, - (Z 1 O) n} -CO-C (R ¹⁰ )
＝ CH ₂ group. Z ¹ represents an alkylene group having 2 to 12 carbon atoms, an arylene group, an aralkylene group or a cycloalkylene group. R ¹⁰ represents hydrogen or a methyl group. n is an integer of 0 to 200. m2 is ₂ to 2
It is an integer of 00. ) And the like.

Examples of the polyvalent isocyanate include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, isophorone diisocyanate, tetramethyl xylene diisocyanate, and 4,4 '
-Dicyclohexylmethane diisocyanate, 1,6-
Hexamethylene diisocyanate, triphenylmethane triisocyanate, tris (isocyanatophenyl)
Thiophosphate and the like.

The compound (A) having the structure represented by the general formula (7) has a polyamide main chain.
In the general formula (7), f is an integer of 2 to 200.
When f exceeds 200, the viscosity usually increases and the dissolution of the cationic photopolymerization initiator (B) becomes difficult, and when it is less than 2, the viscosity becomes low and the fluidity becomes high, so that film formation becomes difficult. . Preferably from 2 to 50, more preferably from 2 to
It is an integer of 20. A ⁷ and A ⁸ are the same or different and are each an alkylene group substituted or unsubstituted with an -XZ group, an arylene group substituted or unsubstituted with an -XZ group, an aralkylene group, Or, it represents a haloalkylene group. In the general formula (7), f A ⁷ and f A ⁸ may be the same or different. It is preferable that at least 5 of the f A ⁷ and the f A ^{8 in} the general formula (7) are a group substituted with a —XZ group.

Specific examples of A ⁷ and A ^{8 in} the general formula (7) include those exemplified as the specific examples of A ³ above.

The compound (A) having the structure represented by the general formula (8) has a polyamide main chain.
In the above general formula (8), g is an integer of 2 to 200.
When g exceeds 200, the viscosity usually increases and the dissolution of the cationic photopolymerization initiator (B) becomes difficult. When it is less than 2, the viscosity becomes low and the fluidity becomes high, so that film formation becomes difficult. . Preferably from 2 to 50, particularly preferably from 2 to
It is an integer of 20. A ⁹ represents an alkylene group substituted or unsubstituted with an -XZ group, an arylene group substituted or unsubstituted with an -XZ group, an aralkylene group, or a haloalkylene group. The g A ⁹ 's in the general formula (8) may be the same or different. Further, it is preferable that at least 5 of the g A ^{9 in} the general formula (8) are a group substituted with a —XZ group.

Specific examples of A ^{9 in} the general formula (8) include those exemplified as A ³ above.

The compound (A) having the structure represented by the general formula (9) has a polycarbonate main chain. In the general formula (9), h is an integer of 2 to 200. When h is more than 200, the viscosity usually becomes high and it becomes difficult to dissolve the cationic photopolymerization initiator (B). . It is preferably an integer of 2 to 50, more preferably 2 to 20. A ¹⁰ is an alkylene group substituted or unsubstituted with an -XZ group, -XZ
Represents an arylene group, an aralkylene group, or a haloalkylene group substituted or unsubstituted by a group. H A ¹⁰ 's in the general formula (9) may be the same or different. Further, it is preferable that at least 5 of the h A ^{10 in} the general formula (9) are a group substituted with a —XZ group.

[0040] Specific examples of the A ¹⁰ in the general formula (9), such as those exemplified as specific examples of the A ³ and the like.

The compound (A) having the structure represented by the general formula (10) has a novolak main chain. In the general formula (10), i represents an integer of 2 to 200. When i is more than 200, the viscosity is usually high and it is difficult to dissolve the cationic photopolymerization initiator (B), and when it is less than 2, the viscosity is low and the fluidity is high, so that film formation is difficult. . It is preferably an integer of 2 to 50, more preferably 2 to 20. Ar represents an aryl group.
Q ² represents a hydrogen atom, a glycidyl group, or a —XZ group. I Q ² in the general formula (10) may be the same or different. Also, at least two of i number Q ² 'in the general formula (10) is -X-Z group.

The compound (A) having a structure represented by any of the above general formulas (2) to (10) is obtained by adding a propenyl ether group represented by the above formula (1) to a side chain of its main chain and its main chain. At both ends. Of these, it is preferable to have it on the side chain and at both ends of the main chain.

The compound (A) having a structure represented by any of the above general formulas (2) to (10) may have a (meth) acryloyl group in addition to a propenyl ether group.

In the present invention, the method for obtaining the compound (A) is not particularly limited. For example, the compound (A) having a structure represented by the general formula (2) has a corresponding polyfunctional allyl ether group. It can be obtained by propenyl rearrangement of a (poly) ether oligomer with an alkali catalyst.

Examples of the above alkali catalyst include potassium hydroxide, sodium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, potassium tert-butoxide, sodium tert-butoxide.
-Butoxide and the like.

When these alkali catalysts are used, the charge ratio of the alkali catalyst ranges from 0.01 to 5 moles to 1.0 mole equivalent of the (poly) ether oligomer having a polyfunctional allyl ether group. , Preferably in the range of 0.1 to 2 mol, a high reaction promoting effect can be obtained.

Examples of the reaction solvent include dimethyl sulfoxide, dimethylformamide, tetrahydrofuran, dioxane, acetonitrile, butanol, ethylene glycol dimethyl ether, methanol, ethanol, propanol, toluene, polyethylene glycol (compound having a molecular weight of 100 to 20,000) and the like. Can be The reaction temperature is 30 to 170 ° C., preferably 6 to 170 ° C.
0-120 ° C.

A known method can be used for the isolation and purification after the reaction. For example, after cooling the reaction solution to room temperature, removing the inorganic salt by extracting the organic layer with toluene or ether and washing with water several times, a method of obtaining the desired product by concentrating the organic layer under reduced pressure, and the like. It is not limited to this method. Preferably, after cooling the reaction solution to room temperature, excess alkali is neutralized with an acid.

The above-mentioned (poly) ether oligomer having a polyfunctional allyl ether group can be obtained, for example, by a desalting etherification reaction of allyl chloride and a polyfunctional alcohol with an alkali catalyst. Examples of the alkali catalyst include potassium hydroxide, sodium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, potassium-t-butoxide, sodium-t-butoxide and the like. The allyl etherification does not have to be complete and, in nmoles, 20%
May have a hydroxyl group remaining.

When these alkali catalysts are used, the charge ratio of alkali is 1.0
By setting the alkali catalyst in the range of 0.8 to 10 mol, preferably in the range of 1 to 2 mol per mol equivalent, a high reaction promoting effect can be obtained. The equivalent ratio of the polyfunctional alcohol to allyl chloride is usually from 1: 1.0 to 10.0, preferably from 1: 1.0 to 2.0.

As the cationic photopolymerization initiator (B) in the present invention, a known cationic photopolymerization initiator can be used. For example, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium phosphate, p- (phenylthio) phenyldiphenylsulfonium hexafluoroantimonate, p- (phenylthio) phenyldiphenylsulfonium hexafluorophosphate, 4-chlorophenyldiphenylsulfonium hexafluorophosphate, 4-chlorophenyldiphenylsulfonium hexafluoroantimonate, bis [4- (diphenylsulfonio) phenyl]
Sulfide bishexafluorophosphate, bis [4- (diphenylsulfonio) phenyl] sulfidebishexafluoroantimonate, (2,4-cyclopentadien-1-yl) [(1-methylethyl) benzene] -Fe- Hexafluorophosphate, diallyliodonium hexafluoroantimonate and the like can be mentioned. These are readily available from the market. For example, SP-150, SP-17 manufactured by Asahi Denka Co., Ltd.
0; manufactured by Ciba-Geigy, Irgacure 261; manufactured by Union Carbide, UVR-6974, UVR-69
90; CD-1012 manufactured by Sartomer Co., Ltd .;

In the present invention, an onium salt is preferably used as the cationic photopolymerization initiator (B). Further, as the onium salt, it is preferable to use at least one of a triarylsulfonium salt and a diaryliodonium salt.

In the present invention, the ratio of the compound (A) to the cationic photopolymerization initiator (B) is usually from 95: 5 to 99.9: 0.01 by weight. If the ratio of the photocationic polymerization initiator (B) is less than 0.01, a sufficient effect of initiating polymerization cannot be obtained. . Preferably it is 96: 4 to 98: 2.

In the photocurable resin composition of the present invention,
For the purpose of adjusting the viscosity, a reactive diluent (C) comprising a compound having a molecular weight of less than 500 represented by the following general formula (11) can be further contained. CH ₃ —CH ＝ CH—O—R ¹ —O—R ² (11)

In the general formula (11), R ¹ is HO-R
It is a residue obtained by removing a hydroxyl group from an alkylene diol, arylene diol, polyether diol or polyester diol represented by ^1- OH. R ² is an alkyl group, an aryl group, an aralkyl group, a cycloalkyl group, or a hydrogen atom.

Examples of the alkylene diol represented by HO-R ¹ -OH include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, Examples include 9-nonanediol, neopentyl glycol, 1,4-cyclohexanediol, and the like. Examples of arylenediol include catechol, bis (2-hydroxyphenyl) methane, bis (4-hydroxyphenyl) methane, bisphenol A, and the like. Examples of the polyether diol include poly (oxyethylene) diol, poly (oxypropylene) diol, poly (oxytetramethylene) diol, an ethylene oxide adduct of bisphenol A, a propylene oxide adduct of bisphenol A, and the like. Examples of polyester diols include poly (ethylene adipate) diol,
Poly (butylene isophthalate) diol, polycaprolactone diol and the like can be mentioned. Of these, poly (oxyethylene) diol and poly (oxypropylene) diol are preferred.

Specific examples of R ^{2 in} the general formula (11) include a hydrogen atom; a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group,
Alkyl groups such as octyl group, nonyl group, decyl group, undecyl group and dodecyl group; aryl groups such as phenyl group, naphthyl group, anthryl group and phenanthryl group; benzyl group, 1-phenyl group, 2-phenyl group and 3- Arylalkyl groups such as phenylpropyl group, 2-phenylpropyl group and 1-phenylpropyl group; and cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group.

The reactive diluent (C) has a molecular weight of 500
Is less than. If it is 500 or more, the solubility of the cationic photopolymerization initiator (B) becomes poor.

The amount of the reactive diluent (C) is usually 5 to 60% by weight, preferably 10 to 10% by weight, based on the total amount of the compound (A) and the cationic photopolymerization initiator (B).
30% by weight. If it exceeds 60% by weight, the curing speed is significantly reduced.

In the photocurable resin composition of the present invention,
If necessary, the composition may further contain a radically polymerizable vinyl compound (D) and a photoradical polymerization initiator (E).

As the radical polymerizable vinyl compound (D), known radical polymerizable vinyl compounds can be used. For example, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,4-butanediol di (meth)
(Meth) acrylate monomers such as acrylate and tripropylene glycol di (meth) acrylate; styrene, vinyl chloride, vinyl acetate, vinyl ether, acrylic acid, methacrylic acid; epoxy (meth) acrylate;
(Meth) acrylate oligomers such as urethane (meth) acrylate and the like can be mentioned.

The amount of the radical polymerizable vinyl compound (D) is preferably 0 to 100 parts by weight, more preferably 0 to 100 parts by weight, based on 100 parts by weight of the compound (A).
50 parts by weight.

As the photo-radical polymerization initiator (E), known photo-radical polymerization initiators can be used. For example, benzoin alkyl ethers such as benzoin ethyl ether and benzoin isobutyl ether;
Examples include acetophenones such as diethoxyacetophenone; and anthraquinones such as benzyldimethylketal.

The amount of the photoradical polymerization initiator (E) is usually 1 to 5% by weight based on the total amount of the compound (A) and the photocationic polymerization initiator (B).
Preferably it is 2 to 5% by weight.

The photocurable resin composition of the present invention may further contain, if necessary, an organic solvent, an epoxy resin (for example, a bisphenol A epoxy resin, a bisphenol F epoxy resin, a tetrabromobisphenol A epoxy resin, A novolak type epoxy resin), a pigment, a colorant, an inorganic filler, a non-reactive resin, and other various additives.

The photocurable resin composition of the present invention can be obtained by, for example, mixing and dissolving each of the above components and others. Further, the photocurable resin composition of the present invention can be easily cured by irradiating ultraviolet rays or electron beams by a conventional method to obtain a cured product. The ultraviolet irradiation device is not particularly limited, and examples thereof include a high-pressure mercury lamp, a low-pressure mercury lamp, and a metal halide lamp. The electron beam irradiation apparatus is not particularly limited, and examples thereof include a scanning irradiation apparatus (manufactured by Nissin Electric Co., Ltd.) and a curtain irradiation apparatus (manufactured by Iwasaki Electric Co., Ltd.).

The compound (A) of the present invention has a structure of the skeleton between the propenyl ether groups or, when the compound has a (meth) acryloyl group in addition to the propenyl ether group, a functional group between these functional groups. By changing the structure of the skeleton, it is possible to adjust flow characteristics and cured physical properties in a wide range. Further, by optimizing the balance between the number of propenyl ether groups and the structure of the polymer main chain skeleton, it is possible to improve the flow characteristics and the cured physical properties. When the polyester has a polyester in the main chain, it is possible to improve the adhesion to metal.

The photo-curable resin composition of the present invention exhibits a suitable viscosity with excellent flow characteristics as compared with a conventional photosensitive resin using an acrylate resin, an epoxy resin, or a vinyl ether resin, and has rapid curability. Further, since there is no polymerization inhibition by oxygen, it has good surface curability.

The photocurable resin composition of the present invention has a remarkably high curing speed in air and excellent curing characteristics, and therefore can be used as a coating agent for various materials such as metals, plastics, paper, glass, rubber, and wood. , Paints, printing inks, forming materials, resist materials, etc.
Particularly, it is suitable as a composition for a resist for a printed wiring board, a printing ink, a paint, a coating agent for paper, a coating agent for metal, a coating agent for optical fiber, a hard coating agent and an adhesive.

[0070]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Synthesis of Compound (A) Synthesis Example 1 Glycerin 4 was added to a 500 ml SUS autoclave.
6.0 g (0.5 mol) and KOH 0.5 g were charged,
264.3 g of ethylene oxide from a pressure dropping funnel
(6.0 mol) was added dropwise, and the mixture was aged at 110 ° C. for 5 hours.
After cooling the system to 80 ° C, 84.2 g of KOH, 9.67 g of n-tetrabutylammonium bromide and 40 g of toluene were added, and 114.8 g (1.5 mol) of allyl chloride was gradually added at 80 ° C over 1 hour. The mixture was dropped and aged for 5 hours. Thereafter, 200 g of water was added, and the excess alkali and the generated salts were washed with water and separated. 50 ° C, 100m
After removing unreacted allyl chloride and toluene from the organic layer under a pressure of mHg, the product was charged into a glass eggplant flask, and potassium-t-butoxide was used as a catalyst at 32.4.
g, 50 g of dimethyl sulfoxide as a reaction solvent was added, and the mixture was aged at 90 ° C. for 15 minutes (rearrangement reaction). Thereafter, 200 g of water was added, and excess alkali was washed with water to remove liquid. Dimethylsulfoxide contained at 80 ° C. under a reduced pressure of 10 mmHg was removed from the product washed with water, and as a compound (A), an ether oligomer having a propenyl ether group at a terminal [hereinafter, referred to as “compound (1)”) was added.
33.4 g were obtained. The product is ¹ H-NMR, ¹³ C-NMR
Confirmed by

Synthesis Example 2 In a 500 ml autoclave made of SUS, 67.1 g (0.5 mol) of trimethylolpropane and 0.5 g of KOH were charged, and ethylene oxide 26 was added through a pressure-resistant dropping funnel.
4.3 g (6.0 mol) was added dropwise and aged at 110 ° C. for 5 hours. After cooling the system to 80 ° C., 84.2 g of KOH,
9.67 g of n-tetrabutylammonium bromide,
40 g of toluene was added, and 114.8 g of allyl chloride was added.
(1.5 mol) was gradually added dropwise at 80 ° C. over 1 hour,
Aged for 5 hours. Thereafter, 200 g of water was added, and the excess alkali and the generated salts were washed with water and separated. 50
After removing unreacted allyl chloride and toluene from the organic layer at 100 ° C. and a pressure of 100 mmHg, the product was charged into a glass eggplant flask, 32.4 g of potassium-t-butoxide was used as a catalyst, and dimethyl sulfoxide was used as a reaction solvent. After adding 50 g, the mixture was aged at 90 ° C. for 15 minutes (rearrangement reaction).
Thereafter, 200 g of water was added, and excess alkali was washed with water to remove liquid. 80 ° C, 10m from water-washed product
The dimethyl sulfoxide contained was removed under a reduced pressure of mHg to obtain 343.5 g of an ether oligomer having a propenyl ether group at the terminal [hereinafter, referred to as “compound (2)”] as compound (A). The product was ¹ H-NMR, ¹³
Confirmed by C-NMR.

Synthesis Example 3 Glycerin 4 was added to a 500 ml SUS autoclave.
6.0 g (0.5 mol) and KOH 0.5 g were charged,
528.6 g of ethylene oxide from a pressure dropping funnel
(12.0 mol) was added dropwise and aged at 110 ° C. for 5 hours. After cooling the system to 80 ° C., 84.2 g of KOH, n-
9.67 g of tetrabutylammonium bromide and 40 g of toluene were added, and 114.8 g of allyl chloride (1.
5 mol) at 80 ° C. over 1 hour, followed by aging for 5 hours. Thereafter, 200 g of water was added, and the excess alkali and the generated salts were washed with water and separated. 50 ° C, 10
After removing unreacted allyl chloride and toluene from the organic layer under a pressure of 0 mmHg, the product was charged into a glass eggplant flask, and potassium-t-butoxide was used as a catalyst in 3 ml of a flask.
2.4 g, dimethyl sulfoxide 50 g as a reaction solvent
And aged at 90 ° C. for 15 minutes (rearrangement reaction). Thereafter, 200 g of water was added, and excess alkali was washed with water to remove liquid. 80 ° C., 10 mmH
g of dimethyl sulfoxide contained under reduced pressure,
As a compound (A), 338.4 g of an ether oligomer having a propenyl ether group at a terminal (hereinafter, referred to as “compound (3)”) was obtained. The product was ¹ H-NMR, ¹³ C
-Confirmed by NMR.

Synthesis Example 4 Glycerin 4 was added to a 500 ml SUS autoclave.
6.0 g (0.5 mol) and KOH 0.5 g were charged,
696.0 g of propylene oxide from a pressure dropping funnel
(12.0 mol) was added dropwise and aged at 110 ° C. for 5 hours. After cooling the system to 80 ° C., 84.2 g of KOH, n-
9.67 g of tetrabutylammonium bromide and 40 g of toluene were added, and 114.8 g of allyl chloride (1.5 g) was added.
Mol) was gradually added dropwise at 80 ° C. over 1 hour and aged for 5 hours. Thereafter, 200 g of water was added, and the excess alkali and the generated salts were washed with water and separated. 50 ° C, 100
After removing unreacted allyl chloride and toluene from the organic layer under a pressure of mmHg, the product was charged into a glass eggplant flask, and potassium-t-butoxide was used as a catalyst.
4 g and 50 g of dimethyl sulfoxide as a reaction solvent were added, and the mixture was aged at 90 ° C. for 15 minutes (rearrangement reaction). Thereafter, 200 g of water was added, and excess alkali was washed with water to remove liquid. Dimethyl sulfoxide contained at 80 ° C. under reduced pressure of 10 mmHg was removed from the product washed with water, and an ether oligomer having a propenyl ether group at the terminal [hereinafter, referred to as “compound (4)”) was added as compound (A).
19.4 g were obtained. The product is ¹ H-NMR, ¹³ C-NMR
Confirmed by

Synthesis Example 5 In a 500 ml SUS autoclave, 67.1 g (0.5 mol) of trimethylolpropane and 0.5 g of KOH were charged, and propylene oxide 3 was added from a pressure dropping funnel.
48.5 g (6.0 mol) was added dropwise, and the mixture was aged at 110 ° C. for 5 hours. After cooling the system to 80 ° C, KOH 84.2
g, n-tetrabutylammonium bromide 9.67
g, 40 g of toluene and 114.8 g of allyl chloride.
(1.5 mol) was gradually added dropwise at 80 ° C. over 1 hour,
Aged for 5 hours. Thereafter, 200 g of water was added, and the excess alkali and the generated salts were washed with water and separated. 50
After removing unreacted allyl chloride and toluene from the organic layer at 100 ° C. and a pressure of 100 mmHg, the product was charged into a glass eggplant flask, 32.4 g of potassium-t-butoxide was used as a catalyst, and dimethyl sulfoxide was used as a reaction solvent. After adding 50 g, the mixture was aged at 90 ° C. for 15 minutes (rearrangement reaction).
Thereafter, 200 g of water was added, and excess alkali was washed with water to remove liquid. 80 ° C, 10m from water-washed product
The dimethyl sulfoxide contained was removed under a reduced pressure of mHg to obtain 349.5 g of an ether oligomer having a propenyl ether group at a terminal (hereinafter, referred to as “compound (5)”) as compound (A). The product was ¹ H-NMR, ¹³
Confirmed by C-NMR.

Examples 1 to 5 and Comparative Examples 1 to 3 Each component was blended according to the blending composition shown in Table 1 (the numerical values are parts by weight), mixed and dissolved to obtain the photocurable resin composition of the present invention. Obtained. This is coated on a glass plate with a bar coater at 20 μm.
Then, the minimum energy to reach tack-free was measured using an ultraviolet irradiation device (one high-pressure mercury lamp of 80 W / cm) at a distance of 10 cm and an irradiation intensity of 160 mW / cm ² . The gloss, adhesion, and hardness were evaluated as follows. Table 2 shows the obtained results.

Evaluation method Tack-free minimum energy: Expressed as an irradiation amount (ultraviolet light mJ / cm ² ) until tack on the surface after curing is eliminated. Gloss: The gloss after curing was visually determined. ○ ・ ・ ・ Excellent in gloss △ ・ ・ ・ Slightly decreased × ・ ・ ・ ・ No gloss Adhesion: When cured, the cellophane tape (trade name) is applied to the surface and peeled off. 、, when only the applied resin was peeled off, ×, and △ is between ○ and ×. Hardness: When the surface after curing is scratched with a nail and is not damaged, ○ is given when the surface is easily scratched, and Δ is in the middle.

[0078]

[Table 1]

The compounds shown in Table 1 are as follows. Epoxy group-containing ether oligomer (i): Compound obtained by introducing an epoxy group into the terminal by reacting epichlorohydrin instead of allyl chloride in Synthesis Example 1. Acryloyl group-containing ether oligomer (ii): Synthesis Example 1 , A compound in which an acryloyl group is introduced into the terminal by reacting methyl acrylate instead of allyl chloride SP-170 (* 1): manufactured by Asahi Denka Kogyo Co., Ltd., 50% diluted polyphenylsulfonium hexafluoroantimonate, light Cationic polymerization initiator UVR-6974 (* 2): manufactured by Union Carbide,
p- (phenylthio) phenyldiphenylsulfonium hexafluoroantimonate, 50% dilution of a mixture of bis [4- (diphenylsulfonio) phenyl] sulfidebishexafluoroantimonate, photo cationic polymerization initiator UVR-6990 (* 3): Manufactured by Union Carbide,
Photocationic polymerization initiator Irgacure 184 (* 4): manufactured by Ciba-Geigy,
Photo cationic polymerization initiator

[0080]

[Table 2]

Synthesis Example 6 of Compound (A) Synthesis Example 6 After adding 0.093 g of boron trifluoride etherate as a catalyst to 46.3 g (0.5 mol) of epichlorohydrin, the mixture was reacted at 40 ° C. for about 2 hours. Was. The reaction product was neutralized with sodium hydroxide and washed with water. Thus, about 46.0 g of yellow transparent polyepichlorohydrin was obtained. This polyepichlorohydrin had a number average molecular weight by GPC of 1330 and a viscosity of 5.9 poise (25 ° C.). 46.0 g of this polyepichlorohydrin was heated to 80 ° C. with stirring, and 33.6 g (0.6 mol) of KOH, 9.67 g of n-tetrabutylammonium bromide, and 40 parts of toluene 40
g after adding 34.8 g of allyl alcohol (0.6 g).
Mol) was gradually added dropwise at 80 ° C. over 1 hour and aged for 5 hours. Thereafter, 200 g of water was added and excess alkali was added.
The generated salt and excess allyl alcohol are washed with water and separated,
The toluene was removed from the organic layer at 50 ° C. under a pressure of 100 mmHg to obtain 53.0 g of a polyallyl ether compound.
The obtained product had a number average molecular weight of 150 by GPC.
0, viscosity 10.2 poise (25 ° C.), the molar ratio of allyl ether group, hydroxyl group, and chlorine confirmed by ¹ H-NMR was 62: 8: 30, and the allyl etherification rate was 85%. 50.0 g of polyallyl ether was charged into a glass eggplant flask, 32.4 g of potassium-t-butoxide as a catalyst and 50 g of dimethyl sulfoxide as a reaction solvent were added, and the mixture was aged at 90 ° C. for 15 minutes (rearrangement reaction).
Thereafter, 200 g of water was added, and excess alkali was washed with water and separated. Dimethyl sulfoxide was distilled off from the obtained product at 80 ° C. under a reduced pressure of 10 mmHg to obtain 48.4 g of a compound having a propenyl ether group at the terminal (hereinafter referred to as “compound (6)”) as compound (A). Obtained. The product was confirmed by ¹ H-NMR and ¹³ C-NMR to have a 98% rearrangement ratio of an allyl group to a propenyl group.

Synthesis Example 7 After adding 0.093 g of boron trifluoride etherate as a catalyst to 37.0 g (0.5 mol) of glycidol,
The reaction was performed at 40 ° C. for about 3 hours. The reaction product was neutralized with sodium hydroxide and washed with water. In this way, about 36.5 g of yellow transparent polyglycidol was obtained. This polyglycidol had a number average molecular weight of 1480 and a viscosity of 1
0.9 poise (25 ° C.). 36.8 g of this polyglycidol was heated to 80 ° C. with stirring, and KOH 33.6 g was added.
g (0.6 mol), 9.67 g of n-tetrabutylammonium bromide and 40 g of toluene were added thereto, and 46.0 g (0.6 mol) of allyl chloride was gradually added dropwise at 80 ° C. over 1 hour. Aged for hours. Then, add water to 200
g, and the excess alkali and the generated salt were washed with water and separated. Unreacted allyl chloride and toluene were removed from the organic layer at 50 ° C. under a pressure of 100 mmHg to obtain 50.2 g of a polyallyl ether compound. The product obtained is GPC
Number average molecular weight 1400, viscosity 30.2 poise (2
5 ° C.) and the allyl etherification rate confirmed by ¹ H-NMR was 90%. 50.0 g of polyallyl ether was charged into a glass eggplant flask, and potassium-
32.4 g of t-butoxide and 50 g of dimethyl sulfoxide as a reaction solvent were added, and the mixture was aged at 90 ° C. for 15 minutes (rearrangement reaction). Thereafter, 200 g of water was added, and excess alkali was washed off with water. From the obtained product, 80 ° C., 10
Under a reduced pressure of mmHg, water was removed, and a compound having a propenyl ether group at the terminal [hereinafter, referred to as a compound (A)]
"Compound (7)"] 48.5 g was obtained. The product is
¹ H-NMR and ¹³ C-NMR confirmed that the rearrangement ratio of the allyl group to the propenyl group was 98%.

Synthesis Example 8 After heating 29.0 g of methyl ethyl ketone to 80 ° C.,
A solution obtained by diluting a mixture of 58.1 g (0.5 mol) of hydroxyethyl acrylate and 0.58 g of azobisisobutyronitrile with 29.0 g of methyl ethyl ketone was used.
The mixture was dropped at 2 ° C. over 2 hours and aged for 3 hours. The obtained poly (2-hydroxyethyl acrylate) had a number average molecular weight of 2,000 by GPC. This poly (2-
28.0 g of hydroxyethyl acrylate) was added to 60 g of methyl ethyl ketone, and the temperature was raised to 80 ° C. while stirring.
After adding 33.6 g (0.6 mol) of OH and 9.67 g of n-tetrabutylammonium bromide, 46.0 g (0.6 mol) of allyl chloride was gradually added dropwise at 80 ° C. over 1 hour, and added for 5 hours. Matured. Thereafter, 200 g of water was added, and the excess alkali and the generated salt were washed with water and separated.
Unreacted allyl chloride and methyl ethyl ketone were removed from the organic layer at 50 ° C. under a pressure of 100 mmHg to obtain 58.2 g of a polyallyl ether compound. The allyl etherification rate of the obtained product was 79% by ¹ H-NMR.
Add 80.0 g of polyallyl ether to a glass eggplant flask.
g, potassium-t-butoxide as a catalyst
2.4 g, 50 g of dimethyl sulfoxide as a reaction solvent
And aged at 90 ° C. for 15 minutes (rearrangement reaction). Thereafter, 200 g of water was added, and excess alkali was washed with water to remove liquid. From the obtained product, 80 ° C., 10 mmHg
Under reduced pressure, water was removed to obtain 62.4 g of a compound having a propenyl ether group at a terminal (hereinafter, referred to as “compound (8)”) as compound (A). The product is ¹ H-N
It was confirmed by MR and ¹³ C-NMR that the rearrangement ratio of the allyl group to the propenyl group was 99%.

Synthesis Example 9 32.0 g of methyl ethyl ketone was heated to 80 ° C.
A solution obtained by diluting a mixture of 64.1 g (0.5 mol) of hydroxyethyl methacrylate and 0.64 g of azobisisobutyronitrile with 32.0 g of methyl ethyl ketone was used.
The solution was added dropwise at 0 ° C. over 2 hours and aged for 3 hours. The number average molecular weight of the obtained poly (2-hydroxyethyl methacrylate) was 3,500. 63.5 g of this poly (2-hydroxyethyl methacrylate) was added to 50 g of methyl ethyl ketone, the temperature was raised to 80 ° C. with stirring, and KOH 3
After adding 3.6 g (0.6 mol) and 9.67 g of n-tetrabutylammonium bromide, allyl chloride 4
6.0 g (0.6 mol) was gradually added dropwise at 80 ° C. over 1 hour, followed by aging for 5 hours. Thereafter, 200 g of water was added, and the excess alkali and the generated salt were washed with water and separated. 50
Unreacted allyl chloride and methyl ethyl ketone were removed from the organic layer at 100 ° C. and a pressure of 100 mmHg to obtain 95.2 g of a polyallyl ether compound. The allyl etherification rate of the obtained product was 75% based on ¹ H-NMR. 90.0 g of polyallyl ether was charged into a glass eggplant flask, and potassium-t-butoxide was used as a catalyst at 32.4 g.
g, 50 g of dimethyl sulfoxide as a reaction solvent was added, and the mixture was aged at 90 ° C. for 15 minutes (rearrangement reaction). Thereafter, 200 g of water was added, and excess alkali was washed with water and separated. Water was removed from the obtained product at 80 ° C. under a reduced pressure of 100 mmHg to obtain 80.1 g of a compound having a propenyl ether group at the terminal [hereinafter referred to as “compound (9)”] as compound (A). . The product was ¹ H-NMR, ¹³ C-
According to NMR, the rearrangement ratio of the allyl group to the propenyl group was 97%.
%.

Synthesis Example 10 22.5 g of polyvinyl alcohol (polymerization degree: 200, sapon value: 89 mol%) was heated to 80 ° C. with stirring in an autoclave, and 33.6 g of KOH, 9.67 g of n-tetrabutylammonium bromide, toluene After the addition of 40 g, 46.0 g (0.6 mol) of allyl chloride were added at 80 ° C. for 1 hour.
The solution was gradually dropped over time and aged for 5 hours. Thereafter, 200 g of water was added, and the excess alkali and the generated salt were washed with water and separated. Unreacted allyl chloride and toluene were removed from the organic layer at 50 ° C. under a pressure of 100 mmHg to obtain 52.5 g of polyallyl ether. The allyl etherification rate of the obtained product was 78% based on ¹ H-NMR. 50.0 g of polyallyl ether was charged into a glass eggplant flask, and potassium-t-butoxide was used as a catalyst.
4 g and 50 g of dimethyl sulfoxide as a reaction solvent were added, and the mixture was aged at 90 ° C. for 15 minutes (rearrangement reaction). Thereafter, 200 g of water was added, and excess alkali was washed with water and separated. Water was removed from the obtained product at 80 ° C. under a reduced pressure of 10 mmHg to obtain 33.6 g of a compound having a propenyl ether group at a terminal (hereinafter, referred to as “compound (10)”) as compound (A). . The product was ¹ H-NMR, ¹³ C-
According to NMR, the rearrangement ratio of the allyl group to the propenyl group was 97%.
%.

Examples 6 to 10 and Comparative Examples 4 to 6 The components were blended, mixed and dissolved according to the blending compositions shown in Table 3 (the numerical values are parts by weight) to obtain the photocurable resin composition of the present invention. Obtained. This was applied to a copper plate and a PMMA plate with a bar coater so as to have a thickness of 20 μm.
W / cm high-pressure mercury lamp) and distance 10c
m and the irradiation intensity were 160 mW / cm ² , and the minimum energy to reach tack-free was measured. Adhesion (copper,
PMMA) and the surface hardness were cured with an irradiation energy of 500 mJ / cm ² (other conditions were the same as those described above) and evaluated as follows. Table 4 shows the obtained results.

Evaluation method Tack-free minimum energy: The irradiation energy (ultraviolet mJ / cm ² ) until tack on the surface after curing is eliminated. Adhesion: According to the test method of JIS D0202, cross-cuts were made on each of the cured test pieces in a grid pattern, and then the peeling state after the peeling test using cellotape (trade name) was visually determined. Evaluation criteria: も の No change was observed at 100/100 ○ Slightly peeled off at 100/100 △ 50/100 to 90/100 × 0/100 to 50/100 Surface hardness: each cured The subsequent test piece was evaluated by pencil hardness.

[0088]

[Table 3]

The compounds shown in Table 3 are as follows. Propenyl ether group-containing compound (iii): CH _{3-
CH = CH-O- (CH 2} CH 2 O) 6 -H acrylate group-containing compound _{(iv): CH 2 = CH} -C
_{(= O) O- (CH 2} CH 2 O) 12 -C (= O) -CH
= CH ₂ epoxy group-containing compound (v): EP-828 (manufactured by Yuka Shell Co., bisphenol-type epoxy resin) Alicyclic epoxy terminal group compound (vi): ERL-422
1 (manufactured by UCC, alicyclic epoxy resin) UVR-6974 (* 2): manufactured by Union Carbide,
p- (phenylthio) phenyldiphenylsulfonium hexafluoroantimonate, 50% dilution of a mixture of bis [4- (diphenylsulfonio) phenyl] sulfidebishexafluoroantimonate, photocationic polymerization initiator Irgacure 184 (* 4): Ciba-Geigy,
Photo cationic polymerization initiator

[0090]

[Table 4]

Synthesis of Compound (A) Synthesis Example 11 In a SUS autoclave, dipentaerythritol 24 was added.
6.2 g (1.0 mol) and 20.0 g of KOH were charged, and 660.1 g of ethylene oxide was added through a dropping funnel.
(15.0 mol) was added dropwise, followed by aging at 170 ° C. for 5 hours. Thereafter, 500 g of a saline solution was added thereto, and the excess potassium hydroxide and the generated salt were separated and removed to obtain 788.6 g of an ethylene oxide adduct of dipentaerythritol. In an autoclave, 500 g of the ethylene oxide adduct of dipentaerythritol was heated to 80 ° C. with stirring, 33.6 g of KOH, 9.67 g of n-tetrabutylammonium bromide and 200 g of toluene were added, and then 397.8 g of allyl chloride (5. .2 mol) was gradually added dropwise at 80 ° C. over 1 hour, and aged for 2 hours.
The temperature was raised to ℃ and aged for 3 hours (rearrangement reaction). Thereafter, 300 g of water was added, and the excess alkali and the generated salt were washed with water and separated. Removing unreacted allyl chloride and toluene from the organic layer at 50 ° C. under a pressure of 100 mmHg;
Compound (A) having a propenyl ether group at the terminal [hereinafter referred to as “compound (11)”] 710.
3 g were obtained. The product was confirmed by ¹ H-NMR and ¹³ C-NMR.

Synthesis Example 12 In a SUS autoclave, dipentaerythritol 24 was added.
6.2 g (1.0 mol) and 20.0 g of KOH were charged, and 793.0 g of ethylene oxide was added through a dropping funnel.
(18.0 mol) was added dropwise, and the mixture was aged at 170 ° C. for 5 hours. Thereafter, 500 g of a saline solution was added thereto, and an excess of potassium hydroxide and a generated salt were separated and removed to obtain 798.6 g of an ethylene oxide adduct of dipentaerythritol. In an autoclave, 500 g of this ethylene oxide adduct of dipentaerythritol was heated to 80 ° C. with stirring, and 33.6 g of KOH, 9.67 g of n-tetrabutylammonium bromide and 200 g of toluene were added, and 535.5 g of allyl chloride (7 2.0 mol) at 80 ° C over 1 hour, and after aging for 2 hours, 170
The temperature was raised to ℃ and aged for 3 hours (rearrangement reaction). Thereafter, 300 g of water was added, and the excess alkali and the generated salt were washed with water and separated. Removing unreacted allyl chloride and toluene from the organic layer at 50 ° C. under a pressure of 100 mmHg;
Compound (A) having a propenyl ether group at the terminal [hereinafter referred to as “compound (12)”] 720.
3 g were obtained. The product was confirmed by ¹ H-NMR and ¹³ C-NMR.

Synthesis Example 13 Synthesis of ethylene oxide adduct of allyl alcohol 58.1 g of allyl alcohol was added to a SUS autoclave.
(1.0 mol) and KOH (5.8 g) were charged, and 132.2 g (3.0 mol) of ethylene oxide was added from a dropping funnel.
And aged at 170 ° C. for 5 hours. Thereafter, 100 g of saline was added thereto, and the excess potassium hydroxide and the generated salt were separated and removed to obtain 147 g of an ethylene oxide adduct of allyl alcohol. 2. Synthesis of (Poly) ether Oligomer Having Propenyl Ether Group at the Terminal 0.06.3 g of boron trifluoride etherate was added to 46.3 g (0.5 mol) of epichlorohydrin as a catalyst under cooling.
Was dropped, and reacted at 40 ° C. for about 2 hours. The reaction product was neutralized with sodium hydroxide and washed with water. Thus, about 46.0 g of yellow transparent polyepichlorohydrin was obtained. This polyepichlorohydrin had a number average molecular weight by GPC of 650 and a viscosity of 5.9 poise (25 ° C.). 46.0 g of this polyepichlorohydrin was stirred under 8
The temperature was raised to 0 ° C., and after adding 33.6 g of KOH, 9.67 g of n-tetrabutylammonium bromide and 40 g of toluene, 113.4 g (0.6 mol) of an ethylene oxide adduct of allyl alcohol was added at 80 ° C. for 1 hour. The mixture was slowly dropped and aged for 5 hours, and further aged at 170 ° C. for 3 hours (rearrangement reaction). Thereafter, 200 g of water was added, and the excess alkali, the generated salt and the excess ethylene oxide adduct of allyl alcohol were washed with water and separated and removed. 50
Toluene was removed from the organic layer at 100 ° C. and a pressure of 100 mmHg to obtain 127.5 g of a (poly) ether oligomer having a propenyl ether group at a terminal (hereinafter, referred to as “compound (13)”) as compound (A). The product is ¹ H
-NMR and ¹³ C-NMR were used.

Synthesis Example 14 Synthesis of 1.2-hydroxyethyl acrylate ethylene oxide adduct 116.1 g (1.0 mol) of 2-hydroxyethyl acrylate and 5.8 g of KOH were charged into an autoclave made of SUS, and ethylene was added from a dropping funnel. Oxide 132.
2 g (3.0 mol) was added dropwise, and the mixture was aged at 170 ° C. for 5 hours. Thereafter, 100 g of a saline solution was added thereto, and the excess potassium hydroxide and the generated salt were separated and removed.
3.6 g were obtained. 2. Synthesis of (Poly) ether Oligomer Having Propenyl Ether Group at Terminal Terminal After heating 29.0 g of methyl ethyl ketone to 80 ° C.,
124.2 g of an ethylene oxide adduct of hydroxyethyl acrylate and 0.5 of azobisisobutyronitrile
A solution obtained by diluting the mixture with 8 g with 29.0 g of methyl ethyl ketone was added dropwise at 80 ° C. over 2 hours, and the mixture was aged for 3 hours. The number average molecular weight of the obtained poly (2-hydroxyethyl acrylate ethylene oxide adduct) is 250.
It was 0. 100 g of this poly (2-hydroxyethyl acrylate ethylene oxide adduct) solution was heated to 80 ° C. with stirring in an autoclave, and KOH 33.6 was added.
g, n-tetrabutylammonium bromide 9.67
g, then add 46.0 g (0.6 mol) of allyl chloride.
At 80 ° C. over 1 hour and aged for 5 hours. Thereafter, 200 g of water was added, and the excess alkali and the generated salts were washed with water and separated. 50 ° C, 100mm
After removing unreacted allyl chloride and methyl ethyl ketone from the organic layer under a pressure of Hg, the product was charged into a glass eggplant-shaped flask, and potassium-t-butoxide was used as a catalyst in a flask.
2.4 g, dimethyl sulfoxide 50 g as a reaction solvent
And aged at 90 ° C. for 15 minutes (rearrangement reaction). Thereafter, 200 g of water was added, and excess alkali was washed with water to remove liquid. 80 ° C., 10 mmH
g of dimethyl sulfoxide contained under reduced pressure,
As the compound (A), a (poly) ether oligomer having a propenyl ether group at the terminal [hereinafter referred to as “compound (1)
4) "] 360.5 g. The product is ¹ H-N
Confirmed by MR and ¹³ C-NMR.

Examples 11 to 14, Comparative Examples 7 to 9 Each component was blended according to the blending composition shown in Table 5 (the numerical values are parts by weight), mixed and dissolved to obtain the photocurable resin composition of the present invention. Obtained. This was applied to a copper plate with a bar coater so as to have a thickness of 20 μm, and was tack-free using an ultraviolet irradiation device (one high-pressure mercury lamp of 80 W / cm) at a distance of 10 cm and an irradiation intensity of 160 mW / cm ^2. The minimum energy was measured. Copper adhesion and surface hardness are 5
The composition was cured with an irradiation energy of 00 mJ / cm ² (the other conditions were the same as those described above) and evaluated as follows. Table 6 shows the obtained results.

Evaluation method Tack-free minimum energy: Expressed as an irradiation amount (ultraviolet light mJ / cm ² ) until tack on the surface after curing is eliminated. Adhesion: According to the test method of JIS D0202, cross-cuts were made on each of the cured test pieces in a grid pattern, and then the peeling state after the peeling test using cellotape (trade name) was visually determined. Evaluation criteria: も の No change was observed at 100/100 ○ Slightly peeled off at 100/100 △ 50/100 to 90/100 × 0/100 to 50/100 Surface hardness: each cured The subsequent test piece was evaluated by pencil hardness.

[0097]

[Table 5]

The compounds shown in Table 5 are as follows. Propenyl ether group-containing compound (iii): CH _{3-
CH = CH-O- (CH 2} CH 2 O) 6 -H acrylate group-containing compound _{(iv): CH 2 = CH} -C
_{(= O) O- (CH 2} CH 2 O) 12 -C (= O) -CH
= CH ₂ epoxy group-containing compound (v): EP-828 (manufactured by Yuka Shell Co., bisphenol-type epoxy resin) Alicyclic epoxy terminal group compound (vi): ERL-422
1 (manufactured by UCC, alicyclic epoxy resin) UVR-6974 (* 2): manufactured by Union Carbide,
p- (phenylthio) phenyldiphenylsulfonium hexafluoroantimonate, 50% dilution of a mixture of bis [4- (diphenylsulfonio) phenyl] sulfidebishexafluoroantimonate, photocationic polymerization initiator Irgacure 184 (* 4): Ciba-Geigy,
Photo cationic polymerization initiator

[0099]

[Table 6]

Synthesis of Compound (A) Synthesis Example 15 172.1 g (1.0 mol) of dimethyl adipate, 145.3 g (1.1 mol) of glycerin monoallyl ether, and 0.3% of tetrabutoxytitanate as a catalyst
g, and then esterified at 200 ° C. for about 2 hours. To this reaction was added 0.3 g of tris (triphenylphosphine) ruthenium (II) chloride,
A rearrangement reaction was performed at 130 ° C. for 5 hours, and a polyester oligomer having a propenyl ether group on a side chain as compound (A) [hereinafter, referred to as “compound (15)”] 299.4
g was obtained.

Synthesis Example 16 Synthesis of propenyl ether containing OH group 57.1 g (1.0 mol) of allyl alcohol and KOH
0.5 g, and 132.1 g (3.0 mol) of ethylene oxide were added dropwise from a pressure dropping funnel.
For 5 hours. Further, 0.5 g of KOH was added, and 16
Aged at 0 ° C. for 5 hours (rearrangement reaction). After that, add 20
0 g was added, and excess alkali was washed with water to remove liquid, and OH
151.3 g of a group-containing propenyl ether was obtained. 2. Synthesis of polyester oligomer having terminal propenyl ether group 730.5 g (5.0 mol) of adipic acid, 600.9 g (4.0 mol) of triethylene glycol and 0.3 g of tetrabutoxytitanate as a catalyst were charged.
The reaction was performed at about 2 hours. Further, after adding 56.9 g of OH-containing propenyl ether and reacting at 200 ° C. for 3 hours, 500 g of toluene was added and reprecipitated in methanol to obtain a polyester oligomer having a propenyl ether group at the terminal as compound (A). [Hereinafter referred to as “compound (16)”] 970.5 g was obtained.

Synthesis Example 17 OH group-containing propenyl ether 7 shown in Synthesis Example 16
After charging 5.7 g, pyromellitic anhydride 76.4 g, and tetrabutoxytitanate 0.1 g as a catalyst, about 2 g were added.
The mixture was reacted at 00 ° C. for 2 hours, added with 200 g of water, washed with water and separated and removed to obtain 115.2 g of a compound having a propenyl ether group at a terminal (hereinafter referred to as “compound (17)”) as compound (A). Was.

Synthesis Example 18 44 g of ethylene glycol was added to a SUS autoclave.
(0.71 mol) and 0.5 g of KOH, a mixture of 220 g (5.0 mol) of ethylene oxide and 505 g (5.0 mol) of allyl glycidyl ether was added dropwise from a pressure dropping funnel, and the mixture was heated at 110 ° C. for 5 hours. React
Further, 0.5 g of KOH was added and the mixture was aged at 160 ° C. for 5 hours (rearrangement reaction). Thereafter, toluene and water were added to the reaction product, and excess alkali was washed with water and separated. Toluene is distilled off under reduced pressure from the product washed with water to give compound (A)
A polyether diol having a hydroxyl value of 145.5 having a propenyl ether group at the terminal of the molecular side chain [hereinafter, referred to as
769 g of "compound (18)" was obtained. The product is
Confirmed by ¹ H-NMR and ¹³ C-NMR.

Synthesis Example 19 In a SUS autoclave, methyl ethyl ketone 100 was added.
g, "Compound (18)" obtained in Synthesis Example 18 308.4 g
(0.4 mol), 66.6 isophorone diisocyanate
g (0.3 mol) and 0.1 g of dibutyltin dilaurate as a catalyst, and reacted at 110 ° C. for 5 hours. Then, methyl ethyl ketone was distilled off under reduced pressure. Hereinafter, referred to as “compound (19)”, 375 g was obtained. The number average molecular weight of this oligomer determined by GPC was 40.
00.

Synthesis Example 20 An autoclave made of SUS was charged with 679.6 g of a phenol novolak resin (number of nuclei: 8) and 3.8 g of KOH, melted at 130 ° C., and ethylene oxide 316.7 g was melted at 130 ° C.
g and the mixture was aged at 130 ° C. for 9 hours to obtain an ethylene oxide adduct of a phenol novolak resin (average addition of 1 mol per phenol hydroxyl group). The addition reaction rate of ethylene oxide calculated from the value of the hydroxyl value was 98%. 200 g of ethylene oxide adduct of the obtained phenol novolak resin was dissolved in 400 g of dimethoxydiethylene glycol, and 64.9 g of sodium hydroxide was dissolved.
After adding 124.1 g of allyl chloride and aging at 90 ° C. for 7 hours, unreacted allyl chloride was distilled off at 50 ° C. under reduced pressure. The allyl etherification rate was 95%. 50 g of dimethoxydiethylene glycol and 10.3 g of KOH were added to 50 g of the obtained allyl etherified product,
After aging for a period of time (rearrangement reaction). After aging, 100 ℃, 50m
Dimethoxydiethylene glycol was distilled off at mHg, 50 g of toluene and 50 g of water were added, and the alkali was washed with water and separated and removed. As a compound (A), a novolak resin having a propenyl ether group at the terminal [hereinafter referred to as “compound (2)
0) was obtained.

Examples 15 to 20 and Comparative Examples 10 to 12 The components were blended, mixed and dissolved according to the blending compositions shown in Table 7 (the numerical values are parts by weight) to obtain the photocurable resin composition of the present invention. Obtained. This was applied to a copper plate with a bar coater so as to have a thickness of 20 μm, and was tack-free using an ultraviolet irradiation device (one high-pressure mercury lamp of 80 W / cm) at a distance of 10 cm and an irradiation intensity of 160 mW / cm ^2. The minimum energy was measured. Copper adhesion, surface hardness is 50
The composition was cured with an irradiation energy of 0 mJ / cm ² (other conditions were the same as those described above) and evaluated as follows.
Table 8 shows the obtained results.

Evaluation method Tack-free minimum energy: Expressed as an irradiation amount (ultraviolet light mJ / cm ² ) until tack on the surface after curing is eliminated. Adhesion: According to the test method of JIS D0202, cross-cuts were made on each of the cured test pieces in a grid pattern, and then the peeling state after the peeling test using cellotape (trade name) was visually determined. Evaluation criteria: も の No change was observed at 100/100 ○ Slightly peeled off at 100/100 △ 50/100 to 90/100 × 0/100 to 50/100 Surface hardness: each cured The subsequent test piece was evaluated by pencil hardness.

[0108]

[Table 7]

The compounds shown in Table 7 are as follows. Compound having a propenyl ether group (vii): Synthesis Example 1
OH group-containing propenyl ether represented by 6 Acrylate group-containing compound (iv): CH ₂ ＣＨCH—C
_{(= O) O- (CH 2} CH 2 O) 12 -C (= O) -CH
= CH ₂ epoxy group-containing compound (v): EP-828 (manufactured by Yuka Shell Co., bisphenol-type epoxy resin) Alicyclic epoxy terminal group compound (vi): ERL-422
1 (manufactured by UCC, alicyclic epoxy resin) UVR-6974 (* 2): manufactured by Union Carbide,
p- (phenylthio) phenyldiphenylsulfonium hexafluoroantimonate, 50% dilution of a mixture of bis [4- (diphenylsulfonio) phenyl] sulfidebishexafluoroantimonate, photocationic polymerization initiator Irgacure 184 (* 4): Ciba-Geigy,
Photo cationic polymerization initiator

[0110]

[Table 8]

Synthesis of Compound (A) Synthesis Example 21 1. Synthesis of propenyl ether containing OH group 57.1 g (1.0 mol) of allyl alcohol and KOH
0.5 g, and 132.1 g (3.0 mol) of ethylene oxide were added dropwise from a pressure dropping funnel.
For 5 hours. Further, 0.5 g of KOH was added, and 16
Aged at 0 ° C. for 5 hours (rearrangement reaction). After that, add 20
0 g was added, and excess alkali was washed with water to remove liquid, and OH
151.3 g of a group-containing propenyl ether was obtained. 2. Synthesis of compound having propenyl ether group and acryloyl group 90.1 g of OH group-containing propenyl ether, 50.5 g of acrylic acid, and tetrabutoxy titanate as catalyst.
After charging 1 g, the mixture was reacted at 200 ° C. for about 2 hours. Thereafter, 100 g of water and 8 g of sodium hydroxide are added thereto, and the mixture is washed with water to remove an excess of acrylic acid. The compound (A) having a propenyl ether group and an acryloyl group [hereinafter, referred to as “compound (21)”] 181 .1g
I got The product was confirmed by ¹ H-NMR and ¹³ C-NMR.

Synthesis Example 22 OH group-containing propenyl ether 9 shown in Synthesis Example 21
After charging 0.1 g, 146.14 g of adipic acid and 0.1 g of tetrabutoxytitanate as a catalyst, the mixture was charged at 200 ° C.
For about 2 hours. Thereafter, 100 g of water and 20 g of sodium hydroxide were added, and the mixture was washed with water to remove an excess of adipic acid, thereby obtaining 180.5 g of a carboxylic acid having a propenyl ether group at a terminal. Further, after charging 180.5 g of a carboxylic acid having a propenyl ether group at the terminal and 58.7 g of 2-hydroxyethyl acrylate, 0.1 g of tetrabutoxytitanate was charged and reacted at 200 ° C. for about 2 hours. Thereafter, 100 g of water was added thereto, and the mixture was washed with water to remove an excess of 2-hydroxyethyl acrylate.
191.5 g was obtained. The product was ¹ H-NMR,
^It was confirmed by ¹³ C-NMR.

Synthesis Example 23 87.1 g (0.5 mol) of toluene diisocyanate and 200 g of toluene were charged, and after heating to 60 ° C., 90.1 g of the OH group-containing propenyl ether shown in Synthesis Example 21 was prepared.
Was added dropwise at 60 ° C. over 5 hours and aged for 2 hours.
Thereafter, after the temperature was raised to 80 ° C., 58.7 g (0.5 mol) of 2-hydroxyethyl acrylate was added dropwise over 30 minutes, the mixture was aged for 1 hour, and toluene was removed at a pressure of 100 mmHg. ), And 188.7 g of a compound having a propenyl ether group and an acryloyl group (hereinafter, referred to as “compound (23)”) was obtained. The product is ¹
Confirmed by H-NMR and ¹³ C-NMR.

Synthesis Example 24 558.1 g (1.0 mol) of glycidyl ether of 10 mol of ethylene oxide adduct of allyl alcohol and tris (triphenylphosphine) ruthenium (10 mol) were placed in a glass reactor equipped with a stirrer and a thermometer. II) 0.3 g of chloride was charged and aged at 130 ° C. for 5 hours (rearrangement reaction) to obtain polyoxyethylene glycidyl ether having a propenyl ether group at the terminal. 72.2 g (1.0 mol) of acrylic acid was added thereto, and
After aging for a period of time, an oligomer having a propenyl ether group and an acryloyl group at its terminals [hereinafter, referred to as compound (A)]
630.3 g of "compound (24)" was obtained. The product was confirmed by ¹ H-NMR and ¹³ C-NMR.

Examples 21 to 24 and Comparative Examples 13 to 15 The components were blended according to the blending compositions (the numerical values are parts by weight) shown in Table 9, mixed and dissolved to obtain the photocurable resin composition of the present invention. Obtained. This was applied to a copper plate with a bar coater so as to have a thickness of 20 μm, and was tack-free using an ultraviolet irradiation device (one high-pressure mercury lamp of 80 W / cm) at a distance of 10 cm and an irradiation intensity of 160 mW / cm ^2. The minimum energy was measured. Copper adhesion, surface hardness is 50
The composition was cured with an irradiation energy of 0 mJ / cm ² (other conditions were the same as those described above) and evaluated as follows.
Table 10 shows the obtained results.

Evaluation method Tack-free minimum energy: Expressed as an irradiation amount (ultraviolet light mJ / cm ² ) until tack on the surface after curing is eliminated. Adhesion: According to the test method of JIS D0202, cross-cuts were made on each of the cured test pieces in a grid pattern, and then the peeling state after the peeling test using cellotape (trade name) was visually determined. Evaluation criteria: も の No change was observed at 100/100 ○ Slightly peeled off at 100/100 △ 50/100 to 90/100 × 0/100 to 50/100 Surface hardness: each cured The subsequent test piece was evaluated by pencil hardness.

[0117]

[Table 9]

The compounds shown in Table 9 are as follows. Acrylate group-containing compound (iv): CH ₂ ＣＨCH—C
_{(= O) O- (CH 2} CH 2 O) 12 -C (= O) -CH
= CH ₂ epoxy group-containing compound (v): EP-828 (manufactured by Yuka Shell Co., bisphenol-type epoxy resin) Alicyclic epoxy terminal group compound (vi): ERL-422
1 (manufactured by UCC, alicyclic epoxy resin) UVR-6974 (* 2): manufactured by Union Carbide,
p- (phenylthio) phenyldiphenylsulfonium hexafluoroantimonate, 50% dilution of a mixture of bis [4- (diphenylsulfonio) phenyl] sulfidebishexafluoroantimonate, photocationic polymerization initiator Irgacure 184 (* 4): Ciba-Geigy,
Photo cationic polymerization initiator

[0119]

[Table 10]

[0120]

Since the photocurable resin composition of the present invention has the above-mentioned constitution, when used as a photosensitive resin composition, the photocurable resin composition of the present invention is more effective than a conventional photosensitive resin using an acrylate resin, an epoxy resin or a vinyl ether resin. It also has a rapid curing property, and by optimizing the balance between the number of functional groups of propenyl ether and the structure of the polymer main chain skeleton, can exhibit extremely excellent flow characteristics and cured resin properties.

Continued on the front page (31) Priority claim number Japanese Patent Application No. Hei 8-129029 (32) Priority date Hei 8 (1996) April 24 (33) Priority claim country Japan (JP) (31) Priority claim number Special Nippon Hei 8-131290 (32) Priority Date Hei 8 (1996) April 26 (33) Priority Country Japan (JP)

Claims (15)

[Claims] 1. A propenyl ether group-containing compound (A) having a propenyl ether group represented by the following formula (1) in the molecule and having a number average molecular weight of 500 or more, and a cationic photopolymerization initiator ( A photocurable resin composition comprising B). CH ₃ —CH ＝ CH—O— (1) 2. A compound having a propenyl ether group (A)
Is a compound having at least five propenyl ether groups represented by the formula (1). 3. A compound having a propenyl ether group (A)
Is a compound having at least 10 propenyl ether groups represented by the formula (1) and a number average molecular weight of 1,000 or more. 4. A compound having a propenyl ether group (A)
Is a compound having at least one main chain selected from the group consisting of polyether, polyvinyl, polyester, polyurethane, polyamide, polycarbonate, and novolak. 5. A compound having a propenyl ether group (A)
Is a compound having at least five propenyl ether groups represented by the formula (1) at the terminal of the side chain. 6. A compound having a propenyl ether group (A)
Is a compound having a structure represented by any one of the following general formulas (2) to (10). Embedded image In the formula (2), a represents an integer of 2 to 200. A ¹ is,
—X—Z represents an alkylene group substituted or unsubstituted, an arylene group, an aralkylene group, a haloalkylene group, or a residue obtained by ring-opening polymerization of glycidyl ether. X represents a divalent organic group. Z is
It represents a propenyl ether group represented by the following formula (1). CH ₃ —CH ＝ CH—O— (1) In the formula (3), b represents an integer of 2 to 200. Q ¹ is,
Represents a hydrogen atom, a hydroxyl group, an alkyl group, an aryl group, a haloalkyl group, a haloaryl group, an alkoxycarbonyl group, an acetoxy group, or a -XZ group. In the equation (4), c
Represents an integer of 2 to 200. A ² is a residue of an alkylene diol substituted or unsubstituted with an -XZ group, a residue of an arylene diol substituted or unsubstituted with a -XZ group, or -XZ Represents the residue of a polyether diol substituted or unsubstituted with a group. A ³ represents an alkylene group substituted or unsubstituted with an -XZ group, an arylene group substituted or unsubstituted with an -XZ group, an aralkylene group, or a haloalkylene group. Equation (5)
In the formula, d represents an integer of 2 to 200. A ⁴ is -XZ
Represents an alkylene group substituted or unsubstituted by a group, an arylene group substituted or unsubstituted by an -XZ group, an aralkylene group, or a haloalkylene group. In the formula (6), e represents an integer of 2 to 200. A ⁵ represents a diisocyanate residue. A ⁶ is,
A residue of an alkylene diol substituted or unsubstituted with an -XZ group, a residue of an arylene diol substituted or unsubstituted with an -XZ group, -X-
A residue of a (poly) ether diol substituted or unsubstituted with a Z group, or a residue of a polyester diol substituted or unsubstituted with a -XZ group. In the formula (7), f represents an integer of 2 to 200.
A ⁷ and A ⁸ are the same or different and are each an alkylene group substituted or unsubstituted with an -XZ group, -X
Represents an arylene group, an aralkylene group, or a haloalkylene group substituted or unsubstituted with a -Z group. In the formula (8), g represents an integer of 2 to 200. A ⁹
Represents an alkylene group substituted or unsubstituted with an -XZ group, an arylene group substituted or unsubstituted with an -XZ group, an aralkylene group, or a haloalkylene group. In the formula (9), h is 2 to 200
Represents an integer. A ¹⁰ represents an alkylene group substituted or unsubstituted with an -XZ group, an arylene group substituted or unsubstituted with an -XZ group, an aralkylene group, or a haloalkylene group. Equation (10)
In the formula, i represents an integer of 2 to 200. Ar represents an aryl group. Q ² represents a hydrogen atom, a glycidyl group, or-
Represents an XZ group. At least two of the i Q ² in the formula (10) represent a —XZ group. 7. The divalent organic group X has at least one group selected from the group consisting of an ether group, a carbonate group, an ester group, an imino group, an amide group, a urethane group, a urea group and a sulfide group. The photocurable resin composition according to claim 6, which is a hydrocarbon group which may be used. 8. A compound having a propenyl ether group (A)
Is a compound having a propenyl ether group represented by the following formula (1) at both ends of the main chain represented by any one of the general formulas (2) to (10). . CH ₃ —CH ＝ CH—O— (1) 9. The photocurable resin composition according to claim 1, wherein the cationic photopolymerization initiator (B) is an onium salt. 10. The photocurable resin composition according to claim 9, wherein the cationic photopolymerization initiator (B) is at least one of a triarylsulfonium salt and a diaryliodonium salt. 11. The weight ratio of the compound (A) containing a propenyl ether group to the cationic photopolymerization initiator (B) is 9:
The photocurable resin composition according to claim 1, wherein the ratio is 5: 5 to 99.9: 0.01. 12. Further represented by the following general formula (11):
And a reactive diluent (C) comprising a compound having a molecular weight of less than 500 is added in an amount of 5 to 60% by weight based on the total amount of the propenyl ether group-containing compound (A) and the cationic photopolymerization initiator (B). The photocurable resin composition according to claim 1, which contains. CH ₃ —CH ＝ CH—O—R ¹ —O—R ² (11) In the formula (11), R ¹ is an alkylene diol, arylene diol, polyether diol or polyester represented by HO—R ¹ —OH. It represents a residue obtained by removing a hydroxyl group from a diol. R ² represents an alkyl group, an aryl group, an aralkyl group, a cycloalkyl group, or a hydrogen atom. 13. The photocurable resin composition according to claim 1, further comprising a radical polymerizable vinyl compound (D) and a photoradical polymerization initiator (E). 14. A cured product obtained by curing the photocurable resin composition according to claim 1. 15. A resist for a printed wiring board, a printing ink, a paint, a coating agent for a paper, a coating agent for a metal, and a coating for an optical fiber, comprising the photocurable resin composition according to claim 1. Agent, hard coat agent or adhesive.