JP2010174210A - Photocurable type resin composition and cured product thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photocurable type resin composition with a clear difference in the curability due to the presence or absence of light irradiation. <P>SOLUTION: The photocurable type resin composition includes (a) a compound of a 2-aminotropone derivative shown by formula (1), (b) a compound having two or more structures of 3-mercaptopropionic acid ester in the molecule and (c) a resin having two or more functional groups reactive with a thiol group, wherein R<SP>1</SP>and R<SP>2</SP>are each independently hydrogen, alkyl or aryl, R<SP>3</SP>-R<SP>7</SP>are each independently hydrogen, carboxyl, alkoxycarbonyl, cyano, formyl, acyl, nitro, nitroso, alkyl, aryl, hydroxy, thiol, alkoxy, halogen or amino, and R<SP>1</SP>-R<SP>7</SP>may be bound to each other to form a saturated ring or an unsaturated ring, and may independently have an univalent group made by elimiating one hydrogen atom from the compound shown by formula (1) as a substituent. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a photocurable resin composition and a cured product thereof.

  Resin photocuring technology is superior to conventional thermosetting technology in that it is not only capable of curing at low temperature and in a short time, but also enables fine processing by photopatterning. Widely used in the field. Resin photocuring techniques are roughly classified into three types: a radical type, a cationic type including an acid curable type, and an anionic type including a base curable type. Among these, radical type photocuring technology is the mainstream. However, (meth) acrylic acid polymers used in this photocuring technique generally have a large cure shrinkage, and there is room for improvement in heat resistance and adhesiveness.

  A number of compounds have been developed as photoacid generators used in acid-curing photocuring techniques. However, since the photoacid generator used in the acid-curing type generates strong protonic acid when irradiated with light, metals are easily corroded, and further study is required for practical use in the field of electronic materials.

  On the other hand, as one type of anionic photocuring technology for curing an anion curable resin by light irradiation, a base curable photocuring technology using a photobase generator is known. Patent Document 1 and Non-Patent Document 1 disclose carbamic acid derivatives as compounds that generate amines by light irradiation. Patent Documents 2 and 3 disclose photobase generators in which carbon dioxide gas is not by-produced. Patent Document 4 discloses a technique for increasing basicity by changing a 1,4-dihydropyridine skeleton to a pyridine skeleton by light irradiation. Patent Document 5 discloses a technique of using aminotropones as a photobase generator.

Japanese Patent Laid-Open No. 10-77264 JP 2005-264156 A Japanese Patent Laid-Open No. 2003-212856 JP 2003-20339 A International Publication No. 2008/072651 Pamphlet

UV / EB Curing Technology III, 1997, CM Publishing, P.I. 78

  However, with respect to the photobase generator, there is a problem that patterning with light may become unclear because the difference in curability according to the presence or absence of light irradiation is not sufficient. In particular, in the case of electronic materials, such a problem is particularly important because an extremely high-definition pattern is required, and a photocurable resin composition that has a clear difference in curability depending on the presence or absence of light irradiation is desired. It has been.

  Then, this invention is made | formed in view of the said situation, and it aims at providing the photocurable resin composition with which the difference in sclerosis | hardenability by the presence or absence of light irradiation is clear.

  As a result of intensive studies to solve the above problems, the present inventors have formulated a photocurable resin composition having a clear difference in curability depending on the presence or absence of light irradiation by blending an aminotropone derivative and a polythiool having a specific structure. And the hardened | cured material was obtained and the present invention was completed.

（式中、Ｒ^１とＲ^２は、互いに独立的に、水素原子、アルキル基、又はアリール基を表し、Ｒ^３〜Ｒ^７は、互いに独立的に、水素原子、カルボキシル基、アルコキシカルボニル基、シアノ基、ホルミル基、アシル基、ニトロ基、ニトロソ基、アルキル基、アリール基、ヒドロキシ基、チオール基、アルコキシ基、ハロゲン原子、又はアミノ基を表す。Ｒ^１〜Ｒ^７は、互いに結合し、飽和環又は不飽和環を形成していてもよく、それぞれ独立に、式（１）で表される化合物から１つの水素原子が脱離した１価の基を置換基として有していてもよい。）
（ｂ）３−メルカプトプロピオン酸エステルの構造を分子内に２つ以上含有する化合物と、
（ｃ）チオール基との反応性を有する官能基を２つ以上含有する樹脂と、
を含有する、光硬化型樹脂組成物。
［２］
チオール基との反応性を有する官能基を２つ以上含有する樹脂が、エポキシ樹脂である、［１］記載の光硬化型樹脂組成物。
［３］
３−メルカプトプロピオン酸エステルの構造を分子内に２つ以上含有する化合物が、ペンタエリスリトールテトラキス−３−メルカプトプロピオナート及び／又はジペンタエリスリトールヘキサキス−３−メルカプトプロピオナートである、［１］又は［２］に記載の光硬化型樹脂組成物。
［４］
２−アミノトロポン誘導体が、下記式（２）又は（３）で表される化合物である、［１］〜［３］のいずれか一項に記載の光硬化型樹脂組成物。

［５］
［１］〜［４］のいずれか一項に記載の光硬化型樹脂組成物を少なくとも光照射によって硬化させることにより得られる硬化物。 The present invention is as follows.
[1]
(A) a 2-aminotropone derivative represented by the following formula (1);

(In the formula, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, or an aryl group, and R ^{3 to} R ⁷ each independently represent a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, A cyano group, a formyl group, an acyl group, a nitro group, a nitroso group, an alkyl group, an aryl group, a hydroxy group, a thiol group, an alkoxy group, a halogen atom, or an amino group, R ^{1 to} R ⁷ are bonded to each other; A saturated ring or an unsaturated ring may be formed, and each may independently have a monovalent group in which one hydrogen atom is eliminated from the compound represented by formula (1) as a substituent. .)
(B) a compound containing two or more 3-mercaptopropionic acid ester structures in the molecule;
(C) a resin containing two or more functional groups having reactivity with a thiol group;
Containing a photocurable resin composition.
[2]
The photocurable resin composition according to [1], wherein the resin containing two or more functional groups having reactivity with a thiol group is an epoxy resin.
[3]
The compound containing two or more 3-mercaptopropionate structures in the molecule is pentaerythritol tetrakis-3-mercaptopropionate and / or dipentaerythritol hexakis-3-mercaptopropionate [1 ] Or the photocurable resin composition according to [2].
[4]
The photocurable resin composition according to any one of [1] to [3], wherein the 2-aminotropone derivative is a compound represented by the following formula (2) or (3).

[5]
A cured product obtained by curing the photocurable resin composition according to any one of [1] to [4] at least by light irradiation.

  ADVANTAGE OF THE INVENTION According to this invention, the photocurable resin composition and its hardened | cured material which have a clear difference in sclerosis | hardenability by the presence or absence of light irradiation can be provided.

  Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail. The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be implemented with appropriate modifications within the scope of the gist thereof.

The photocurable resin composition of the present embodiment contains the following components (a) to (c).
(A) a 2-aminotropone derivative represented by the following formula (1):

(In the formula, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, or an aryl group, and R ^{3 to} R ⁷ each independently represent a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, A cyano group, a formyl group, an acyl group, a nitro group, a nitroso group, an alkyl group, an aryl group, a hydroxy group, a thiol group, an alkoxy group, a halogen atom, or an amino group, R ^{1 to} R ⁷ are bonded to each other; A saturated ring or an unsaturated ring may be formed, and each may independently have a monovalent group in which one hydrogen atom is eliminated from the compound represented by formula (1) as a substituent. .)
(B) a compound containing two or more structures of 3-mercaptopropionic acid ester in the molecule;
(C) A resin containing two or more functional groups having reactivity with thiol groups.

<(A) component>
The 2-aminotropone derivative represented by the formula (1) can be synthesized by a known method. For example, by applying the method described in Daiichi Organic Chemistry, Vol. 13, Non-Benzene Aromatic Ring Compounds, Supervised by Fujio Kotake, Asakura Shoten Co., Ltd., 1957, various compounds can be synthesized. However, it is convenient to react with various amines after tosylating the hydroxy group of tropolones with p-toluenesulfonyl chloride or methyl ether with diazomethane or dimethyl sulfate.

In Formula (1), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, or an aryl group, and R ^{3 to} R ⁷ each independently represent a hydrogen atom, a carboxyl group, or an alkoxycarbonyl group. Cyano group, formyl group, acyl group, nitro group, nitroso group, alkyl group, thiol group, aryl group, hydroxy group, alkoxy group, halogen atom, amino group.

  Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a propenyl group, a butyl group, an isobutyl group, a tert-butyl group, a butenyl group, an isobutenyl group, a benzyl group, and a cyclohexyl group. In terms of compatibility with the component c), an isopropyl group is preferred.

  The aryl group is preferably a phenyl group.

  Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarboxyl group, and a hydroxyethoxycarbonyl group, and the methoxycarbonyl group is preferable in terms of compatibility with the component (c).

  As the acyl group, an acetyl group is preferable.

  Examples of the alkoxy group include a methoxy group, an ethoxy group, and a propoxy group, and a methoxy group is preferable in terms of compatibility with the component (c). The halogen atom is preferably chlorine or bromine in terms of stability.

  As amino group, in addition to unsubstituted amino group, mono-substituted amino group includes methylamino group, ethylamino group, propylamino group, isopropylamino group, butylamino group, isobutylamino group, cyclohexylamino group, benzylamino group Group, phenylamino group, and among them, methylamino group is preferable in terms of compatibility with component (c). Examples of the disubstituted amino group include dimethylamino group, diethylamino group, diisopropylamino group, dibutylamino group, Examples thereof include a diisobutylamino group, a dicyclohexylamino group, a dibenzylamino group, a diphenylamino group, a pyrrolidino group, a piperidino group, and a morpholino group. Among them, a dimethylamino group is preferable in terms of compatibility with the component (c).

R ^{1 to} R ⁷ may be bonded to each other to form a saturated ring or an unsaturated ring. For example, a pyrazole ring, an isoxazole ring, an isothiazole ring, an imidazole ring, an oxazole ring, a thiazole ring, a triazole ring, An azole ring such as a tetrazole ring may be formed. R ^{1 to} R ⁷ may each independently have a monovalent group in which one hydrogen atom is eliminated from the compound represented by the formula (1) as a substituent.

In the formula (1), a compound in which R ^{1 to} R ⁷ are any one of a hydrogen atom, an alkyl group, and an aryl group is particularly preferable because of excellent storage stability. Here, the storage stability means that it can be stored stably for a long period of time when it is not irradiated with light. Among them, a compound in which at least one of R ¹ and R ² is a hydrogen atom is preferable. More preferred compounds include 2-aminotropone derivatives represented by the following formula (2) or (3).

When R ² is a hydrogen atom in the formula (1), the structure of the formula (1) has a tautomeric relationship (see the following formula (4)). Therefore, in this embodiment, when the 2-aminotropone derivative can have a tautomeric relationship represented by the formula (4) or the like, the tautomeric structure is equivalent.

  In this embodiment, basicity can be expressed using a seven-membered ring intramolecular photomolecular cyclization reaction. For example, basicity can be expressed by cleaving a conjugated system that has reached the entire seven-membered ring by a photomolecular cyclization reaction represented by the following formula (5) and increasing the electron density on the nitrogen atom. .

  Although seven-membered rings are known to cause such intramolecular cyclization reactions (for example, O, L, Chapman, Advances in Photochemistry, Vol. 1, p. 323 (1963)) Similar reactions have been observed in various molecules regardless.

  Although the compounding quantity of 2-aminotropone derivative represented by Formula (1) in the photocurable resin composition of this embodiment is not specifically limited, (c) 0.001-100 mass parts with respect to 100 mass parts of component Is preferable, and 0.005-80 mass parts is more preferable. By setting it to 0.001 part by mass or more, a sufficiently practical curing rate can be obtained. By setting it to 100 parts by mass or less, excellent physical properties of the cured product can be obtained.

<(B) component>
In the photocurable resin composition of the present embodiment, the compound containing two or more structures of (b) 3-mercaptopropionic acid ester is not limited. Specific examples include compounds containing two or more structures represented by the following formula (6). An esterified product of 3-mercaptopropionic acid and a polyol having 2 or more carbon atoms is preferable, and an ester compound with a polyol having 2 to 30 carbon atoms is more preferable.

  For example, tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate, trimethylolpropane tris-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, dipentaerythritol hexakis-3- Mercaptopropionate and the like can be mentioned, among which pentaerythritol tetrakis-3-mercaptopropionate or dipentaerythritol hexakis-3-mercaptopropionate is more preferable.

  In the photocurable resin composition of the present embodiment, the compound having two or more 3-mercaptopropionic acid ester structures in the molecule is (total amount of SH groups) / (epoxy resin) with respect to 100 parts by mass of the epoxy resin. Is preferably contained so as to have a ratio of 0.5 / 1.5 to 1.5 / 0.5 in terms of (total amount of epoxy groups) (equivalent ratio). It is preferable to contain so that it may become a ratio of 2 / 0.8. When the photocurable resin composition contains the above compound in such a ratio, the curability tends to be further improved.

<(C) component>
In the photocurable resin composition of the present embodiment, (c) the resin containing two or more functional groups having reactivity with the thiol group (-SH) is not particularly limited, and a known resin is used. Can do. The functional group having reactivity with the thiol group is not particularly limited, and examples thereof include a double bond and an epoxy group. In this embodiment, examples of the resin containing two or more functional groups having reactivity with thiol groups include epoxy resins, acrylic resins, methacrylic resins, maleimide resins, allyl ether resins, vinyl ether resins, and cyclic resins. Examples include polyene resins and epoxy resins, and among them, epoxy resins are particularly preferable from the viewpoint of high storage stability. The epoxy resin is not particularly limited, and general-purpose ones can be used. For example, the following can be exemplified.

  As glycidyl ethers of dihydric phenols, bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, bisphenol S diglycidyl ether, halogenated bisphenol A diglycidyl ether, tetrachlorobisphenol A diglycidyl ether, catechin diglycidyl ether, resorcinol Diglycidyl ether, hydroquinone diglycidyl ether, 1,5-dihydroxynaphthalenediglycidyl ether, dihydroxybiphenyl diglycidyl ether, octachloro-4,4'-dihydroxyphenyl diglycidyl ether, tetramethylbiphenyl diglycidyl ether, 9,9'- Bis (4-hydroxyphenyl) furenediglycidyl ether, 2 moles of bisphenol A and epic Diglycidyl ether obtained from Rohidorin 3 moles of reaction.

  Examples of polyglycidyl ethers of polyhydric phenols having 3 to 6 or more valences include pyrogallol triglycidyl ether, dihydroxynaphthylcresol triglycidyl ether, tris (hydroxyphenyl) methane triglycidyl ether, dinaphthyltriglycidyl ether, tetrakis ( 4-hydroxyphenyl) ethanetetraglycidyl ether, p-glycidylphenyldimethyltolyl bisphenol A glycidyl ether, trismethyl-tert-butyl-butylhydroxymethane triglycidyl ether, 4,4′-oxybis (1,4-phenylethyl) tetracresol Glycidyl ether, 4,4′-oxybis (1,4-phenylethyl) phenyl glycidyl ether, bis (dihydroxynaphthalene) te Laglycidyl ether, glycidyl ether of phenol or cresol novolac resin, glycidyl ether of limonene phenol novolak resin, polyglycidyl ether of polyphenol obtained by condensation reaction of phenol and glycoxal, glutaraldehyde, or formaldehyde, and condensation reaction of resorcin and acetone And polyglycidyl ethers of polyphenols obtained by the above.

  Diglycidyl ethers of aliphatic dihydric alcohols include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether. Examples thereof include glycidyl ether, polytetramethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, diglycidyl ether of bisphenol A alkylene oxide [ethylene oxide or propylene oxide] adduct, and the like.

  Examples of polyglycidyl ethers of 3 to 6 or higher aliphatic alcohols include trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, pentaerythritol tetraglycidyl ether, sorbitol hexaglycidyl ether, polyglycerol polyglycidyl ether, and the like. .

  Examples of the glycidyl ester type include glycidyl esters of aromatic polycarboxylic acids such as phthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, trimellitic acid triglycidyl ester, and the like.

  Examples of glycidyl esters of aliphatic or cycloaliphatic polycarboxylic acids include aromatic nucleus hydrogenated aromatic dicarboxylic acid glycidyl ester, dimer acid diglycidyl ester, diglycidyl oxalate, diglycidyl malate, diglycidyl succinate. Nate, diglycidyl glutarate, diglycidyl adipate, diglycidyl pimelate, (co) polymer of glycidyl (meth) acrylate, tricarbyl acid triglycidyl ester and the like.

  Examples of glycidylamines of aromatic amines having active hydrogen atoms include N, N-diglycidyltoluidine, N, N, N ′, N′-tetraglycidyldiaminodiphenylmethane, N, N, N ′, N′-tetraglycidyl. Examples include diaminodiphenyl sulfone, N, N, N ′, N′-tetraglycidyldiethyldiphenylmethane, N, N, O-triglycidylaminophenol and the like.

  Examples of glycidylamines of alicyclic amines having an active hydrogen atom include hydrogenated products of N, N, N ′, N′-tetraglycidylxylylenediamine. Examples of glycidylamines of heterocyclic amines having an active hydrogen atom include triglycidyl isocyanurate and trisglycidylmelamine.

  Examples of chain aliphatic epoxides include epoxidized butadiene and epoxidized soybean oil. Alicyclic epoxides include vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, bis (2,3-epoxycyclopentyl) ether, ethylene glycol bisepoxy dicyclopentyl ether, 3,4-epoxy-6-methyl. Cyclohexylmethyl-3 ′, 4′-epoxy 6′-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, and bis (3,4-epoxy-6-methylcyclohexylmethyl) butylamine Etc.

  In the present embodiment, two or more epoxy resins can be used in combination. A glycidyl ether type and a glycidyl ester type are preferable, and a glycidyl ether type is more preferable.

  In the photocurable resin composition of this embodiment, you may further contain a phenol resin. Examples of the phenolic resin include phenolic resins such as novolak resins and resol resins, and among these, novolak resins are preferable. Examples of the novolak resin include a phenol novolak resin and a cresol novolak resin, and a cresol novolak resin is more preferable.

  From the viewpoint of curability, the amount of the phenol resin is preferably 0.001 to 100 parts by mass, more preferably 0.01 to 90 parts by mass with respect to 100 parts by mass of the epoxy resin.

  In the photocurable resin composition of this embodiment, you may further contain the organic solvent as needed. Although it does not specifically limit as an organic solvent, For example, ethers, such as diethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether; Ethylene glycol monomethyl ether, ethylene glycol monoethyl Glycol monoethers such as ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether (so-called cellosolves); ketones such as methyl ethyl ketone, acetone, methyl isobutyl ketone, cyclopentanone, cyclohexanone Ethyl acetate and acetate N-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, acetate esters of the above glycol monoethers (for example, methyl cellosolve acetate, ethyl cellosolve acetate), methoxypropyl acetate, ethoxypropyl acetate, Esters such as dimethyl oxalate, methyl lactate, ethyl lactate; alcohols such as methanol, ethanol, isopropanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, glycerin; methylene chloride, 1,1-dichloroethane, 1 , 2-dichloroethylene, 1-chloropropane, 1-chlorobutane, 1-chloropentane, chlorobenzene, bromobenzene, o-dichlorobenzene, m-dichlorobenzene, etc. Halogenated hydrocarbons; Amides such as N, N-dimethylformamide and N, N-dimethylacetamide; Pyrrolidones such as N-methylpyrrolidone; Lactones such as γ-butyrolactone; Sulfoxides such as dimethylsulfoxide, hexane, Examples include chain or cyclic saturated hydrocarbons such as cyclohexane and heptane, and other organic polar solvents. Furthermore, examples of the organic solvent include aromatic hydrocarbons such as benzene, toluene, and xylene, and other organic nonpolar solvents. These organic solvents can be used individually by 1 type or in combination of 2 or more types.

  In the photocurable resin composition of the present embodiment, if necessary, barium sulfate, barium titanate, silicon oxide powder, finely divided silicon oxide, amorphous silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, You may contain well-known inorganic fillers, such as aluminum hydroxide and mica powder. Thereby, various characteristics, such as the adhesiveness of a hardening body and a base material, and the hardness of a hardening body, can be improved.

  In the photocurable resin composition of the present embodiment, phthalocyanine blue, phthalocyanine green, iodin green, disazo yellow, crystal violet, titanium oxide, as necessary, within a range that does not impair the effects of the present embodiment. Coloring agents such as carbon black and naphthalene black; polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, tert-butylcatechol, pyrogallol, and phenothiazine; thickeners such as asbestos, olben, benton, and montmorillonite; silicones, fluorines, Defoaming agents such as polymers; additives such as leveling agents, imidazole, thiazole, triazole, and adhesion-imparting agents such as silane coupling agents; hindered phenolic antioxidants, hindered amines Agent (HALS), etc. may be contained in appropriate.

  In the photocurable resin composition of this embodiment, you may contain 1 type, or 2 or more types of well-known photoradical initiators, such as a benzophenone, a benzophenone derivative, an acetophenone, and an acetophenone derivative, as needed.

  The photocurable resin composition of this embodiment can be cured by light irradiation. At that time, only light irradiation may be performed, light irradiation and heating may be performed simultaneously, or heating may be performed after the light irradiation.

Although it can select suitably about the light source and conditions of light irradiation, it is preferable to carry out using the irradiation light of a 150-750 nm wavelength range. More specifically, it is preferable to perform light irradiation at a dose of 0.01 to 100 J / cm ² using a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp and / or a metal halide lamp. Thereby, a photocurable resin composition can be hardened | cured efficiently.

The light irradiation is preferably performed at a dose of 0.05 to 20 J / cm ² using irradiation light in a wavelength range of 200 to 400 nm.

  The heating temperature in the case of heating is not particularly limited as long as it is a temperature below the decomposition point of the resin composition, preferably 30 to 400 ° C, more preferably 50 to 300 ° C. The heating time in the case of heating is preferably 1 second to 3 hours, and more preferably 30 seconds to 1 hour in order to perform curing more sufficiently.

  The photocurable resin composition of this embodiment can form a pattern using this. The method for forming the pattern is not particularly limited, and can be performed as follows, for example.

  First, a photomask is applied to the surface of a coating film or a molded body obtained by applying the photocurable resin composition of the present embodiment to a substrate. When this is irradiated with light, a latent image can be formed by curing a coating film or a portion of the molded body (light irradiation portion) irradiated with light in a pattern shape through a photomask or the like.

  Next, if necessary, the solubility of the light-irradiated part of the coating film or molded body can be selectively reduced by performing post-treatment such as heat treatment on the coated film or molded body after light irradiation. it can.

  Subsequently, using a developer such as an aqueous solution or an organic solvent, a pattern can be formed by selectively removing the non-irradiated portion of the coating film or molded body.

  In addition, the method of apply | coating the photocurable resin composition of this embodiment to a base material is not specifically limited. Specific examples thereof include, for example, flexographic printing method, gravure printing method, offset printing method, gravure offset printing method, screen printing method, ink jet method, spray method, spin coating method, roll coating method, electrostatic coating method, curtain coating method. Known methods such as the method can be mentioned.

  Light irradiation and heating to a coating film or a molded product obtained by applying the photocurable resin composition of the present embodiment to a substrate can be performed in the same manner as described above. There are no particular limitations on the developer used when the light-irradiated portion of the coating film or molded body is selectively removed, and examples include basic aqueous solutions, acidic aqueous solutions, neutral aqueous solutions, and organic solvents. The developer can be appropriately selected in consideration of curable components such as a polymer precursor contained in the photocurable resin composition.

  Although it does not specifically limit as basic aqueous solution, For example, tetramethylammonium hydroxide (TMAH) aqueous solution, potassium hydroxide aqueous solution, sodium hydroxide aqueous solution, magnesium hydroxide aqueous solution, calcium hydroxide aqueous solution, sodium hydrogencarbonate aqueous solution, 1st grade Examples thereof include aqueous solutions of secondary and tertiary amines, and aqueous solutions of hydroxide ions and ammonium ion salts.

  The alkali concentration of the basic aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass. The solute contained in the basic aqueous solution may be used alone or in combination of two or more. The concentration is preferably 50% or more of the total mass, more preferably 70% or more. The basic aqueous solution only needs to contain water, and may further contain a solvent other than water, such as an organic solvent. One basic aqueous solution is used alone, or two or more basic aqueous solutions are used in combination.

  The acidic aqueous solution is not particularly limited as long as it has a pH lower than 7. Examples of the acidic aqueous solution include aqueous solutions of organic acids such as lactic acid, acetic acid, oxalic acid, and malic acid, and aqueous solutions of hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid.

  The neutral aqueous solution is not particularly limited as long as it can selectively remove the light non-irradiated site. Examples of the neutral aqueous solution include an aqueous solution of a water-soluble solvent such as ethanol.

  Although it does not specifically limit as an organic solvent used as a developing solution, For example, ethers, such as diethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether; Ethylene glycol monomethyl ether , Glycol monoethers (so-called cellosolves) such as ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether; methyl ethyl ketone, acetone, methyl isobutyl ketone, cyclopentanone, Ketones such as cyclohexanone Ethyl acetate, butyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, acetate esters of the above glycol monoethers (for example, methyl cellosolve acetate, ethyl cellosolve acetate), methoxypropyl acetate Esters such as ethoxypropyl acetate, dimethyl oxalate, methyl lactate, ethyl lactate; alcohols such as methanol, ethanol, isopropanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, glycerin; methylene chloride, 1, 1-dichloroethane, 1,2-dichloroethylene, 1-chloropropane, 1-chlorobutane, 1-chloropentane, chlorobenzene, bromobenzene, o-dichlorobenzene, -Halogenated hydrocarbons such as dichlorobenzene; amides such as N, N-dimethylformamide and N, N-dimethylacetamide; pyrrolidones such as N-methylpyrrolidone; lactones such as γ-butyrolactone; dimethyl sulfoxide and the like Examples thereof include sulfoxides, chain-like or cyclic saturated hydrocarbons such as hexane, cyclohexane and heptane, and other organic polar solvents. Furthermore, examples of the organic solvent include aromatic hydrocarbons such as benzene, toluene, and xylene, and other organic nonpolar solvents. These organic solvents are used alone or in combination of two or more.

  Further, these organic solvents may be used as a mixed solvent in combination with water, a basic aqueous solution, an acidic aqueous solution and / or a neutral aqueous solution. Thereby, a better pattern shape can be obtained.

  The photocurable resin composition of the present embodiment can exhibit sufficient photocuring properties without problems such as generation of bubbles due to by-products such as carbon dioxide gas and a decrease in insulation reliability due to containing an ionic component. it can.

  Since the photocurable resin composition of this embodiment has a sufficiently large difference in curability depending on the presence or absence of light irradiation, a clear pattern can be formed. Therefore, the photocurable resin composition of the present embodiment and the cured product thereof can be used for a wide range of applications, and can meet demands for short-time curing and precision patterning in electronic material applications and the like. By-products are not generated when the resin composition of the present embodiment is cured, and high-precision photo-patterning is possible. Therefore, the resin composition is particularly preferably used as a resin for electronic materials that require severe photo-patterning properties. Can do.

  Further, a compound containing two or more 3-mercaptopropionic acid ester structures in the molecule has its own odor compared to a compound having a similar structure conventionally used, for example, 2-mercaptoacetic acid ester type. It has a small amount of thermal stability and has the advantage of less decomposition and odor generation due to heating.

  The photocurable resin composition of the present embodiment includes paints, adhesives such as conductive adhesives, inks such as printing inks, resist materials such as photoresists and solder resists, coverlays, coating materials, various automobile parts, electric・ Electronic materials, semiconductor devices, semiconductor materials, semiconductor sealing materials, semiconductor liquid molding materials, die bonding materials, underfill materials, optical materials, optical fibers, optical fiber adhesives, optical waveguide materials, optical circuit components, color filters, flexible Display film, liquid crystal sealant, LED sealant, organic EL sealant, interlayer insulation film, wiring coating film, antireflection film, hologram, building material, 3D modeling, filler, molding material, etc. It can be applied to various fields and products (articles).

  The composition of the photocurable resin composition of the present embodiment can be adjusted according to various properties such as desired heat resistance, dimensional stability, and insulation in these applications. In particular, regarding the use of the adhesive, the photocurable resin composition of the present embodiment is not limited to adhesives for bonding wood, building materials, plastics, leather, etc., but also circuits such as anisotropic conductive adhesives, silver pastes, and silver films. It can be used as a semiconductor element adhesive material such as an anisotropic conductive material for flip chip for connecting a semiconductor element such as a connection material or flip chip and a printed wiring board.

  Hereinafter, the present embodiment will be described in more detail by way of examples. However, the present embodiment is not limited to these examples.

[Example 1]
<Synthesis of 2-aminotropone derivative>
A mixture of 2-methoxy-4-isopropyl tropone and 2-methoxy-6-isopropyl tropone (2.0 g, 11.2 mmol) synthesized according to a conventional method from 4-isopropyl tropolone (manufactured by Asahi Kasei Finechem Co., Ltd.) and diazomethane. ) And 1,2-propanediamine (207 mg, 2.8 mmol) were dissolved in 10 mL of ethanol and heated and stirred at reflux temperature for 24 hours. After the ethanol was distilled off under reduced pressure, a 2-aminotropone derivative (1,2 was obtained by column chromatography (“Wakogel C-300” manufactured by Wako Pure Chemical Industries, Ltd., using ethyl acetate as a developing solvent)). -Bis (2-oxo-4 (6) -isopropyl-1,3,5-cycloheptatrienylamino) propane, see Table 1) was isolated. The yield was 915 mg (2.5 mmol), and the yield based on 1,2-propanediamine was 89%.
The obtained 2-aminotropone derivative was confirmed by ¹ H-NMR (“ECA-500” manufactured by JEOL Ltd.).

<Photocurable resin composition>
70 parts by mass of a bisphenol A type epoxy resin (product name “AER250” manufactured by Asahi Kasei Chemicals Corporation), 30 parts by mass of pentaerythritol tetrakis-3-mercaptopropionate (manufactured by SC Organic Chemical Co., Ltd., PEMP), and synthesis The photocurable resin composition was obtained by mixing 10 parts by mass of the 2-aminotropone derivative. The obtained photocurable resin composition was applied on a glass plate to form a coating film having a thickness of 100 μm.
First, this coating film was heated at 120 ° C. The heating time until curing started was measured and set as the curing time. The curing time was 185 minutes.
Next, this coating film was irradiated with ultraviolet rays (wavelength: 365 nm) of 30 mW / cm ² for 5 minutes under a nitrogen atmosphere (irradiation amount: 9 J / cm ² ). Then, this coating film was heated at 120 degreeC. The heating time until curing started was measured and set as the curing time. The curing time was 3 minutes. In addition, the measurement of the time when hardening starts was measured by visual observation with a stylus.

[Example 2]
70 parts by mass of a bisphenol A type epoxy resin (manufactured by Asahi Kasei Chemicals Corporation, trade name “AER250”), 30 parts by mass of dipentaerythritol-hexakis-3-mercaptopropionate (manufactured by SC Organic Chemical Co., Ltd., DPMP) Then, 10 parts by mass of the 2-aminotropone derivative synthesized by the method of Example 1 was mixed to obtain a photocurable resin composition.

The obtained photocurable resin composition was applied on a glass plate to form a coating film having a thickness of 100 μm.
First, this coating film was heated at 120 ° C. The heating time until curing started was measured and set as the curing time. The curing time was 173 minutes.
Next, this coating film was irradiated with ultraviolet rays (wavelength: 365 nm) of 30 mW / cm ² for 5 minutes under a nitrogen atmosphere (irradiation amount: 9 J / cm ² ). Then, this coating film was heated at 120 degreeC. The heating time until curing started was measured and set as the curing time. The curing time was 3 minutes.

Example 3
<Synthesis of 2-aminotropone derivative>
A mixture of 2-methoxy-4-isopropyl tropone and 2-methoxy-6-isopropyl tropone (2.0 g, 11.2 mmol) synthesized according to a conventional method from 4-isopropyl tropolone (manufactured by Asahi Kasei Finechem Co., Ltd.) and diazomethane. ) And 4.0 g of 25 mass% ammonia (ammonia content: 4.0 g, 235 mmol) were mixed and heated and stirred at 50 ° C. for 24 hours. After cooling to 25 ° C., extraction was performed 3 times with 10 mL of dichloromethane. Dichloromethane was distilled off under reduced pressure, and then a column chromatograph (manufactured by Wako Pure Chemical Industries, Ltd., “Wakogel C-300” was used with ethyl acetate as a developing solvent.) Was used to prepare a 2-aminotropone derivative (2- A mixture of amino-4-isopropyltropone and 2-amino-6-isopropyltropone; see Table 1) was isolated. The yield was 1.2 g (7.4 mmol), and the yield based on a mixture of 2-methoxy-4-isopropyltropone and 2-methoxy-6-isopropyltropone was 66%.
The obtained 2-aminotropone derivative was confirmed by ¹ H-NMR (manufactured by JEOL Ltd., “ECA-500”).

<Photocurable resin composition>
70 parts by mass of a bisphenol A type epoxy resin (trade name “AER250” manufactured by Asahi Kasei Chemicals Corporation), 30 parts by mass of pentaerythritol-tetrakis-3-mercaptopropionate (SCMP, manufactured by SC Organic Chemical Co., Ltd.), 10 parts by mass of the synthesized 2-aminotropone derivative was mixed to obtain a photocurable resin composition.
The obtained photocurable resin composition was applied on a glass plate to form a coating film having a thickness of 100 μm.
First, this coating film was heated at 120 ° C. The heating time until curing started was measured and set as the curing time. The curing time was 178 minutes.
Next, this coating film was irradiated with ultraviolet rays (wavelength: 365 nm) of 30 mW / cm ² for 5 minutes under a nitrogen atmosphere (irradiation amount: 9 J / cm ² ). Then, this coating film was heated at 120 degreeC. The heating time until curing started was measured and set as the curing time. The curing time was 3 minutes.

[Comparative Example 1]
70 parts by mass of a bisphenol A type epoxy resin (manufactured by Asahi Kasei Chemicals Corporation, trade name “AER250”), 30 parts by mass of tetrakis (mercaptoacetic acid) pentaerythritol (manufactured by Wako Pure Chemical Industries, Ltd.), The photocurable resin composition was obtained by mixing 10 parts by mass of the 2-aminotropone derivative synthesized by the method. The obtained photocurable resin composition was applied on a glass plate to form a coating film having a thickness of 100 μm.

First, this coating film was heated at 120 ° C. The heating time until curing started was measured and set as the curing time. The curing time was 48 minutes.
Next, this coating film was irradiated with ultraviolet rays (wavelength: 365 nm) of 30 mW / cm ² for 5 minutes under a nitrogen atmosphere (irradiation amount: 9 J / cm ² ). Then, this coating film was heated at 120 degreeC. The heating time until curing started was measured and set as the curing time. The curing time was 3 minutes.

  The results of Examples 1 to 3 and Comparative Example 1 are shown in Table 1.

  In Examples 1 to 3, the difference in curing time depending on the presence or absence of light irradiation was 170 to 182 minutes, whereas in Comparative Example 1 was 45 minutes. As mentioned above, according to the present Example, it was shown that the photocurable resin composition of this embodiment is a photocurable resin composition with a clear difference in curability depending on the presence or absence of light irradiation. As a result, it was shown that the photocurable resin composition of this embodiment can form a clear pattern by light irradiation, can be cured in a short time, and can be precisely patterned.

  The photocurable resin composition and the cured product thereof according to the present invention can be widely used including paints, adhesives, inks, resist materials, various automobile parts, electric / electronic materials, etc. It can be suitably used as a resin for electronic materials.

Claims (5)

(A) a 2-aminotropone derivative represented by the following formula (1);
(B) a compound containing two or more 3-mercaptopropionic acid ester structures in the molecule;
(C) a resin containing two or more functional groups having reactivity with a thiol group;
Containing a photocurable resin composition.

(In the formula, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, or an aryl group, and R ^{3 to} R ⁷ each independently represent a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, A cyano group, a formyl group, an acyl group, a nitro group, a nitroso group, an alkyl group, an aryl group, a hydroxy group, a thiol group, an alkoxy group, a halogen atom, or an amino group, R ^{1 to} R ⁷ are bonded to each other; A saturated ring or an unsaturated ring may be formed, and each may independently have a monovalent group in which one hydrogen atom is eliminated from the compound represented by formula (1) as a substituent. .)   The photocurable resin composition according to claim 1, wherein the resin containing two or more functional groups having reactivity with the thiol group is an epoxy resin.   The compound containing two or more 3-mercaptopropionate structures in the molecule is pentaerythritol tetrakis-3-mercaptopropionate and / or dipentaerythritol hexakis-3-mercaptopropionate. Item 3. The photocurable resin composition according to Item 1 or 2. The photocurable resin composition according to any one of claims 1 to 3, wherein the 2-aminotropone derivative is a compound represented by the following formula (2) or (3).

  Hardened | cured material obtained by hardening the photocurable resin composition as described in any one of Claims 1-4 by light irradiation at least.