JP4999393B2 - Cationic photosensitive composition and cured product thereof - Google Patents

Description

  The present invention forms a cured coating film in the atmosphere by irradiation with energy rays, and the formed coating film is a paint, an adhesive, an ink, a film coating, a resist material, more specifically, a UV ink for inkjet printing. , UV ink for gravure printing, UV ink for flexographic printing, UV ink for offset printing, UV ink for screen printing, UV ink for metal printing, sealing material for display panels such as liquid crystal and organic EL, adhesive for optical disc bonding, The present invention relates to a photosensitive composition useful as a surface protective layer forming material, an antireflection film forming coating material, a hard coating material, a resist material for semiconductor manufacturing, a resist material for fine wiring, and a cured product thereof.

Curing systems using energy rays such as ultraviolet rays have become an effective method for improving productivity and solving recent environmental problems. The current mainstream of photo-curing systems is radical curing systems using (meth) acrylate materials, but cationic curing materials using materials such as epoxy, vinyl ether, oxetane, etc. Excellent surface and thin film curability because it is difficult to receive, (b) small cure shrinkage, good adhesion to a wide range of substrates, (c) long life of active species, gradually curing after light irradiation (Dark reaction), and it has excellent features compared to radical curing systems such as the ability to keep the amount of residual monomers low. In recent years, paints, adhesives, display sealants, printing inks, three-dimensional modeling, silicone systems Application to release papers, photoresists, sealants for electronic components, etc. has been studied (Non-Patent Document 1).
As compounds mainly used in the photocationic curing system, glycidyl type epoxy compounds, alicyclic epoxy compounds (Patent Document 1), oxetane compounds (Non-Patent Document 2), vinyl ether compounds (Patent Documents 2, 3, 4, 5), etc. Can be illustrated. These compounds have excellent curability compared to radical systems because they do not cause curing inhibition by oxygen even in the air.

上記問題の発生を防止するために、系内に予め塩基を含有させて発生する酸を補足する方法が考えられるが、この方法では、光により発生した酸が、カチオン重合を引き起こす前に塩基により補足されてしまうので、重合反応が効率よく進まない。 On the other hand, in the photocationic curing system, an acid may exist in the cured product because a photoacid generator that generates an acid by light that is an energy ray is used. As the mechanism of acid generation, the acid generated by light remains as it is without being used for the curing reaction (polymerization reaction), or the active end (oxiranium ion) of the growth polymer exists in the system by the following reaction. An acid generated by being deactivated by a small amount of water is considered. These acids can corrode the base metal. Particularly in applications of electronic materials, these acids can cause problems such as device degradation.

In order to prevent the occurrence of the above problem, a method of supplementing the acid generated by previously containing a base in the system is conceivable. However, in this method, the acid generated by light is caused by the base before causing cationic polymerization. Since it is supplemented, the polymerization reaction does not proceed efficiently.

US Pat. No. 3,794,576 Japanese Patent Laid-Open No. 06-298911 JP 09-328634 A Japanese Patent No. 2667934 Japanese Patent Laid-Open No. 04-120182 JP 2003-048591 A JP 2003-048950 A Masahiro Tsunooka, et al. “Industrial development of cationic curing technology” MATERIAL STAGE, Technical Information Association, May 10, 2002, Vol. 2, No. 2, p. 39-92 Photocationic Polymerizability of 3-Ethyl-3-hydroxymethyloxetane / Epoxide Combination System, Hiroshi Sasaki, Tojo Synthetic Research Annual Report TREND 2005 No.8

The composition of the present invention has excellent photocurability (surface curability, internal curability) without being inhibited by oxygen in the atmosphere, and the photocured product has various groups such as resin, metal, and glass. An object of the present invention is to provide a cationic photosensitive composition that exhibits good adhesion to a material and does not corrode a metal substrate. Such a curable composition is useful as a constituent material for coating materials, UV inks, adhesives, sealants for flat panel displays (FPD) such as organic EL, and resist materials.
As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by including a specific thermal amine generator in the composition before curing by an energy ray in the cationic curing reaction. Invented the invention.

（但し、R1, R2はアルキル基またはフェニル基、R3, R4, R5, R6は水素、アルキル基、またはフェニル基を表す。R1, R2, R3の内二種ないし全てが同じ環状アルキル基の一部であっても良く、R4, R5, R6の内二種ないし全てが同じ環状アルキル基の一部であっても良い。R7はアルキル基またはフェニル基、R8, R9, R10は水素、アルキル基、またはフェニル基を表す。R7, R8が同じ環状アルキル基の一部であっても良く、R9, R10 が同じ環状アルキル基の一部であっても良い。R11はアルキレン基を表す。R12, R13, R14 はアルキル基またはフェニル基を表す。R15, R16, R17 はアルキル基またはフェニル基を表す。)
２．カチオン重合性を有する化合物が、分子中にエポキシ基を２個以上有するエポキシ化合物、オキセタン化合物、ビニルエーテル化合物からなる群から選ばれる一種以上である上記１に記載の組成物、

That is, the present invention
1. (a) a cationic polymerizable composition comprising a compound having cationic polymerizability, (b) an energy ray-sensitive cationic polymerization initiator, and (c) a thermal amine generator , wherein the thermal amine generator has the following general formula ( 1) a cationically polymerizable composition which is an adduct formed by reacting one or more amines selected from the structures of (2), (3) and (4) with an isocyanate ,

(However, R1, R2 represents an alkyl group or a phenyl group, and R3, R4, R5, R6 represent hydrogen, an alkyl group, or a phenyl group. Among R1, R2, and R3, two or all of the same are cyclic alkyl groups. 2 or all of R4, R5 and R6 may be part of the same cyclic alkyl group, R7 is an alkyl group or a phenyl group, R8, R9 and R10 are hydrogen and an alkyl group. R7 and R8 may be part of the same cyclic alkyl group, R9 and R10 may be part of the same cyclic alkyl group, R11 represents an alkylene group, R12, R13, R14 represents an alkyl group or a phenyl group, and R15, R16, R17 represent an alkyl group or a phenyl group.)
2 . 2. The composition according to 1 above, wherein the compound having cationic polymerizability is at least one selected from the group consisting of an epoxy compound having two or more epoxy groups in the molecule, an oxetane compound, and a vinyl ether compound.

3. 3. The composition according to 1 or 2 above, wherein the compound having cationic polymerizability is at least one selected from the group consisting of an epoxy compound having two or more epoxy groups in the molecule, an oxetane compound, and a vinyl ether compound,
4). The composition according to any one of the above 1 to 3, wherein the energy ray-sensitive cationic polymerization initiator is a sulfonium salt and / or an iodonium salt,
5. The composition according to any one of the above 1 to 4, wherein the amine is an amine having a boiling point of 120 ° C or higher,
6). Curing composition characterized by irradiating the composition according to any one of 1 to 5 above with energy rays and curing the composition, and further performing a heat treatment,
It is.

  Oxygen in the atmosphere does not inhibit the curing reaction and has excellent photocurability (surface curability, internal curability), and the photocured product has good adhesion to various substrates such as resin, metal, and glass. To provide a cationic photosensitive composition that shows and does not corrode metal substrates.

The present invention will be specifically described below.
The compound (a) having a cationic polymerizable group in the present invention is a compound that is polymerized by hydrogen ions or Lewis acid, and includes a glycidyl ether type epoxy compound, an alicyclic epoxy compound, a compound having a vinyl ether group, and an oxetanyl group. Compounds having a propenyl ether group, and alkoxysilanes. One or a plurality of the functional groups are contained in one molecule. Different types of functional groups may exist in one molecule. Among these, at least one selected from the group consisting of an epoxy compound having two or more epoxy groups in the molecule, an oxetane compound, and a vinyl ether compound is preferable because of its good curing reactivity. Although there is no restriction | limiting in particular in the usage-amount of these components, the compound which has an epoxy group, and the compound which has an oxetanyl group are 30 to 90 wt%, respectively, Preferably it is 60 to 90 wt%. The compound having a vinyl ether group is 1 to 50 wt%, preferably 1 to 30 wt%. Moreover, alkoxysilanes are 1 to 50%, Preferably it is 1 to 30 wt%.

  Specific examples of glycidyl ether type epoxy compounds include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, phenol novolac type epoxy compounds, cresol novolak type epoxy compounds, hydrogenated bisphenol A type epoxy compounds, and bisphenol A alkylene oxide adducts. Diglycidyl ether, diglycidyl ether of bisphenol F alkylene oxide adduct, diglycidyl ether of hydrogenated bisphenol A alkylene oxide adduct, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, Butanediol diglycidyl ether, hexanediol diglycidyl ether, cyclohexane dimethanol Diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, trimethylolpropane di and / or triglycidyl ether, pentaerythritol tri and / or tetraglycidyl ether, sorbitol hepta and / or hexaglycidyl ether, resorcin diglycidyl ether And dicyclopentadiene / phenol-added glycidyl ether, methylenebis (2,7-dihydroxynaphthalene) tetraglycidyl ether, 1,6-dihydroxynaphthalenediglycidyl ether, and the like.

  Specific examples of the alicyclic epoxy compound include 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy. ) Cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene dioxide, 4-vinylepoxycyclohexane, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4- Epoxy-6-methylcyclohexyl-3,4-epoxy-6-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol di (3,4-epoxycyclohexylme L) ether, ethylene bis (3,4-epoxycyclohexanecarboxylate), propylene bis (3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1, Examples include 4-cyclohexanedimethanol di (3,4-epoxycyclohexanecarboxylate), 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, and the like.

As bifunctional alicyclic epoxy compounds, Celoxide 2021, 2080, 3000 (manufactured by Daicel Chemical Industries), UVR-6110, 6105, 6128, ERLX-4360 (manufactured by Dow Chemical Japan), trifunctional or more polyfunctional As the alicyclic epoxy compound, Epolide GT300, GT400 (manufactured by Daicel Chemical Industries) or the like can be used.
Of these, alicyclic epoxy compounds are preferred because of their excellent cationic polymerization reactivity. These compounds having an epoxy group can be used alone or in combination of two or more.

(Rはアルキル基、ヒドロキシアルキル基、ビニル基、ビニル基を有するアルキル基、アリール基を有するアルキル基、アクリロイル基、メタクリロイル基を表す。)
これらの中で、Rがヒドロキシアルキル基である化合物が好ましい。分子内に水酸基を有するビニル化合物を用いることにより、優れた硬化性と接着性、耐水性を有する硬化物を与える光硬化性が得ることができる。その理由は明確にはなっていないが、水酸基を有する化合物は、酸を触媒としてエポキシ基やオキセタニル基と反応した場合、水酸基をポリマー骨格に導入することになるので、このことにより硬化性、接着性、耐水性を向上させると推定される。 The compound having a vinyl ether group is a compound having the following general formula.

(R represents an alkyl group, a hydroxyalkyl group, a vinyl group, an alkyl group having a vinyl group, an alkyl group having an aryl group, an acryloyl group, or a methacryloyl group.)
Of these, compounds in which R is a hydroxyalkyl group are preferred. By using a vinyl compound having a hydroxyl group in the molecule, it is possible to obtain photocurability that gives a cured product having excellent curability, adhesion, and water resistance. The reason for this is not clear. However, when a compound having a hydroxyl group reacts with an epoxy group or oxetanyl group using an acid as a catalyst, the hydroxyl group is introduced into the polymer skeleton. It is presumed to improve the water resistance and water resistance.

  Examples of the vinyl ether compound having a hydroxyl group include hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, cyclohexanedimethanol monovinyl ether, cyclohexanediol monovinyl ether, 9-hydroxynonyl vinyl ether, propylene glycol monovinyl ether, neopentyl glycol monovinyl ether, glycerol divinyl ether, glycerol mono Vinyl ether, trimethylolpropane divinyl ether, trimethylolpropane monovinyl ether, pentaerythritol monovinyl ether, pentaerythritol divinyl ether, pentaerythritol trivinyl ether, diethylene glycol monovinyl ether, triethylene glycol monovinyl ether, tetraethylene Glycol monovinyl ether, tricyclodecane diol monovinyl ether and tricyclodecanedimethanol monovinyl ether and the like. Of these, hydroxyalkyl vinyl ethers such as hydroxybutyl vinyl ether are preferable because the cured film has a good balance between flexibility and high degree.

(ここでR1は水素、アルキル基、アリール基、オキセタニルアルキル基、シリルアルキル基、アリールアルキル基、ヒドロキシアルキル基、オキシアルキレン基、オキセタニルオキシフェニレン基、フェノキシアルキル基、を表す。R2はアルキル基、アリール基、アリールアルキル基をあらわす。) The compound having an oxetanyl group refers to a compound having a trimethylene oxide structure that is a four-membered ring ether in the molecule, and is preferably a compound represented by the following general formula.

(Where R1 represents hydrogen, an alkyl group, an aryl group, an oxetanylalkyl group, a silylalkyl group, an arylalkyl group, a hydroxyalkyl group, an oxyalkylene group, an oxetanyloxyphenylene group, or a phenoxyalkyl group. R2 represents an alkyl group, Represents an aryl group or an arylalkyl group.)

テトラアルコキシシランとしては、テトラメトキシシラン、テトラエトキシシラン、テトラブトキシシランなどが例示できる。これらの中で、テトラエトキシシランが硬化性に優れており好ましい。テトラアルコキシシランは、酸を触媒として、ポリシロキサンを生成する。テトラアルコキシシランを用いることで、粘度が低く、高度と柔軟性のバランスに優れた硬化膜を得ることができる。 The compound having a propenyl ether group is a compound represented by the following general formula. (R represents an alkyl group, a hydroxyalkyl group, a vinyl group, an alkyl group having a vinyl group, an alkyl group having an aryl group, an acryloyl group, or a methacryloyl group.)

Examples of the tetraalkoxysilane include tetramethoxysilane, tetraethoxysilane, and tetrabutoxysilane. Of these, tetraethoxysilane is preferred because of its excellent curability. Tetraalkoxysilane generates polysiloxane using an acid as a catalyst. By using tetraalkoxysilane, a cured film having a low viscosity and an excellent balance between altitude and flexibility can be obtained.

The (b) energy beam-sensitive cationic polymerization initiator used in the present invention is a compound capable of generating a substance that initiates cationic polymerization by energy beam irradiation, and particularly preferably generates a Lewis acid by irradiation. It is an onium salt. Specific examples include a diazonium salt of a Lewis acid, an iodonium salt of a Lewis acid, a sulfonium salt of a Lewis acid, and the like. In these, the cation portion is aromatic diazonium, aromatic iodonium, aromatic sulfonium, respectively, and the anion portion is BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , [BX ₄ ] ⁻ (where X is a phenyl group substituted with at least two fluorine or trifluoromethyl groups) and the like. Specifically, boron tetrafluoride phenyldiazonium salt, phosphorus hexafluoride diphenyliodonium salt, antimony hexafluoride diphenyliodonium salt, arsenic hexafluoride tri-4-methylphenylsulfonium salt, antimony tetrafluoride Examples include tri-4-methylphenylsulfonium salt, diphenyliodonium salt of tetrakis (pentafluorophenyl) boron, acetylacetone aluminum salt and orthonitrobenzylsilyl ether mixture, phenylthiopyridium salt, phosphorus hexafluoride allene-iron complex, etc. Can do. More specifically, CD-1012 (trade name: manufactured by SARTOMER), PCI-019, PCI-021 (trade name: manufactured by Nippon Kayaku Co., Ltd.), Optmer SP-150, Optomer SP-170 (trade name: Asahi) Manufactured by Denka Co., Ltd.), UVI-6990 (trade name: manufactured by Dow Chemical Co., Ltd.), CPI-100P, CPI-100A (trade name: manufactured by San-Apro), TEPBI-S (trade name: manufactured by Nippon Shokubai Co., Ltd.), RHODROSIL PHOTOINITITOR 2074 (Trade name: manufactured by Rhodia), IRGACURE250 (Ciba Specialty Chemicals) and the like. These can be used alone or in combination of two or more.

The content of these (b) energy ray-sensitive cationic polymerization initiators in the cationic polymerizable composition is preferably 0.1 to 10 wt%, more preferably 0.2 to 5 wt%. When the content is more than 10 wt%, the light transmittance is lowered and the film bottom is not sufficiently cured, which is not preferable. On the other hand, when the amount is less than 0.1 wt%, the amount of the cationic substance generated by energy beam irradiation is insufficient, and sufficient curability cannot be obtained.
The (c) thermal amine generator in the present invention refers to a compound that generates an amine compound by heating. Examples of these compounds include amine and isocyanate adducts, ketimine compounds, carboxylic acid ammonium salts, ammonium phosphate salts, and microencapsulated amines. Among these, an adduct of amine and isocyanate is preferable. In particular, an adduct composed of a sterically hindered amine and an isocyanate can dissociate the amine at a relatively low temperature of 100 to 200 ° C.
The amount of these (c) thermal amine generators is (c) / (b) = 10/1 to 0.5 / 1 in an equivalent ratio to the (b) energy ray-sensitive cationic polymerization initiator. Is preferable, and (c) / (b) = 5/1 to 0.5 / 1 is more preferable.

（但し、R1, R2はアルキル基またはフェニル基、R3, R4, R5, R6は水素、アルキル基、またはフェニル基を表す。R1, R2, R3の内二種ないし全てが同じ環状アルキル基の一部であっても良く、R4, R5, R6の内二種ないし全てが同じ環状アルキル基の一部であっても良い。R7はアルキル基またはフェニル基、R8, R9, R10は水素、アルキル基、またはフェニル基を表す。R7, R8が同じ環状アルキル基の一部であっても良く、R9, R10が同じ環状アルキル基の一部であっても良い。R11はアルキレン基を表す。R12, R13, R14はアルキル基またはフェニル基を表す。R15, R16, R17はアルキル基またはフェニル基を表す。) The adduct comprising the above amine and isocyanate is an addition obtained by reacting at least one amine selected from the following general formulas (1), (2), (3) and (4) with a polyisocyanate. Is the body.

(However, R1, R2 represents an alkyl group or a phenyl group, and R3, R4, R5, R6 represent hydrogen, an alkyl group, or a phenyl group. Among R1, R2, and R3, two or all of the same are cyclic alkyl groups. 2 or all of R4, R5 and R6 may be part of the same cyclic alkyl group, R7 is an alkyl group or a phenyl group, R8, R9 and R10 are hydrogen and an alkyl group. R7 and R8 may be part of the same cyclic alkyl group, R9 and R10 may be part of the same cyclic alkyl group, R11 represents an alkylene group, R12, R13, R14 represents an alkyl group or a phenyl group, and R15, R16, R17 represent an alkyl group or a phenyl group.)

In the present invention, as the isocyanate for synthesizing an adduct with an amine, monoisocyanate or polyisocyanate having a plurality of isocyanate groups in one molecule is used. Polyisocyanate is preferable, and in this case, the isocyanate group generated after the amine is dissociated reacts with the hydroxyl group if present in the resin. In this case, the isocyanate also has a function as a crosslinking agent. As the isocyanate, aromatic isocyanate and aliphatic isocyanate can be used. Aromatic isocyanate generally has a lower amine generation temperature of the adduct.
The compounds of the above general formulas (1) and (2) are compounds in which a substituent having a large steric hindrance is contained in one or both carbons adjacent to the nitrogen atom as described above. The compound of the general formula (3) is imidazole or a derivative thereof, and the compound of the general formula (4) is pyrazole or a derivative thereof. Regarding the substituents R1 to R17 of each compound, in the case of an alkyl group, a linear, branched, or cyclic alkyl group is included, and in the case of a phenyl group, an alkyl-substituted phenyl group or a condensed ring is included. These amines react with isocyanates to form urea compounds. When the isocyanate is the target product and the amine is transferred out of the reaction system, the urea compound is called blocked isocyanate in the field of paint (Patent Documents 6 and 7). In the present invention, the generated amine is contained in the system. In order to remain as a proton trapping agent, the adduct is different from the blocked isocyanate in that it becomes a thermal amine generator. Therefore, the boiling point of the amine is preferably higher than the thermal amine generation temperature, and specifically 120 ° C. or higher is preferable.

In the present invention, the urea compound formed by reacting a specific amine and isocyanate is presumed to have the property that the bond between the carbonyl carbon and the nitrogen atom on the amine side is easily broken due to the steric hindrance or electronic reason. For this reason, the isocyanate is easily regenerated by heating to 100 to 150 ° C., and the generated amine acts as a proton scavenger, and when the generated isocyanate has a hydroxyl group in the system, it reacts with it and is taken in as a polymer. It is. It is presumed that it reacts with a chain extender to produce a polyurethane and / or polyurea resin.
Specific examples of amines represented by the above general formulas (1) and (2) include 2,6-dimethylpiperidine, 2,6-dimethyl-4-alkylpiperidine, diisopropylamine, N-ethyl t-butylamine, 2,2, 6,6,-Tetramethylpiperidine, N-methylcyclohexylamine, N-propylsec butylamine, N-methylbenzylamine, N-isopropylcyclohexylamine, N-isopropylbenzylamine, Nt-butylbenzylamine, dicyclohexylamine, di-t -Butylamine etc. are mentioned. Of these, 2,6-dimethylpiperidine, 2,6-dimethyl-4-alkylpiperidine, N-ethyl t-butylamine, diisopropylamine, and Nt-butylbenzylamine are particularly preferred because of their low amine dissociation temperatures.

Examples of the compound represented by the general formula (3) include imidazole, 2-methylimidazole, 2-alkylimidazole, 4-alkylimidazole, 5-alkylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2- Examples include undecyl imidazole, 2-heptadecyl imidazole, 2-phenyl-4-methylimidazole, and compounds in which hydrogen bonded to carbon of these compounds is substituted with an alkyl group.
Examples of the compound represented by the general formula (4) include pyrazole, alkyl-substituted pyrazole, and compounds in which hydrogen bonded to carbon of these compounds is substituted with an alkyl group.
The thermal amine generator in the present invention is preferably prepared by reacting isocyanate with the specific amine compound of the present invention at a charge equivalent ratio (amine equivalent / isocyanate equivalent) of 1. This reaction is usually performed at room temperature, but may be performed at a temperature up to about 100 ° C. The amine is easily dissociated by heating the thermal amine generator to about 100 ° C. or higher. When synthesizing the adduct, a solvent may or may not be used, but if a solvent is used, an aromatic solvent, a hydrocarbon solvent, a ketone solvent, an amide solvent, a sulfoxide system Examples of solvents that can be used include solvents, ester solvents, alcohol solvents, and ether solvents.

As the isocyanate, either monoisocyanate or polyisocyanate can be used, and polyisocyanate is preferable because the amine dissociation word serves as a crosslinking agent. Diisocyanates include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), p-phenylene diisocyanate, xylylene diisocyanate (XDI), naphthalene diisocyanate (NDI), tolidine diisocyanate (TODI), hydrogenated diphenylmethane diisocyanate (H12MDI), water Examples include hydrogenated xylylene diisocyanate (H6XDI), hydrogenated tolylene diisocyanate (H6TDI), transcyclohexane 1,4-diisocyanate, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), and the like.
Examples of the tri- or higher functional polyisocyanate include compounds derived from diisocyanates and triphenylmethane triisocyanate. Specific examples of the polyisocyanate derived from the diisocyanate compound include isocyanurate-modified products, allophanate-modified products, burette-modified products, and urea-modified products.

In the present invention, a polyol-modified polyisocyanate obtained by modifying these polyisocyanates with a polyol may be used. By this method, the solubility of the adduct composed of isocyanate and amine can be improved. Polyol modification means that a polyol and a polyisocyanate are charged and reacted at a ratio of an equivalent ratio (isocyanate group equivalent / hydroxyl group equivalent) exceeding 1 to obtain a compound having isocyanate groups at both ends of the molecule. This reaction usually proceeds at room temperature, but may be performed at a temperature up to about 150 ° C. The urethanization catalyst may or may not be used, and the solvent may or may not be used.
As the solvent, aromatic solvents, hydrocarbon solvents, ketone solvents, amide solvents, sulfoxide solvents, ester solvents, alcohol solvents, ether solvents can be used. The polyol used here is a polyhydric alcohol compound, a low molecular diol or a high molecular diol having two hydroxyl groups in the molecule, or a low molecular polyol having an average number of hydroxyl groups exceeding 2 in the molecule. Or it is a polymer polyol. These polyols may be used alone or in combination.

Low molecular weight diols have the general formula
HO-R-OH
(Wherein R represents an alkylene group or an oxyalkylene group). Among these, an alkylene group or oxyalkylene group having 2 to 12 carbon atoms in R in the general formula is preferable. Specific examples include ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, propylene glycol, neopentyl glycol, 1,5-pentanediol, 3-methyl 1,5-pentanediol, 1.6- Such as hexanediol.
Examples of the low molecular weight triol include trimethylolethane, trimethylolpropane, glycerin, sorbitol, and quadrol.
Examples of the polymer diol include polycarbonate diol, polyether diol, polyester diol, and polycaprolactone diol.

In the photosensitive composition of the present invention, a photosensitizer can be used in combination with the energy ray-sensitive cationic polymerization initiator (b). The photosensitizer is not particularly limited as long as it increases the sensitivity of the energy ray-sensitive cationic polymerization initiator (b) to light or expands the photosensitive wavelength region. Benzophenone, 4,4′- Bis (diethylamino) benzophenone, acetophenone, perylene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, thioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, CS-7001 (Nippon Soda), xanthone, 1- Examples thereof include hydroxycyclohexyl phenyl ketone and phenothiazine.
In the photosensitive composition of the present invention, a polymerization initiator having a function of generating a substance that initiates cationic polymerization by heating can be used in combination with the polymerization initiator (b) used in the present invention. Specific examples include thermal acid generators such as phenylbenzylalkylsulfonium salts.

In the present invention, examples of usable compounds in addition to the above compounds include aliphatic polyhydric alcohol compounds having two or more hydroxyl groups in the molecule. These compounds are effective in improving the mechanical strength and surface hardness of the cured film. The aliphatic polyhydric alcohol is an aliphatic polyhydric alcohol that does not contain an aromatic ring, and may be a low molecule, an oligomer, or a polymer. The molecule may or may not contain oxygen atoms excluding the hydroxyl group. Examples of the case where the aliphatic polyhydric alcohol includes an oxygen atom excluding a hydroxyl group include an ester bond, an ether bond, a carbonate bond, and an acetal bond. As the aliphatic polyhydric alcohol, acyclic, monocyclic, bridged cyclic, and spirocyclic polyhydric alcohols can be widely used. Specifically, ethylene glycol, diethylene glycol, polyethylene glycol, pentanediol, hexanediol, neopentyl glycol, trimethylolpropane, trimethylolbutane, pentaerythritol, glycerin, dimethylolcyclohexane, tricyclodecane dimethanol (di (hydroxymethyl) ) Tricyclo [5,2,1,0 ^2,6 ] decane), polyacrylates containing hydroxyethyl methacrylate, polyvinyl alcohol, polyester diol, polyester polyol, polyether diol, polyether polyol, polycarbonate diol, polycarbonate polyol, polybutadiene diol , Polybutadiene polyol, polycaprolactone diol, polycaprolactone polyol, hydrogenated polypheno Le resins, and hydrogenated terpene resins are exemplified.

In the photosensitive composition of the present invention, a phenol resin, a derivative thereof, a terpene resin, or the like can be used in combination for improving the mechanical properties and adhesiveness of the photocured film. Examples of the phenol resin include novolak and resol. The use of novolak resin is preferable because it improves the mechanical strength and heat resistance of the cured film.
In the photosensitive composition of the present invention, a polyfunctional vinyl ether or oxetane containing no hydroxyl group can be used in combination. Examples of such vinyl ethers include ethylene glycol divinyl ether, butanediol divinyl ether, cyclohexanedimethanol divinyl ether, cyclohexanediol divinyl ether, trimethylolpropane trivinyl ether, pentaerythritol tetravinyl ether, glycerol trivinyl ether, triethylene glycol divinyl ether, Examples include diethylene glycol divinyl ether. Such oxetanes include 1,4-bis ([(3-ethyloxetane-3-yl) methoxy] methyl) benzene, bis [1-ethyl (3-oxetanyl)] methyl ether, 1,3- Bis [(3-ethyloxetane-3-yl) methoxy] benzene, 4,4′-bis [(3-ethyloxetane-3-yl) methoxy] biphenyl, phenol novolac oxetane, oxetanylsilsesquioxane, etc. Can do.

  In addition, other compounds exhibiting cationic polymerizability can be added to such an extent that the curability and film physical properties at the time of curing are not adversely affected. As these compounds, for example, low molecular weight epoxy compounds other than those mentioned above can be used as diluents, and cyclic lactone compounds, cyclic acetal compounds, cyclic thioether compounds, spiro orthoester compounds and the like can be mentioned. Also, conventionally used diols such as polyethylene glycol such as ethylene glycol, propylene glycol, diethylene glycol and triethylene glycol and polypropylene glycol, polyhydric alcohols such as glycerin, trimethylolpropane and pentaerythritol can be used.

In the composition of the present invention, the hydroxyl concentration of the aliphatic polyhydric alcohol (defined as the number of moles of the aliphatic polyhydric alcohol × the number of hydroxyl groups in one molecule) and the hydroxyl concentration of the hydroxy compound (the number of moles of hydroxy compound × in one molecule) Is preferably equal to or lower than the epoxy group concentration of the epoxy compound (defined as the number of moles of epoxy compound × the number of epoxy groups in one molecule), more preferably the functional group concentration of the epoxy group. 1 is 0.8 or less. This is because if the phenolic hydroxyl group concentration or the hydroxyl group concentration is excessive compared to the epoxy group concentration in the photosensitive composition, the hydrophilicity of the cured film becomes too high, resulting in insufficient water resistance or weakened cured film. This is because the cured film characteristics become insufficient.
In the photosensitive composition of the present invention, a radical polymerizable compound such as (meth) acrylate monomers and oligomers and vinyl (meth) acrylate, a photo radical initiator, an antifoaming agent, a leveling agent, and a polymerization are further included as necessary. Inhibitors, waxes, antioxidants, non-reactive polymers, fine particle inorganic fillers, silane coupling agents, light stabilizers, ultraviolet absorbers, antistatic agents, slip agents, and the like can also be added.

  Addition of the fine particle inorganic filler and the silane coupling agent is effective in reducing the moisture permeability of the coating film. Examples of such fine particle inorganic fillers are inorganic fillers having an average primary particle diameter of 0.005 to 10 μm, and specifically include silica, alumina, talc, calcium carbonate, mica and the like. The fine particle inorganic filler can be used both untreated and surface-treated, and examples of the finely divided inorganic filler subjected to surface treatment include methoxylated, trimethylsilylated, octylsilylated, or surface treated with silicone oil. These can be used alone or in combination of two or more. The silane coupling agent is an alkoxysilane compound having a reactive group such as an epoxy group, a carboxyl group, or a methacryloyl group. Specifically, γ-glycidoxypropyltrimethoxysilane, trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like can be mentioned, and one of these can be used alone or in combination of two or more. Can be used.

The photosensitive composition of the present invention is useful as a paint, an adhesive, an ink, a film coating, a resist material, etc. because of its excellent high-speed curability, low curing shrinkage and excellent adhesion to various substrates. It is. More specifically, examples include UV ink for inkjet printing, UV ink for gravure printing, UV ink for flexographic printing, UV ink for offset printing, UV ink for screen printing, UV ink for metal printing, and OP varnish for printed matter. . Also, sealing materials for display panels such as liquid crystal, organic EL and electronic paper, adhesives for bonding optical disks, surface protective layer forming materials for Blu-ray disks, next-generation optical disks, coating materials for forming antireflection films, hard It is useful as a coating material, a resist material for semiconductor production, a resist material for fine wiring, a solar cell sealant, and the like.
Further, since the photosensitive composition of the present invention can cure a thin film at high speed in the air, it is also suitable as a coating material for resin films, substrates and the like that are required to be cured at high speed without heating. used. As such an example, a coating material for forming an antireflection film used for FPD or the like can be mentioned.

<Characteristic evaluation of cured film>
(1) Tack-free exposure (TFED): The film after exposure was palpated and the minimum exposure required for the surface to harden and become non-sticky was determined.
○: TFED 120 mJ / cm ² or less ×: TFED 120 mJ / cm ^{2 or} more (2) Corrosiveness: After forming a cured film (thickness: about 12 μm) on a copper plate (C1100P), constant temperature and humidity of 80 ° C. and 90% RH It was left in the tank for 100 hours. The appearance after standing was visually evaluated.
○: No black spot corrosion ×: Black spot corrosion

[Example 1]
Preparation of Blocked Polyisocyanate Solution 94.8 g of tetrahydrofuran (THF) and 4.74 g (0.058 mol) of 2-methylimidazole were collected in a 200 ml four-necked flask containing a stirrer. After stirring until dissolved at room temperature, polyisocyanate of hexamethylene diisocyanate (NCO group 23.1 wt%, trade name “Duranate TPA100”, manufactured by Asahi Kasei Chemicals Corporation, 10 g (0.055 mol) was added at room temperature. Thereafter, a cooling tube was attached, and the mixture was stirred for 30 minutes in a nitrogen atmosphere, then heated to 40 ° C. and stirred for 2 hours, and then taken out.The resulting blocked polyisocyanate was liquid, fluid, red The characteristic absorption peak of the NCO group was not detected in the outer absorption spectrum, and the NCO group was completely blocked.

Curing Test and Corrosion Test Component (1) 58 parts by weight of 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, Component (2) 17 parts by weight of hydroxybutyl vinyl ether, Component (3) Energy rays 7-part by weight of sulfonium PF ₆ salt type CPI-100P (product name: manufactured by San Apro) as a sensitive cationic polymerization initiator, p- having a content of phenol 3-5 nuclei of 50 wt% as a polynuclear phenol compound A composition of 3 parts by weight of tert-Bu-phenol novolac resin (PAPS series: manufactured by Asahi Organic Materials Co., Ltd.) and 15 parts by weight of tetraethoxysilane as a component (5) reactive organosilicon compound was prepared. A transparent photosensitive composition was obtained by sufficiently mixing 3 parts by weight of the prepared blocked polyisocyanate with the composition added thereto.
In order to evaluate the characteristics of the photosensitive composition, first, coating was performed using a bar coater to a film thickness of 12 μm, and then TFED was measured with a 400 W high-pressure mercury lamp exposure machine (manufactured by Sen Special Light Source Co., Ltd.). The curability was good. Next, the copper substrate was irradiated with ultraviolet light equivalent to TFED, and the obtained cured film was left in a dryer at 120 ° C. for 30 minutes. After that, when corrosivity was evaluated, corrosion was suppressed. These results are shown in Table 1.

[Example 2]
Preparation of blocked polyisocyanate solution In a 100 ml three-necked flask containing a stirrer, 25.5 g of dimethylformamide (DMF) and 4.5 g (0.032 mol) of isopropylcyclohexylamine are taken and dissolved at room temperature. It was. Further, 31.39 g of DMF and 5.54 g of “Duranate TPA100” were taken in a separatory funnel and dissolved at room temperature, and then dropped in a nitrogen atmosphere at room temperature over about 30 minutes. Thereafter, the mixture was stirred at room temperature for 30 minutes and then taken out. The obtained blocked polyisocyanate was liquid and fluid, and the characteristic absorption peak of the NCO group was not detected in the infrared absorption spectrum, and the NCO group was completely blocked.

Curing Test and Corrosion Test Component (1) 60 parts by weight of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, component (2) 18 parts by weight of hydroxybutyl vinyl ether, component (3) energy ray sensitive cation 4 parts by weight of sulfonium PF ₆ salt type CPI-100P (product name: manufactured by San Apro) as a polymerization initiator, p-tert- having a content of phenol 3-5 nuclei of 50 wt% as a component (4) polynuclear phenol compound A composition of 3 parts by weight of a Bu-phenol novolac resin (PAPS series: Asahi Organic Materials Co., Ltd.) and 15 parts by weight of tetraethoxysilane as a component (5) reactive organosilicon compound was prepared. A transparent photosensitive composition was obtained by sufficiently mixing 3 parts by weight of the prepared blocked polyisocyanate with the composition added thereto.
Thereafter, evaluation was performed in the same manner as in Example 1. The curability was good and corrosion was suppressed. These results are shown in Table 1.

[Comparative Example 1]
The composition of Example 1 was cured using a composition to which no blocked polyisocyanate was added. Thereafter, the corrosivity was evaluated without performing the heat treatment. The copper plate was corroded. The results are shown in Table 1.
[Comparative Example 2]
After forming a cured film using the composition of Example 1, the corrosivity was evaluated without performing the heat treatment (120 ° C. × 30 minutes) of Example 1. The copper plate was corroded. The results are shown in Table 1.

  The composition of the present invention is useful as a constituent material for coating materials, UV inks, adhesives, sealants for flat panel displays (FPD) such as organic EL, and resist materials.

Claims (5)

(a) a cationic polymerizable composition comprising a compound having cationic polymerizability, (b) an energy ray-sensitive cationic polymerization initiator, and (c) a thermal amine generator , wherein the thermal amine generator has the following general formula ( 1) A cationically polymerizable composition which is an adduct formed by reacting one or more amines selected from the structures of (2), (3) and (4) with an isocyanate .

(However, R1, R2 represents an alkyl group or a phenyl group, and R3, R4, R5, R6 represent hydrogen, an alkyl group, or a phenyl group. Among R1, R2, and R3, two or all of the same are cyclic alkyl groups. 2 or all of R4, R5 and R6 may be part of the same cyclic alkyl group, R7 is an alkyl group or a phenyl group, R8, R9 and R10 are hydrogen and an alkyl group. R7 and R8 may be part of the same cyclic alkyl group, R9 and R10 may be part of the same cyclic alkyl group, R11 represents an alkylene group, R12, R13, R14 represents an alkyl group or a phenyl group, and R15, R16, R17 represent an alkyl group or a phenyl group.)   The composition according to claim 1, wherein the compound having cationic polymerizability is at least one selected from the group consisting of an epoxy compound having two or more epoxy groups in the molecule, an oxetane compound, and a vinyl ether compound. The composition according to claim 1 or 2 , wherein the energy ray-sensitive cationic polymerization initiator is a sulfonium salt and / or an iodonium salt. The composition according to any one of claims 1 to 3 , wherein the amine is an amine having a boiling point of 120 ° C or higher. A cured composition, wherein the composition according to any one of claims 1 to 4 is cured by irradiation with an energy ray and further subjected to a heat treatment.