TWI480293B - A photohardenable resin and a photohardenable resin composition - Google Patents

Description

Photocurable resin and photocurable resin composition

The present invention relates to a cured product which is excellent in photocurability, heat resistance, adhesion, and flexibility, and a composition containing the same.

The photocurable resin, in particular, a UV curable resin, is used in a wide range of applications from the viewpoints of rapid curing and energy saving, and is widely used for an adhesive, a printing ink, various coating agents, and the like. Further, the photoresist which is mixed with the carboxyl group-containing resin to impart alkali developability is used as a resist for circuit formation for use in a printed circuit board, or as a plating resist, a solder resist, or the like. Others can be used as a color filter or a black matrix or a protective agent for flat display applications.

The UV curable resin is generally a polyester acrylate, an epoxy acrylate, a urethane acrylate or the like (for example, refer to Patent Documents 1 to 3), and almost all of them are from the viewpoint of rapid hardenability. It is a liquid compound. However, this form of resin is indeed imparted with rapid hardening properties, and conversely, there are many problems in the residual properties of many electronic materials such as reflow resistance or solder heat resistance. Further, in general, the quick-curing resin has a marked hardening shrinkage, and the obtained cured product is brittle and has poor adhesion. It is a property that is strongly required for adhesives, printing inks, various coating agents, etc., and it is necessary to develop (meth) which has such heat resistance and adhesion. Acrylate resin.

On the other hand, environmental issues have been widely discussed in recent years. Recently, new materials are attracting attention. They are not derived from compounds of petroleum resources but from natural materials. Among them, the inventors noticed lactic acid. Lactic acid is not a compound derived from petroleum resources, and fermented lactic acid obtained by fermentation of a natural product can be used. Further, since the molecule has a functional group which can be easily chemically modified, such as a carboxyl group or a hydroxyl group, a wide variety of molecular designs can be made. Further, depending on the molecular design, the proportion of carbon derived from natural materials can be increased, and thus a very environmentally friendly material can be provided.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 3446840

[Patent Document 2] Japanese Patent No. 3543409

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2004-123780

The present invention has been made in view of the above-described background, and it is an object of the present invention to provide a photocurable resin which is excellent in heat curable property and excellent in heat resistance, adhesion, and flexibility by using lactic acid as one of the starting materials. And a photocurable resin composition containing the same;

In order to achieve the aforementioned object, according to the present invention, there can be provided a photocurable resin characterized by having an epoxy compound (a), lactic acid or polylactic acid (b), and (meth)acrylic acid having an acid group or an isocyanate group. The monomer (c) is obtained by reacting as an essential monomer component, and has a molecular structure represented by the following formula (I).

(wherein, Ac represents a (meth)acryloxy group, R ¹ represents a residue of the compound (a) in which a ring group formed by ring-opening of an epoxy group-containing compound (a), and R ² represents a carbonyloxy or urethane-bonded moiety; n represents an integer from 1 to 99, and m represents 0 or 1).

In the present specification, the term "(meth)acrylic" refers to the term "acrylic acid", "methacrylic acid", and the like, and relates to (meth)acryloxy group, (meth)acrylic acid, (A). The base acrylate or other similar performance is also the same.

In a suitable form, the photocurable resin is a structural unit represented by the following general formula (II) as an essential repeating unit.

(wherein, Ac represents a (meth) propylene decyloxy group, R ² represents a carbonyloxy group or a urethane-bonded node site, fc represents a hydroxy group or a (meth) propylene decyloxy group, and R ³ A hydrocarbon group having 1 to 10 carbon atoms, n is an integer from 1 to 99, m is 0 or 1, and a dotted line indicates a bond with another structural unit.

In a more suitable aspect, in the above formula (I) or (II), a node having a carbonyloxy group or a urethane bond represented by R ² is a formula a1. A2, or the object represented by a3.

(In the above formula, R ₄ represents an alkylene group having 1 to 10 carbon atoms, R ₅ represents a hydrocarbon group having 1 to 20 carbon atoms, R ₆ represents an alkylene group having 1 to 30 carbon atoms, and R ₇ represents carbon. Atom number 1~10 alkyl group).

In other suitable embodiments, the photocurable resin has an average of 0.1 to 2.0 (meth) acryloxy groups per molecule of the epoxy compound.

In a particularly suitable aspect, the aforementioned epoxy compound (a) is an epoxy resin (a') having two or more epoxy groups in one molecule, and (meth)acrylic acid having an acid group or an isocyanate group. The monomer (c) is a (meth)acrylic acid, and has a molecular structure obtained by reacting a (meth)acrylic acid with a hydroxyl group-containing resin of a reaction product of the epoxy resin (a') and lactic acid.

Among other suitable forms, the aforementioned epoxy compound (a) is an epoxy resin (a') having two or more epoxy groups in one molecule, and (meth)acrylic acid having an acid group or an isocyanate group. The monomer (c) is a (meth) acrylonitrile alkyl isocyanate and has a reaction of (meth) propylene decyl alkyl isocyanate with the above epoxy resin (a') with lactic acid or polylactic acid (b) The structure obtained by reacting the hydroxyl group-containing resin of the product.

In another suitable aspect, the aforementioned epoxy compound (a) has a molecular structure which is a reaction between an acid anhydride or a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate monomer in one molecule. An epoxy resin (a') having two or more epoxy groups, and the epoxy resin (a') is reacted with a hydroxyl group-containing resin of a reaction product of lactic acid or polylactic acid (b).

Further, according to the present invention, there is also provided a photocurable resin containing a carboxyl group, which is obtained by reacting an acid anhydride (d) with the photocurable resin.

Further, according to the present invention, there is provided a photocurable resin composition comprising at least one photohardening selected from the group consisting of the photocurable resin (A) and the carboxyl group-containing photocurable resin (A'). The resin and the photopolymerization initiator (B) are essential components.

Further, the carboxyl group-containing photocurable resin (A') may further contain a carboxyl group-containing resin (C) or a thermosetting component (D).

The photocurable resin of the present invention contains an epoxy compound (a), lactic acid or polylactic acid (b), and a (meth)acrylic monomer (c) having an acid group or an isocyanate group as essential monomer components. By using lactic acid as one of the starting materials, an environmentally-friendly cured product can be formed, and since the structural portion represented by the above formula (I) is an essential repetitive unit, it is excellent in UV curability. A cured product excellent in heat resistance, adhesion, and flexibility.

By reacting such functional groups of the (meth)acrylic monomer (c) having an acid group or an isocyanate group with a terminal hydroxyl group produced by the reaction of the epoxy compound (a) with lactic acid or polylactic acid (b) The photocurable resin of the present invention can be easily obtained. In such a manner, the unsaturated double bond of the (meth)acrylic monomer (c) is introduced into a portion away from the main chain of the resin via the lactic acid skeleton, thereby exhibiting excellent photoreactivity while introducing lactic acid. By the skeleton, a cured product having hydrophilicity and adhesion and flexibility can be obtained. Further, depending on the molecular design, the lactic acid content can be greatly increased, and a photocurable resin which is mild to the environment can be obtained. Further, heat resistance can be imparted by selectively reacting an epoxy compound reactive with lactic acid. Further, at this time, a substance which selectively reacts with lactic acid and can impart heat resistance is easily obtained by using an epoxy resin.

Hereinafter, the photocurable resin of the present invention will be specifically described in detail.

First, when a polyfunctional cresol novolac type epoxy resin is used as the component (a), lactic acid is used as the component (b), and (meth)acrylic acid is used as the component (c), photohardening as shown by the following formula can be obtained. Resin.

Further, when a polyfunctional cresol novolac type epoxy resin is used as the component (a), lactic acid is used as the component (b), and (meth)acrylic anhydride is used as the component (c), light represented by the following formula can be obtained. Curable resin.

Further, when a polyfunctional cresol novolac type epoxy resin is used as the component (a), lactic acid is used as the component (b), and 2-propenyloxyethyl isocyanate is used as the component (c), the following formula can be obtained. A photocurable resin as shown.

Further, it is considered that a polyfunctional cresol novolac type epoxy resin is used for the component (a), a lactic acid is used for the component (b), and a polyisocyanate compound and a hydroxyl group-containing (meth)acrylate monomer are reacted with the component (c). In the case of a substance (for example, a reaction product of isophorone diisocyanate and hydroxyethyl (meth)acrylate), a photocurable resin as shown by the following formula can be obtained.

In addition, the total count of the overlapping units a and b, the total count of c, d, and e, the total count of f and g, and the total count of h and i are used as (a). The number of epoxy groups of the epoxy resin of the component is not more than the number of epoxy groups, and can be arbitrarily adjusted depending on the reaction ratio of the component (b) and the component (c) to the component (a).

The reaction of the above components (a) to (c) may be carried out by simultaneously using lactic acid or polylactic acid (b) and a (meth)acrylic monomer (c) having an acid group or an isocyanate group together with the epoxy compound (a). The reaction method is either a method of first reacting lactic acid or polylactic acid (b), and then a method of reacting the (meth)acrylic monomer (c) having an acid group or an isocyanate group. Such a reaction is carried out in the presence or absence of an organic solvent as described later, and in the presence of a polymerization inhibiting agent such as hydroquinone or oxygen, and is usually carried out at about 50 to 150 °C. In this case, a tertiary amine such as triethylamine or a tertiary ammonium salt such as triethylbenzylammonium chloride or an imidazole compound such as 2-ethyl-4-methylimidazole or a phosphorus compound such as triphenylphosphine may be added as necessary. As a catalyst.

In addition, in the above reaction, the ratio of each component (the ratio of the raw materials to be charged) is 0.2 equivalent to the epoxy group of the epoxy compound (a), and the carboxyl group of the lactic acid or polylactic acid (b) is 0.2~ 1.1 equivalent, and the total of the hydroxyl group produced by the reaction of the epoxy group of the component (a) with the carboxyl group of the component (b) and the residual hydroxyl group of the lactic acid or the polylactic acid (b) is 1 equivalent, and has an acid group or an isocyanate The acid group or the isocyanate group of the (meth)acrylic monomer (c) is preferably a ratio of 0.05 to 1.0 equivalent. When the carboxyl group of the lactic acid or the polylactic acid (b) is less than 0.2 equivalent in terms of 1 equivalent of the epoxy of the epoxy compound (a), the heat resistance and the adhesion of the object of the present invention are not sufficiently obtained. The effect of improving the flexibility is, on the other hand, more than 1.1 equivalents, and even if it is used in excess, only one equivalent is theoretically reacted. Therefore, the amount of such compounds remaining in an unreacted state increases, which causes a decrease in the physical properties of the cured product. Therefore, it is not good.

The photocurable resin (A) obtained in such a manner is preferably 0.1 to 2.0 equivalents of (meth)acryloxy group based on 1 equivalent of the final epoxy group.

In addition, the weight average molecular weight of the photocurable resin (A) obtained by the above reaction varies depending on the resin skeleton, and is generally 2,000 to 150,000, more preferably 5,000 to 100,000. When the weight average molecular weight is less than 2,000, there is a case where the dryness of the touch-sensitive property of the coating film is poor, the moisture resistance of the coating film after the exposure is poor, and the film is reduced at the time of development, and the resolution is largely deteriorated. On the other hand, when the weight average molecular weight exceeds 150,000, workability is deteriorated and storage stability is poor. Further, the weight average molecular weight can be measured by, for example, GPC or the like under the following conditions.

Measuring device: "HLC-8220 GPC" manufactured by Tosoh Corporation, pipe column: protection column "H _XL -L" manufactured by Tosoh Corporation

+TSK-GEL G2000HXL made by Tosoh Corporation

+TSK-GEL G2000HXL made by Tosoh Corporation

+TSK-GEL G3000HXL made by Tosoh Corporation

+TSK-GEL G4000HXL made by Tosoh Corporation

Detector: RI (differential refractometer)

Determination conditions:

Column temperature: 40 ° C

Developing solvent: tetrahydrofuran

Flow rate: 1.0ml/min

Further, the double bond equivalent of the photocurable resin (A) is preferably 100 g / equivalent to 1000 g / equivalent. From the viewpoint of improving photocurability, it is preferably 100 g / equivalent to 600 g / equivalent. Further, from the viewpoint of improving flexibility, it is preferred that the double bond equivalent is 500 g/eq or more.

The epoxy compound (a) used for the synthesis of the photocurable resin (A) may, for example, be 2-hydroxyethyl (meth)acrylate glycidyl ether or 2-hydroxypropyl (meth)acrylate. Glycidyl ether, 3-hydroxypropyl (meth) acrylate glycidyl ether, 2-hydroxybutyl (meth) acrylate glycidyl ether, 4-hydroxybutyl (meth) acrylate glycidyl ether, (methyl) Epoxy-containing ethylenically unsaturated monomer such as 2-hydroxypentyl acrylate glycidyl ether, 6-hydroxyhexyl methacrylate (meth) acrylate or glycidyl (meth) acrylate, bisphenol A type Epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, brominated bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, biphenol epoxy resin, bisphenol Type epoxy resin, phenol novolak type epoxy resin, cresol novolac type epoxy resin, brominated phenol novolak type epoxy resin, bisphenol A phenolic type epoxy resin and other glycidyl ether compounds; terephthalic acid dihydrate a glycidyl ester compound such as glyceride, hexahydrophthalic acid diglycidyl ester or dimer acid diglycidyl ester; triglycidyl group Cyanurate, N,N,N',N'-tetraglycidyl m-xylenediamine, N,N,N',N'-tetraglycidyl bisaminomethylcyclohexane, N , an alicyclic epoxy resin such as N-diglycidylamine or an alicyclic epoxy resin such as 3,4-epoxycyclohexanecarboxylate, glycidyl methacrylate, and styrene and methyl methacrylate A conventionally known epoxy compound or epoxy resin such as a copolymer, a copolymer of glycidyl methacrylate and a copolymer of cyclohexylmaleimide or the like.

For the lactic acid or the polylactic acid (b), for example, Musashino lactic acid (registered trademark) F manufactured by Musashino Chemical Research Co., Ltd., or the like can be suitably used. Further, a lactic acid oligomer having a moderately repetitive structure in which lactic acid is dehydrated and condensed between molecules can also be used.

(meth)acrylic acid having an acid group (organic acid group) for the (meth)acrylic monomer (c) having an acid group or an isocyanate group used for the synthesis of the photocurable resin (A) The monomer (c-1) and the (meth)acrylic monomer (c-2) having an isocyanate group may be used singly or in combination of two or more.

Examples of the acid group-containing (meth)acrylic monomer (c-1) include acrylic acid, methacrylic acid, acrylic anhydride, methacrylic anhydride, crotonic acid, cinnamic acid, vinyl acetate, and sorbic acid. A polylactone (meth) acrylate which is a molecule which is obtained by reacting ε-butyrolactone with (meth)acrylic acid, or a (meth)acrylic acid 2 polymer, which may be used alone or in combination of two or more.

The (meth)acrylic monomer (c-2) having an isocyanate group is not particularly affected as long as it is an isocyanate compound having one isocyanate group and one or more ethylenically unsaturated groups in one molecule. limited. Specific examples include, for example, (meth)acryloxyethyl isocyanate, (meth)acryloxyethoxyethyl isocyanate, bis(acryloxymethyl)ethyl isocyanate or Such denatured bodies and the like. For commercial products, there are "KARENZ MOI" (methacryloxyethyl isocyanate), "KARENZ AOI" (acryloxyethoxyethyl isocyanate), and "KARENZ MOI-EG" (methyl). "acrylic ethoxyethoxyethyl isocyanate", "KARENZ MOI-BM" (isocyanate block of KARENZ MOI), "KARENZ MOI-BP" (isocyanate block of KARENZ MOI), "KARENZ BEI" (1 , 1-bis(acryloxymethyl)ethyl isocyanate), sold by Showa Denko Co., Ltd. in the market. In addition, any of these product names are registered trademarks. Further, a compound having one hydroxyl group and one or more ethylenically unsaturated groups in one molecule and a diisocyanate such as isophorone diisocyanate, toluene diisocyanate, tetramethyl xylene diisocyanate or hexamethylene diisocyanate may be used. A semicarbamate compound. These (meth)acrylic monomers (c-2) having an isocyanate group may be used alone or in combination of two or more.

Further, by subjecting the hydroxyl group of the photocurable resin (A) obtained as described above to the acid anhydride (d), the carboxyl group can be further introduced into a carboxyl group to form a carboxyl group-containing photocurable resin which is soluble in an aqueous alkali solution. Resin (A'). In the reaction, the amount of the acid anhydride (d) is generally 0.1 to 1.0 mol per mol of the hydroxyl group 1 mol of the photocurable resin (A), preferably the generated carboxyl group-containing light. The acid value of the curable resin (A') is an addition amount of about 20 to 200 mgKOH/g, preferably 50 to 120 mgKOH/g.

The addition reaction of the acid anhydride (d) to the photocurable resin (A) is carried out in the presence or absence of an organic solvent as described later, and in hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechu It is carried out in the presence of a polymerization inhibiting agent such as phenol or gallic phenol, and is usually carried out at about 50 to 150 °C. In this case, a tertiary amine such as triethylamine or a tertiary ammonium salt such as triethylbenzylammonium chloride, an imidazole compound such as 2-ethyl-4-methylimidazole, or a phosphorus compound such as triphenylphosphine may be added as needed. A metal salt of an organic acid such as lithium, chromium, zirconium, potassium or sodium of naphthenic acid, lauric acid, stearic acid, oleic acid or octenoic acid is used as a catalyst. These catalysts may be used singly or in combination of two or more.

Examples of the acid anhydride (d) include methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic anhydride, and 3,6. - an alicyclic dibasic acid anhydride such as endomethylenetetrahydrophthalic anhydride, methyl endomethylenetetrahydrophthalic anhydride or tetrabromophthalic anhydride; succinic anhydride, maleic anhydride, and itaconic anhydride, An aliphatic or aromatic dibasic acid anhydride such as octenyl succinic anhydride, penta (dodecenyl) succinic anhydride, phthalic anhydride or trimellitic anhydride, or biphenyl tetracarboxylic dianhydride or diphenyl ether tetracarboxylic acid An aliphatic or aromatic tetrabasic acid dianhydride such as dianhydride, butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, pyrogallic anhydride, or diphenyl ketone tetracarboxylic dianhydride can be used. One or more of them.

In the photocurable resin (A) of the present invention and/or the photocurable resin (A') having a carboxyl group obtained as described above, a photopolymerization initiator (B) may be further added, thereby obtaining the present The photocurable resin composition of the invention. The photopolymerization initiator, photoinitiator, and sensitizer which can be suitably used for the photocurable resin composition of the present invention include a benzoin compound, an acetophenone compound, an anthraquinone compound, and a thiophene. A ton ketone compound, a ketal compound, a diphenyl ketone compound, a xanthone compound, or the like.

Specific examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.

Specific examples of the acetophenone compound include, for example, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, and 2,2-diethoxy-2-phenylacetophenone. 1,1-dichloroacetophenone.

Specific examples of the hydrazine compound include 2-methyl hydrazine, 2-ethyl hydrazine, 2-tert-butyl fluorene, and 1-chloro hydrazine.

Specific examples of the thioxanthone compound include, for example, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropyl. Thioxanthone.

Specific examples of the ketal compound include acetophenone dimethyl ketal and benzyl dimethyl ketal.

Specific examples of the diphenyl ketone compound include, for example, diphenyl ketone, 4-benzylidene diphenyl sulfide, 4-benzylidene-4'-methyldiphenyl sulfide, 4-benzene. Methanyl-4'-ethyldiphenyl sulfide, 4-benzylidene-4'-propyldiphenyl sulfide.

Other examples are α-aminoacetophenone-based, mercaptophosphine oxide-based, and oxime-based esters, and specific examples thereof include 2-methyl-1-[4-(methylthio)phenyl]-2- Morpholine propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butan-1-one, 2-(dimethylamino)-2 -[(4-Methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, N,N-dimethylaminoacetophenone, and the like. Examples of commercially available products include IRGACURE 907, IRGACURE 369, and IRGACURE 379 manufactured by Chiba Japan. The commercially available product of the oxime ester-based initiator is CGI-325, IRGACURE OXE01, IRGACURE OXE02 manufactured by Chiba Japan Co., Ltd., N-1919 manufactured by ADEKA Co., Ltd., and the like. The mercaptophosphine oxide-based initiator may, for example, be 2,4,6-trimethylbenzimidyldiphenylphosphine oxide or bis(2,4,6-trimethylbenzylidene). ——Phenylphosphine oxide, bis(2,6-dimethoxybenzylidene)-2,4,4-trimethylpentylphosphine oxide, and the like. The commercially available product includes Lucirin Tpo manufactured by BASF Corporation and IRGACURE 819 manufactured by Chiba Japan Co., Ltd., and the like.

The above description discloses a representative photopolymerization initiator, and is not limited as long as it is a radical active species generated by light irradiation or a substance which contributes to the function of the growth species. Further, it does not cause generation of radicals by itself, and a sensitizer which is conventionally known to have a sensitizing effect can be used for the above photopolymerization initiator. The photopolymerization initiator and the sensitizer may be used singly or in combination of two or more.

In addition, in order to impart alkali developability to the photocurable resin composition of the present invention, a conventional carboxyl group-containing resin (C) other than the above-mentioned carboxyl group-containing photocurable resin (A') can be used.

As a specific example of the carboxyl group-containing resin (C), a compound (any of an oligomer and a polymer) as exemplified below can be suitably used.

(1) obtained by copolymerization of an unsaturated carboxylic acid such as (meth)acrylic acid with a compound containing an unsaturated group such as styrene, α-methylstyrene, lower alkyl (meth) acrylate or isobutylene. Carboxyl containing resin.

(2) Diisocyanate such as aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate or aromatic diisocyanate; and carboxyl group-containing diol compound such as dimethylolpropionic acid or dimethylolbutanoic acid and poly Carbonate-based polyol, polyether-based polyol, polyester-based polyol, polyolefin-based polyol, acrylic polyol, bisphenol A-based alkylene oxide addition diol, phenolic hydroxyl group and alcoholic hydroxyl group A carboxyl group-containing urethane resin produced by addition polymerization of a diol compound such as a compound.

(3) Diisocyanate and bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol type epoxy resin, biphenol A carboxyl group-containing photosensitive amine group produced by addition polymerization of a 2-functional epoxy resin (meth) acrylate such as an epoxy resin or a partial acid anhydride denatured product thereof, a carboxyl group-containing diol compound, and a diol compound Acid ester resin.

(4) In the resin synthesis of the above (2) or (3), a compound having a hydroxyl group and one or more (meth)acrylic groups in the molecule, such as a hydroxyalkyl (meth)acrylate, is added, and the terminal is passed through (A) A acrylated carboxyl group-containing photosensitive urethane resin.

(5) In the synthesis of the resin of the above (2) or (3), a molar reactant such as isophorone diisocyanate and pentaerythritol triacrylate is added to have one isocyanate group and one or more (methyl) in the molecule. The acrylate-based compound is subjected to a (meth) acrylated carboxyl group-containing photosensitive urethane resin.

(6) A carboxyl group-containing photosensitive resin obtained by reacting (meth)acrylic acid with a polyfunctional (solid) epoxy resin having two or more functional groups or more, and adding a dibasic acid anhydride to a hydroxyl group present in a side chain.

(7) reacting (meth)acrylic acid with a polyfunctional epoxy resin which further epoxidizes a hydroxyl group of a bifunctional (solid) epoxy resin with epichlorohydrin, and adding a dibasic acid anhydride to a hydroxyl group produced by the reaction A photosensitive resin of a carboxyl group.

(8) A carboxyl group-containing polyester resin obtained by adding a dibasic acid anhydride to a first-order hydroxyl group produced by reacting a dicarboxylic acid with a bifunctional oxetane resin.

(9) The resin of the above (1) to (8) is further added to a carboxyl group-containing photosensitive resin having a compound having one epoxy group and one or more (meth)acrylic groups in one molecule.

In the photocurable resin composition of the present invention, a thermosetting component (D) may be added in order to impart heat resistance. For the thermosetting component used in the present invention, an amine resin such as a melamine resin or a benzoguanamine resin, a block isocyanate compound, a cyclic carbonate compound, a polyfunctional epoxy compound, or a polyfunctional oxetane compound can be used. A thermosetting resin which is conventionally used, such as an episulfide resin or a melamine derivative. It is particularly suitable to have two or more cyclic ether groups and/or cyclic thioether groups (hereinafter simply referred to as cyclic (thio)ether group) thermosetting components (D) in the molecule.

The thermosetting component (D) having two or more cyclic (thio)ether groups in the molecule is a cyclic ether group having two or more 3, 4 or 5 membered rings in the molecule, or a cyclic sulfur. The compound of any one or two groups of the ether group may, for example, be a compound having at least two or more epoxy groups in the molecule, that is, a polyfunctional epoxy compound (D-1) having at least two in the molecule. a compound of the above oxetanyl group, that is, a polyfunctional oxetane compound (D-2), a compound having two or more thioether groups in a molecule, that is, an episulfide resin (D-3) Wait.

Examples of the polyfunctional epoxy compound (D-1) include jER828, jER834, jER1001, and jER1004 manufactured by Japan Epoxy Resin Co., Ltd., EPICLON 840, EPICLON 850, EPICLON 1050, EPICLON 2055, and Dongdu Chemical Co., Ltd., manufactured by DIC Corporation. EPOTOTE YD-011, YD-013, YD-127, YD-128, DER317, DER331, DER661, DER664 manufactured by Dow Chemical Co., Ltd., ARALDITE 6071, ARALDITE 6084, ARALDITE GY250 from Chiba Japan, ARALDITE GY260, SUMI-EPOXY ESA-011, ESA-014, ELA-115, ELA-128, AER330, AER331, AER661, AER664, etc. manufactured by Sumitomo Chemical Industries Co., Ltd. Bisphenol A type epoxy resin of the product name; jERYL903 manufactured by Japan Epoxy Resin Co., Ltd., EPICLON 152, EPICLON 165 manufactured by DIC Corporation, EPOTOTE YDB-400 manufactured by Dongdu Chemical Co., Ltd., YDB-500, and Dow Chemical Co., Ltd. RD542, ARALDITE 8011 manufactured by Chiba Japan Co., Ltd., SUMI-EPOXY ESB-400 manufactured by Sumitomo Chemical Industries, Ltd., ESB-700, AER711, AER714, etc. by Asahi Kasei Kogyo Co., Ltd. (all of which are trade names) Loop Resin; jER152, jER154 manufactured by Japan Epoxy Resin Co., Ltd., DEN431, DEN438 manufactured by Dow Chemical Co., Ltd., EPICLON N-730, EPICLON N-770, EPICLON N-865 manufactured by DIC Corporation, and EPOTOTE YDCN manufactured by Dongdu Chemical Co., Ltd. 701, YDCN-704, ARALDITE ECN1235, ARALDITE ECN1273, ARALDITE ECN1299, ARALDITE XPY307 manufactured by Chiba Japan Co., Ltd., EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, Sumitomo by Nippon Chemical Co., Ltd. Pharmaceutical company's SUMI-EPOXY ESCN-195X, ESCN-220, Asahi Kasei Kogyo Co., Ltd. AERECN-235, ECN-299, etc. (any of which are trade names) phenolic epoxy resin; EPICLON 830, JER807 manufactured by Japan Epoxy Resin Co., Ltd., EPOTOTE YDF-170, YDF-175, YDF-2004 manufactured by Dongdu Chemical Co., Ltd., ARALDITE XPY306 manufactured by Chiba Japan Co., Ltd., etc. (all of which are trade names) bisphenol F type Epoxy resin; hydrogenated bisphenol A type epoxy resin such as EPOTOTE ST-2004, ST-2007, ST-3000 (trade name) manufactured by Dongdu Chemical Co., Ltd.; jER604 manufactured by Japan Epoxy Resin Co., Ltd., EPOTOTE YH manufactured by Dongdu Chemical Co., Ltd. -434, AR made by Chiba Japan ALDITE MY720, a glycidylamine type epoxy resin such as SUMI-EPOXY ELM-120 manufactured by Sumitomo Chemical Industries Co., Ltd. (any of which is a trade name); an allantoic capsule such as ARALDITE CY-350 (trade name) manufactured by Chiba Japan Co., Ltd. Plain type epoxy resin; CELLOXIDE 2011 manufactured by DAICEL Chemical Industry Co., Ltd., ARALDITE CY175, CY179 manufactured by Chiba Japan Co., Ltd., CY179, etc. (any one is a trade name) alicyclic epoxy resin; YL-made by Japan Epoxy Resin Co., Ltd. 933, TEN, EPPN-501, EPPN-502, etc. of Dow Chemical Co., Ltd. (all of which are trade names) of trishydroxyphenylmethane type epoxy resin; YL-6056, YX-4000 manufactured by Japan Epoxy Resin Co., Ltd. , YL-6121 (any one of which is a trade name), such as bisphenol type or biphenol type epoxy resin or these mixtures; EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30, DIC manufactured by Asahi Kasei Kogyo Co., Ltd. Bisphenol S type epoxy resin such as EXA-1514 (trade name) manufactured by the company; bisphenol A phenolic epoxy resin such as jER157S (trade name) manufactured by Japan Epoxy Resin Co., Ltd.; jERYL-931 manufactured by Japan Epoxy Resin Co., Ltd. Tetraphenol ethane type of ARALDITE 163, etc. (all of which are trade names) manufactured by Chiba Japan Oxygen resin; ARALDITE PT810 manufactured by Chiba Japan Co., Ltd., TEPIC manufactured by Nissan Chemical Industries Co., Ltd. (all of which are trade names), heterocyclic epoxy resin; BLEMMER DGT, etc. made by Nippon Oil Co., Ltd. ; tetrahydroglycidyl xylenyl ethane resin such as ZX-1063 manufactured by Dongdu Chemical Co., Ltd.; ESN-190, ESN-360 manufactured by Nippon Steel Chemical Co., Ltd., HP-4032, EXA-4750, EXA-4700 manufactured by DIC Corporation, etc. Epoxy resin containing naphthyl group; epoxy resin having dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by DIC Corporation; glycidyl methacrylate such as CP-50S and CP-50M manufactured by Nippon Oil Co., Ltd. Polymeric epoxy resin; even copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; epoxy-denatured polybutadiene rubber derivative (for example, PB-3600 manufactured by DAICEL Chemical Industry Co., Ltd.) Etc.), CTBN denatured epoxy resin (for example, YR-102, YR-450, etc. manufactured by Tosho Kasei Co., Ltd.), etc., and are not limited by these. These epoxy resins may be used alone or in combination of two or more. Among these, a phenolic epoxy resin, a heterocyclic epoxy resin, a bisphenol A epoxy resin or the like is particularly preferable.

The above polyfunctional oxetane compound (D-2) may, for example, be bis[(3-methyl-3-oxetanylmethoxy)methyl]ether, bis[(3- Ethyl-3-oxetanylmethoxy)methyl]ether, 1,4-bis[(3-methyl-3-oxetanylmethoxy)methyl]benzene, 1 , 4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, (3-methyl-3-oxetanyl) methacrylate, methyl (3-ethyl-3-oxetanyl) acrylate, (3-methyl-3-oxetanyl)methyl methacrylate, methacrylic acid (3-ethyl-3- Oxetane) methyl esters or polyfunctional oxetanes such as such oligomers or copolymers, in addition to oxetane and phenolic resins, poly(p-hydroxystyrene), Cardo An ether compound of a resin having a hydroxyl group such as a bisphenol, a calixarene, a resorcinol calixarene or a sesquioxane. Other examples thereof include a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth)acrylate.

The compound (D-3) having two or more cyclic thioether groups in the molecule may, for example, be a bisphenol A type episulfide resin YL7000 manufactured by Japan Epoxy Resin Co., Ltd., or the like. Further, an episulfide resin obtained by substituting an oxygen atom of an epoxy group of a novolac type epoxy resin with a sulfur atom by the same synthesis method may be used.

The blending amount of the thermosetting component (D) having two or more cyclic (thio)ether groups in the molecule is a photocurability with respect to the photocurable resin (A) and/or the carboxyl group-containing light. A range of 5 to 70 parts by mass (preferably 10 to 50 parts by mass) of 100 parts by mass of the resin (A') (preferably in the case of using two or more kinds) is suitable. The thermosetting component (D) having two or more cyclic (thio)ether groups in the molecule does not exceed the above range because the carboxyl group remains in the cured coating film, heat resistance, alkali resistance, electrical insulation Sex is lower, so it is not good. On the other hand, when it exceeds the above range, the low molecular weight cyclic (thio)ether group remains in the dried coating film, and the strength of the coating film or the like is lowered, which is not preferable.

When the thermosetting component (D) having two or more cyclic (thio)ether groups in the molecule is used, it is preferred to contain a thermosetting catalyst. Examples of such a thermosetting catalyst include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, and 4-phenylimidazole. Imidazole derivatives such as 1-cyanoethyl-2-phenylimidazole and 1-(2-cyanoethyl)-2-ethyl-4-ylimidazole; dicyanodiamide, benzyldimethylamine, 4-(Dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethyl An amine compound such as benzylamine, a bisamine compound such as diammonium adipate or dinonazelain; a phosphorus compound such as triphenylphosphine or the like. In addition, for the commercially available article, for example, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (a product name of any imidazole-based compound) manufactured by Shikoku Chemicals Co., Ltd., and San-Apro Co., Ltd. U-CAT (registered trademark) 3503N, U-CAT3502T (trade name of any block of isocyanate compound of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (all of which are double-ring type) Compounds and their salts) and the like. It is not particularly limited as long as it is a substance which promotes a thermosetting catalyst of an epoxy resin or an oxetane compound, or a reaction of an epoxy group and/or an oxetane group with a carboxyl group, It can be used alone or in combination of two or more. In addition, guanamine, acetamide, benzoguanamine, melamine, 2,4-diamino-6-methylpropenyloxyethyl-S-triazine, 2-vinyl-2 can also be used. ,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine, isomeric cyanuric acid adduct, 2,4-diamino-6-methyl An S-triazine derivative such as an acryloyloxyethyl-S-triazine ‧isocyanuric acid addition product, and a compound which functions as an adhesion imparting agent and the aforementioned thermosetting contact Use the media together.

The blending amount of the thermosetting catalyst is sufficient in a usual amount, for example, in a group consisting of the photocurable resin (A) and the photocurable resin (A') having a carboxyl group. The photocurable resin or the thermosetting component (D) having two or more cyclic (thio)ether groups in the molecule is preferably 0.1 to 20 parts by mass, preferably 0.5 to 15.0 parts by mass per 100 parts by mass of the thermosetting component (D) having two or more cyclic (thio)ether groups. Share.

In addition to the above-mentioned thermosetting compound, examples of the thermosetting component include an isocyanate compound and a bulk compound thereof, a bismaleimide compound, an oxazine compound, a carbodiimide resin, etc., particularly with a hydroxyl group or a carboxyl group. The selective reaction is preferred, and can be used without particular limitation.

Further, in the curable resin composition of the present invention, a compound having one or more ethylenically unsaturated groups in the molecule may be blended. In order to optimize the hardness, flexibility, and the like of the obtained cured product, various substances can be used, and in view of the photocurability, it is two or more in one molecule. Ethylene unsaturated groups are preferred. Examples of such a compound include diacrylates of diols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; hexanediol, trimethylolpropane, pentaerythritol, and dipentaerythritol; a polyvalent alcohol such as hydroxyethyl isomeric cyanurate or a polyvalent acrylate such as an ethylene oxide adduct or a propylene oxide adduct; phenoxy acrylate, bisphenol A Polyvalent acrylates such as acrylates and ethylene oxide adducts of such phenols or propylene oxide adducts; glycerol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether And polyvalent acrylates of glycidyl ethers such as triglycidyl isocyanurate; and melamine acrylates and/or methacrylates corresponding to the above acrylates.

An epoxy acrylate resin which further reacts acrylic acid with a polyfunctional epoxy resin such as a cresol novolac epoxy resin, or a half of a diisocyanate such as a hydroxy acrylate such as pentaerythritol triacrylate or isophorone diisocyanate may be used. An epoxy urethane acrylate compound in which a urethane compound reacts with a hydroxyl group of the epoxy acrylate resin.

The photocurable resin composition of the present invention can be blended with a colorant. As the coloring agent, a conventionally known coloring agent such as black, white, red, blue, green, or yellow may be used, and any of a pigment, a dye, and a pigment may be used. However, from the viewpoint of environmental load reduction and impact on the human body, it is preferred that halogen is not contained.

In order to enhance the physical strength and the like of the coating film, the photocurable resin composition of the present invention may be blended as necessary. As such a filler, a well-known inorganic or organic filler can be used, and barium sulfate, spherical cerium oxide and talc are particularly suitable. Further, in order to obtain a white appearance or flame retardancy, a metal hydroxide such as titanium oxide, metal oxide or aluminum hydroxide may be used as the extender pigment filler.

The photocurable resin composition of the present invention may further contain a thermal polymerization inhibiting agent or a fine powder which is conventionally used, such as hydroquinone, hydroquinone monomethyl ether, tert-butylcatechol, gallic phenol, phenothiazine, etc., as necessary. Anti-foaming agents such as cerium oxide, organic bentonite, montmorillonite, etc., antifoaming agents and/or homogenizers such as polyfluorene, fluorine, and polymer, imidazole, thiazole, triazole, etc. A well-known additive such as a decane coupling agent, an antioxidant, and a rust inhibitor.

In addition, in order to dissolve the photocurable resin (A), the carboxyl group-containing photocurable resin (A'), and the photosensitive (meth) acrylate compound, the photocurable resin composition of the present invention is further The composition is adjusted to a viscosity suitable for the coating method, and an organic solvent can be blended.

Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, and card. Glycol ethers such as alcohol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, dissolved Cellulose acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate and other acetates; ethanol, propanol, B Alcohols such as diol and propylene glycol; aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum ether, petroleum brain, hydrogenated petroleum brain, and solvent oil. These organic solvents may be used singly or in the form of a mixture of two or more. Further, the blending amount of the organic solvent can be set to an arbitrary amount in accordance with the coating method.

The photocurable resin composition of the present invention can be adjusted to a viscosity suitable for the coating method by, for example, the above-described organic solvent, and can be applied by a dip coating method, a flow coating method, a roll coating method, a bar coater method, or the like. It is applied to a substrate by a method such as a screen printing method or a curtain coating method. Thereafter, the coating film which is dry to the touch is formed by volatilizing (pre-drying) the organic solvent contained in the composition at a temperature of about 60 to 100 °C. Alternatively, the above composition may be applied onto a carrier film and dried, and wound in the form of a film to form a dry film. Such a dry film can be formed into a resin insulating layer by being adhered to a substrate.

Thereafter, the coating film of the photocurable resin composition obtained by irradiation with an active energy ray is irradiated with a high-pressure mercury lamp or a metal halide lamp and irradiated with an active energy ray, whereby the coating film can be easily obtained. Hardened material. The exposed portion of the coating film (the portion irradiated with the active energy ray) is hardened. Further, in the case where patterning is performed on the obtained photocurable resin composition, the patterned photomask is selectively exposed by a contact or non-contact method, or is selectively exposed by an active energy ray, or by a ray The direct exposure apparatus directly exposes the pattern, and the unexposed portion is developed by a dilute aqueous alkali solution (for example, 0.3 to 3% aqueous sodium carbonate solution) to form a resist pattern. Further, in the case of the composition containing the thermosetting component (D), for example, it is heated to a temperature of about 140 to 200 ° C to be thermally cured, whereby the hydroxyl group of the photocurable resin (A) or a carboxyl group is contained. The carboxyl group of the photocurable resin (A') reacts with the thermosetting component (D) having two or more cyclic ether groups and/or a cyclic thioether group in the molecule to form heat resistance and chemical resistance. A cured coating film excellent in properties such as moisture absorption resistance, adhesion, and electrical properties. In addition, even in the case where the thermosetting component (D) is not contained, thermal radical polymerization of the ethylenically unsaturated bond remaining in an unreacted state at the time of exposure can be thermally treated by heat treatment, or in order to improve coating film properties, or Heat treatment (thermosetting) according to purpose and use.

In the above substrate, in addition to a circuit board or a flexible printed circuit board in which a circuit is formed in advance, paper-phenol resin, paper-epoxy resin, glass cloth-epoxy resin, glass-polyamide can also be used. Amine, glass cloth/non-woven fabric-epoxy resin, glass cloth/paper-epoxy resin, synthetic fiber-epoxy resin, fluororesin, polyethylene, PPO, cyanate ester, etc. All grades of composite materials (FR-4) Etc.) Copper-clad laminates, polyimide films, PET films, glass substrates, ceramic substrates, silicon wafers, etc.

The volatilization drying which is carried out after applying the photocurable resin composition of the present invention can be carried out using a hot air circulation type drying furnace, an IR furnace, a hot plate, a convection oven or the like.

For the exposure machine used for the active energy ray irradiation, a transfer type exposure machine capable of irradiating an active energy ray, and in the case of pattern formation, an ultraviolet exposure apparatus equipped with a high pressure mercury lamp or a metal halide lamp or a direct A device (eg, a laser direct imaging device that directly renders an image with a laser by CAD data from a computer). As for the active energy ray, any of the high-pressure mercury lamp, the ultra-high pressure mercury lamp, the metal halide lamp, the gas laser, the solid laser, and the semiconductor laser may be used as long as the maximum wavelength of the light used is in the range of 350 to 410 nm. Further, the exposure amount varies depending on the film thickness and the like, and is generally set to be in the range of 5 to 800 mJ/cm ² (preferably 10 to 500 mJ/cm ² , more preferably 10 to 300 mJ/cm ² ). Inside.

In the case of the development method in the case of developing as described above, an appropriate method such as a dipping method, a shower method, a spray method, or a brush method may be employed. Further, as the developing solution, an aqueous alkali solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium citrate, ammonia or an amine can be used.

[Examples]

The following examples and comparative examples are disclosed, and the present invention is specifically described, but the present invention is not limited by the following examples. In addition, the "parts" and "%" mentioned in the following contents are all based on quality unless otherwise specified.

Resin Synthesis Example 1

In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 100 g of diethylene glycol monoethyl ether acetate and a cresol novolac epoxy resin (made by DIC Co., Ltd., EPICLON N-680, softening point 82 ° C, epoxy) were placed. Equivalent 211) 211 g (1.0 mol), 90% lactic acid (Musashino lactic acid 90F, purity 90%) 100 g (1.0 mol of lactic acid), dibutyl hydroxytoluene 1.51 g And hydroquinone 0.15g, heated to 100 ° C and uniformly dissolved. Next, 1.14 g of triphenylphosphine was placed, and the temperature was raised to 110 ° C while being filled with nitrogen, and the contained water was removed to the outside of the system at any time while the reaction was carried out for 10 hours. Next, after the system was replaced with an air atmosphere, 152 g of diethylene glycol monoethyl ether acetate and 2-propenyloxyethyl isocyanate (Karez AOI, manufactured by Showa Denko Co., Ltd.) were placed in the obtained reaction liquid. The molecular weight was 141) 148 g (1.05 mol), and the reaction was carried out at 85 ° C for 3 hours, and it was confirmed by an infrared spectrophotometer that the peak of the isocyanate group (2270 cm ^-1 ) in the solution disappeared, and the solid content acid value was 12.7 mgKOH/g, and solid. A 64.0% resin solution of the ingredients. The solid component had a double bond equivalent of 429 and a lactic acid content of 20%. This was used as the resin varnish 1. Further, the infrared absorption spectrum of the obtained photocurable resin (measured using a Fourier transform infrared spectrophotometer FT-IR) is disclosed in Fig. 1, and the nuclear magnetic resonance spectrum (solvent CDCl ₃ , reference substance TMS (tetramethyl) The decane)) is disclosed in Figure 2.

Intermediate Synthesis Example 1 (Synthesis of Lactic Acid Oligomers)

In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 90% lactic acid (Musashino lactic acid 90F, purity 90%) 1000 g (10 mol of lactic acid) was placed in a flask equipped with a thermometer, a stirrer, and a reflux condenser. At 120 ° C, the dehydrated water produced by the dehydration and esterification of the contained water and lactic acid was removed to the outside of the system, and the reaction was carried out for 11 hours to obtain a resin solution having an acid value of 207 mgKOH/g. This was used as the lactic acid oligomer intermediate X-1.

Resin Synthesis Example 2

In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 147 g of diethylene glycol monoethyl ether acetate and cresol novolac epoxy resin (made by DIC Co., Ltd., EPICLON N-680, softening point 82 ° C, epoxy) were placed. Equivalent 211) 211 g (1.0 mol), lactic acid oligomer intermediate (X-1) 216 g (0.8 mol), acrylic acid 14.4 g (0.2 mol), ditributyl hydroxytoluene 2.21 g and hydroquinone 0.22 g, heated to 100 ° C and allowed to dissolve evenly. Next, 1.68 g of triphenylphosphine was placed, and the temperature was raised to 110 ° C in an air atmosphere, and the reaction was carried out for 8 hours. Next, 188 g of diethylene glycol monoethyl ether acetate and 2-propenyloxyethyl isocyanate (Karez AOI, molecular weight 141) 106 g (0.75 m) were placed in the obtained reaction liquid. The reaction was carried out at 85 ° C for 3 hours, and it was confirmed by an infrared spectrophotometer that the peak of the isocyanate group (2270 cm ^-1 ) in the solution disappeared, and a resin solution having a solid content of 7.0 mgKOH/g and a solid content of 62.0% was obtained. The solid component had a double bond equivalent of 576 and a lactic acid content of 40%. This was used as the resin varnish 2. Further, the infrared absorption spectrum of the obtained photocurable resin (measured using a Fourier transform infrared spectrophotometer FT-IR) is disclosed in Fig. 3, and the nuclear magnetic resonance spectrum (solvent CDCl ₃ , reference material TMS (tetramethyl) The decane)) is disclosed in Figure 4.

Resin Synthesis Example 3

In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 100 g of diethylene glycol monoethyl ether acetate and cresol novolac epoxy resin (made by DIC Co., Ltd., EPICLON N-680, softening point 82 ° C, Epoxy equivalent 211) 211 g (1.0 mol), 90% lactic acid (Musashino lactic acid 90F, purity 90%) 100 g (1.0 mol of lactic acid), di-tert-butylhydroxytoluene 1.51 g and 0.15 g of hydroquinone were heated to 100 ° C to be uniformly dissolved. Next, 1.14 g of triphenylphosphine was placed, and the temperature was raised to 110 ° C while being filled with nitrogen, and the contained water was removed to the outside of the system at any time while the reaction was carried out for 10 hours. After the system was replaced with an air atmosphere, 181 g of diethylene glycol monoethyl ether acetate and 2-propenyloxyethyl isocyanate (Karez AOI, manufactured by Showa Denko Co., Ltd., molecular weight) were placed in the obtained reaction solution. 141) 148 g (1.05 mol), and the reaction was carried out at 85 ° C for 3 hours, and it was confirmed by an infrared spectrophotometer that the peak of the isocyanate group (2270 cm ^-1 ) in the solution disappeared. Further, 51.7 g (0.34 mol) of tetrahydrophthalic anhydride was placed, and the reaction was carried out at 110 ° C for 3 hours to obtain a resin solution having a solid content of 49.0 mgKOH/g and a solid content of 64%. The solid component had a double bond equivalent of 477 and a lactic acid content of 18%. This was used as the resin varnish 3. Further, the infrared absorption spectrum of the obtained photocurable resin (measured using a Fourier transform infrared spectrophotometer FT-IR) is disclosed in Fig. 5, and the nuclear magnetic resonance spectrum (solvent CDCl ₃ , reference material TMS (tetramethyl) The decane)) is disclosed in Figure 6.

Resin Synthesis Example 4

30.8 g of diethylene glycol monoethyl ether acetate and bisphenol A type epoxy resin (made by DIC Co., Ltd., EPICLON 850, epoxy equivalent 187) 187 g (1.0) were placed in a flask equipped with a thermometer, a stirrer, and a reflux condenser. Mohr), 90% lactic acid (Musashino lactic acid 90F, purity 90%) 100g (lactic acid is 1.0 mole), ditributyl hydroxytoluene 1.39g and hydroquinone 0.14g, Heat to 90 ° C and dissolve it evenly. Next, 0.97 g of triphenylphosphine was placed, and the temperature was raised to 110 ° C while being filled with nitrogen, and the contained water was removed to the outside of the system at any time, and the reaction was carried out for 11 hours. Next, after the system was replaced with an air atmosphere, 91.2 g of diethylene glycol monoethyl ether acetate and 2-propenyloxyethyl isocyanate (Karez AOI, manufactured by Showa Denko Co., Ltd.) were placed in the obtained reaction liquid. The molecular weight was 141) 141 g (1.0 mol), and the reaction was carried out at 85 ° C for 3 hours, and it was confirmed by an infrared spectrophotometer that the peak of the isocyanate group (2270 cm ^-1 ) in the solution disappeared, and the acid value of the solid component was 3.5 mgKOH/g. A solid solution of 76.0% resin solution. The solid component had a double bond equivalent of 418 and a lactic acid content of 22%. This was used as the resin varnish 4. Further, the infrared absorption spectrum of the obtained photocurable resin (measured using a Fourier transform infrared spectrophotometer FT-IR) is shown in Fig. 7, and the nuclear magnetic resonance spectrum (solvent CDCl ₃ , reference substance TMS (tetramethyl) The decane)) is disclosed in Figure 8.

Resin Synthesis Example 5

30.8 g of diethylene glycol monoethyl ether acetate and bisphenol A type epoxy resin (made by DIC Co., Ltd., EPICLON 850, epoxy equivalent 187) 187 g (1.0) were placed in a flask equipped with a thermometer, a stirrer, and a reflux condenser. Mohr), 90% lactic acid (Musashino lactic acid 90F, purity 90%) 100g (lactic acid is 1.0 mole), ditributyl hydroxytoluene 1.39g and hydroquinone 0.14g, Heat to 90 ° C and dissolve it evenly. Next, 0.97 g of triphenylphosphine was placed, and the temperature was raised to 110 ° C while being purged with nitrogen, and the contained water was removed to the outside of the system at any time while the reaction was carried out for 11 hours. After the system was replaced with an air atmosphere, 91.2 g of diethylene glycol monoethyl ether acetate and 2-propenyloxyethyl isocyanate (Karez AOI, manufactured by Showa Denko Co., Ltd.) were placed in the obtained reaction solution. The molecular weight was 141) 141 g (1.0 mol), and the reaction was carried out at 85 ° C for 3 hours, and it was confirmed by an infrared spectrophotometer that the peak of the isocyanate group (2270 cm ^-1 ) in the solution disappeared. Further, 69.9 g (0.46 mol) of tetrahydrophthalic anhydride was placed, and the reaction was carried out at 115 ° C for 4 hours to obtain a resin solution having a solid content of 57.2 mgKOH/g and a solid content of 80.0%. The solid component had a double bond equivalent of 488 and a lactic acid content of 18%. This was used as the resin varnish 5. Further, the infrared absorption spectrum of the obtained photocurable resin (measured using a Fourier transform infrared spectrophotometer FT-IR) is shown in Fig. 9, and the nuclear magnetic resonance spectrum (solvent CDCl ₃ , reference material TMS (tetramethyl) The decane)) is disclosed in Figure 10.

Resin varnish 6

A carboxyl group-containing modified cresol novolac type epoxy acrylate (DICLITEUE-9210, a solid content acid value of 82.9 mgKOH/g, a solid content of 62%, and a double bond equivalent of solid component 361) was used.

Examples 1 to 5 and Comparative Examples 1 to 3

Each component disclosed in Table 1 was blended, stirred, and dissolved in the ratio disclosed in Table 1, to obtain a photocurable resin composition. As a brief test, a photocurable resin composition was applied onto a PET film using an applicator. In Examples 1 to 5 and Comparative Example 1, drying was carried out at 80 ° C for 20 minutes after coating. After the application, the PET film and the photocurable resin composition are adhered to each other, and the composition is cured by UV irradiation at a cumulative light amount of 1000 mJ/cm ² using a metal halide lamp to obtain a target film thickness of about 15 to 20 μm. Hardened coating film.

The state of the hardened film:

In order to confirm the obtained cured state, the cured coating film after UV irradiation was peeled off from the PET film, and the softness and the ease of rupture were evaluated. After UV irradiation, it was rated as ○ for a soft film which was not broken, and × for a significant crack.

Friction test:

For the purpose of testing the hardenability of the cured product, a rubbing test for the hardened material rubbing was performed 50 times using a waste cloth containing acetone. Those who did not dissolve on the surface were judged to be sufficiently hardened to be evaluated as ○; those which were slightly dissolved on the surface were evaluated as ×.

Heat resistance test:

Each of the hardened coating films was placed in a hot air circulating drying oven at 200 ° C and heated for 3 minutes. After heating, it was taken out, and the trace of the melt was visually observed, and the heat resistance test was performed. The melting was not observed at all, and the change was rated as ○, and the part confirmed to be melted, and the changer was rated as ×.

The results of the above tests are summarized and disclosed in Table 2.

From the results disclosed in the above Table 2, it is apparent that the cured product obtained by curing the photocurable resin composition of the present invention has a result of the state of the cured coating film, the friction test, and the heat resistance test. It has the same curability and heat resistance as polyester acrylate and epoxy acrylate. Further, since lactic acid is used as a raw material, a photocurable resin composition which is mild to the environment can be provided by increasing the proportion of carbon derived from nature.

Examples 6 to 12 and Comparative Examples 4 and 5

The resin varnish 1 to 6 was blended in the proportions disclosed in Table 3, mixed with a mixer, and then kneaded in a three-roll mill to prepare an alkali-developing photosensitive resin composition.

Performance evaluation: <Optimum exposure amount>

The photosensitive resin compositions of the above Examples 6 to 12 and Comparative Examples 4 and 5 were applied onto a glass substrate by a screen printing method, and dried in a hot air circulating drying oven at 80 ° C for 30 minutes. After drying, exposure was carried out using a stepping exposure meter (Kodak No. 2) using an exposure apparatus equipped with a high-pressure mercury lamp, and development was carried out (30 ° C, 0.2 MPa, 1 wt% aqueous sodium carbonate solution) for 60 seconds. At the time of the clock, the optimum exposure amount is determined when the pattern of the remaining stage exposure meter is 7 steps.

<developmentality>

The photosensitive resin compositions of the above Examples 6 to 12 and Comparative Examples 4 and 5 were applied onto a glass substrate by a screen printing method to have a film thickness of about 25 μm, and were subjected to a hot air circulation type at 80 ° C. Dry in a drying oven for 30 minutes. After drying, development was carried out by using a 1 wt% aqueous sodium carbonate solution, and the time until the dried coating film was removed was measured by a code table.

Characteristic test:

The photosensitive resin compositions of the above-described examples and comparative examples were applied onto a glass substrate by a screen printing method to have a film thickness of about 20 μm, and dried in a hot air circulating drying oven at 80 ° C for 60 minutes. After drying, exposure was carried out at an optimum exposure amount, and a 1 wt% sodium carbonate aqueous solution at 30 ° C was developed under the conditions of a spray pressure of 0.2 MPa for 60 seconds to obtain a photosensitive pattern. Thereafter, it was heated at 150 ° C for 60 minutes to be hardened. The following characteristics of the obtained hardened coating film were evaluated.

<adhesiveness>

According to the conventional method, the hardened coating film formed on the glass substrate by the above method is cross-cut to have a checkerboard pattern. Next, after the peeling test is performed using the cellophane adhesive tape, the number of remaining checkerboards is as follows. Benchmarks are evaluated.

○: The number of remaining checkerboards is 70 or more and 100 or less.

△: The number of remaining checkers is above 30 and not above 70.

×: The number of residues in the checkerboard is above 0 and not up to 30.

<bending>

By the above method, the glass was replaced, and the hardened coating film formed on the PET of about 40 μm was peeled off, and the softness and the brittleness were evaluated. The softness of the obtained cured film was evaluated as ○, and it was evaluated as × with hard brittleness and no softness.

The results of the foregoing tests are summarized and disclosed in Table 4.

From the results disclosed in the above Table 4, it is apparent that the cured product obtained by curing the photocurable resin composition of the present invention has superior characteristics as compared with the conventional polyester acrylate or epoxy acrylate. . Further, it was surprisingly found that the resin into which the lactic acid skeleton was introduced did not significantly deteriorate the developability as compared with Comparative Example 4 and Comparative Example 5. This is considered to be due to the introduction of the lactic acid skeleton to increase the hydrophilicity. Further, it was found that a cured coating film having excellent photoreactivity, adhesion, and flexibility can be obtained. Further, depending on the molecular design, it is possible to obtain a photocurable resin which can greatly increase the lactic acid content and is mild to the environment.

[Industrial availability]

The photocurable resin and the photocurable resin composition containing the same according to the present invention can be used for various adhesives, printing inks, coating agents, particularly photoresists, or can be advantageously used as a circuit for a printed substrate. Forming a resist, a plating resist, and a solder resist. Others can also be used for color filters, black matrices, protective agents, and the like for flat display.

Fig. 1 shows an IR spectrum pattern of a photocurable resin produced in Resin Synthesis Example 1.

Fig. 2 is a graph showing the nuclear magnetic resonance spectrum of the photocurable resin produced in Resin Synthesis Example 1.

Fig. 3 shows an IR spectrum pattern of the photocurable resin produced in Resin Synthesis Example 2.

Fig. 4 is a view showing a nuclear magnetic resonance spectrum pattern of a photocurable resin produced in Resin Synthesis Example 2.

Fig. 5 shows an IR spectrum pattern of the photocurable resin produced in Resin Synthesis Example 3.

Fig. 6 is a graph showing the nuclear magnetic resonance spectrum of the photocurable resin produced in Resin Synthesis Example 3.

Fig. 7 shows an IR spectrum pattern of the photocurable resin produced in Resin Synthesis Example 4.

Fig. 8 is a graph showing a nuclear magnetic resonance spectrum of a photocurable resin produced in Resin Synthesis Example 4.

Fig. 9 shows an IR spectrum pattern of the photocurable resin produced in Resin Synthesis Example 5.

Fig. 10 shows a nuclear magnetic resonance spectrum pattern of a photocurable resin produced in Resin Synthesis Example 5.

Claims (9)

A photocurable resin characterized in that an epoxy resin (a') having two or more epoxy groups in one molecule, lactic acid or polylactic acid (b) is used as an epoxy resin in an epoxy resin (a') The base group of lactic acid or polylactic acid (b) is reacted in a ratio of 0.2 to 1.1 equivalents to obtain a hydroxyl group-containing resin, and then the resulting hydroxyl group-containing resin and (meth)acrylic acid group having an acid group or an isocyanate group are reacted. The body (c) is obtained by reacting an acid group or an isocyanate group in the (meth)acrylic monomer (c) in an amount of 0.05 to 1.0 equivalent to 1 equivalent of the hydroxyl group in the hydroxyl group-containing resin, and the double bond equivalent is 100. a range of ~600 g/eq, and having the molecular structure represented by the following general formula (I), (wherein, Ac represents a (meth)acryloxy group, and R ¹ represents a residue of the epoxy resin (a') containing a vinyl group formed by ring opening of an epoxy group of the epoxy resin (a'), R ² represents a node site containing a carbonyloxy group or a urethane bond, n represents an integer of 1 to 99, and m represents 0 or 1). The photocurable resin according to the first aspect of the invention, wherein the photocurable resin is a structural unit represented by the following general formula (II) as an essential repeating unit. (wherein, Ac represents a (meth) propylene decyloxy group, R ² represents a carbonyloxy group or a urethane-bonded node site, fc represents a hydroxy group or a (meth) propylene decyloxy group, and R ³ A hydrocarbon group having 1 to 10 carbon atoms, n is an integer from 1 to 99, m is 0 or 1, and a dotted line indicates a bond with another structural unit. The photocurable resin according to claim 1, wherein the node having a carbonyloxy group or a urethane bond represented by the above R ² is represented by the following formula a1, a2, or a3. By, (In the above formula, R ₄ represents an alkylene group having 1 to 10 carbon atoms, R ₅ represents a hydrocarbon group having 1 to 20 carbon atoms, R ₆ represents an alkylene group having 1 to 30 carbon atoms, and R ₇ represents carbon. Atom number 1~10 alkyl group). The photocurable resin according to claim 1, wherein the (meth)acrylic monomer (c) having an acid group or an isocyanate group is (meth)acrylic acid. The photocurable resin according to claim 1, wherein the (meth)acrylic monomer (c) having an acid group or an isocyanate group is a (meth)acrylonitrile alkyl isocyanate. A photocurable resin containing a carboxyl group, which is characterized in that an acid anhydride (d) is reacted with a photocurable resin as claimed in claim 1 By. A photocurable resin composition comprising a photocurable resin (A) according to any one of claims 1 to 5 and a carboxyl group-containing photocurable resin according to claim 6 At least one of the photocurable resin selected from the group consisting of (A') and the photopolymerization initiator (B) are essential components. The photocurable resin composition of claim 7 further contains a carboxyl group-containing resin (C) other than the carboxyl group-containing photocurable resin (A'). The photocurable resin composition of claim 7 or 8 further comprising a thermosetting component (D).