CN102388077B - Photocurable resin and photocurable resin composition - Google Patents

Abstract

The photocurable resin (A) has a molecular structure represented by the following general formula (I). In addition, the carboxyl group-containing photocurable resin (A') is obtained by reacting an acid anhydride (d) with a photocurable resin (A). The photocurable resin composition contains this photocurable resin (A) and/or carboxyl group-containing photocurable resin (A'), and a photopolymerization initiator (B) as an essential component. (wherein, Ac represents a (meth)acryloyloxy group, R ¹ represents a residue of the compound (a) containing an ethylene group formed by ring-opening of the epoxy group of the epoxy compound (a), R ² Represents a linking site containing a carbonyloxy group or a carbamate bond, n represents an integer from 1 to 99, and m represents 0 or 1.)

Description

Photocurable resin and photocurable resin composition

technical field

The present invention relates to a photocurable resin capable of forming a cured product excellent in photocurability, heat resistance, adhesiveness and flexibility, and a composition containing the same.

Background technique

From the viewpoint of rapid curing and energy saving, photocurable resins, especially UV curable resins, are widely used in adhesives, printing inks, various coating agents, and the like. In addition, it is also mixed with a carboxyl group-containing resin to form a photoresist imparted with alkali developability, which is used as a resist for circuit formation, a plating resist, a solder resist, and the like in printed circuit board applications. In addition, it is also used as a color filter, black matrix, and overcoat agent in flat panel display applications.

These UV curable resins are generally polyester acrylates, epoxy acrylates, urethane acrylates, etc. (for example, refer to Patent Documents 1 to 3), and these resins are almost all liquid from the viewpoint of rapid curing properties. compound of. However, although the resin of this form is indeed provided with rapid curing properties, there are many cases where there are problems in heat resistance characteristics required for many electronic materials, such as reflow resistance and soldering heat resistance. In addition, rapid-curing resins generally have significant cure shrinkage, and the resulting cured product is brittle and poor in adhesiveness. In addition to rapid curing and heat resistance, adhesiveness is also a characteristic that is strongly required for adhesives, printing inks, and various coating agents, and it is required to develop a product that combines these heat resistance and adhesiveness (A base) acrylate resin.

On the other hand, in recent years, issues with the theme of the environment are being widely discussed. Recently, new materials derived from natural substances rather than compounds derived from petroleum resources are attracting attention. Among them, the present inventors paid particular attention to lactic acid. Lactic acid is not a compound derived from petroleum resources, and fermented lactic acid obtained by fermentation of natural substances can be used. In addition, since the molecule has a functional group such as a carboxyl group or a hydroxyl group that can be easily modified chemically, various molecular designs can be performed. Furthermore, depending on the molecular design, the proportion of carbon derived from natural substances can be increased, and thus a very environmentally friendly material can be provided.

prior art literature

patent documents

Patent Document 1: Japanese Patent No. 3446840

Patent Document 2: Japanese Patent No. 3543409

Patent Document 3: Japanese Patent Laid-Open No. 2004-123780

Contents of the invention

The problem to be solved by the invention

In view of the above-mentioned background, the object of the present invention is to provide a photocurable resin and a photocurable resin composition containing it, wherein the photocurable resin can be obtained by using lactic acid as one of the starting materials It forms a cured product that is environmentally friendly, has excellent UV curability, and is excellent in heat resistance, adhesiveness, and flexibility.

solutions to problems

In order to achieve the above object, the present invention provides a photocurable resin, which is characterized in that epoxy compound (a), lactic acid or polylactic acid (b), and (meth)acrylic acid having an acid group or an isocyanate group It is obtained by reacting monomer (c) as an essential monomer component, and has a molecular structure represented by the following general formula (I).

(wherein, Ac represents a (meth)acryloyloxy group, R ¹ represents a residue of the compound (a) containing an ethylene group formed by ring-opening of the epoxy group of the epoxy compound (a), R ² Represents a linking site containing a carbonyloxy group or a carbamate bond, n represents an integer from 1 to 99, and m represents 0 or 1.)

In addition, in this specification, the so-called (meth)acrylic acid series is a term collectively referring to acrylic acid series, methacrylic acid series and their mixtures. ) acrylate or other similar expressions are the same.

In a preferred embodiment, the photocurable resin has a structural site represented by the following general formula (II) as an essential repeating unit.

(In the formula, Ac represents a (meth)acryloyloxy group, ^R2 represents a linking site containing a carbonyloxy group or a carbamate bond, fc represents a hydroxyl group or a (meth)acryloyloxy group, and ^R3 is a carbon atom A hydrocarbon group with a number of 1 to 10, n is an integer of 1 to 99, m is 0 or 1, and the dotted line represents a bond with other structural units.)

In a more preferred manner, in the general formula (I) or (II), the linking site represented by R ² having a carbonyloxy group or a carbamate bond is represented by the following general formula a1, a2, or a3 group.

[chemical formula 3]

(In the above formulas, R ⁴ represents an alkylene group with 1 to 10 carbon atoms, R ⁵ represents a hydrocarbon group with 1 to 20 carbon atoms, R ⁶ represents an alkylene group with 1 to 30 carbon atoms, R ⁷ represents a carbon An alkylene group having 1 to 10 atoms.)

In another preferred aspect, the photocurable resin is a resin having an average of 0.1 to 2.0 (meth)acryloyloxy groups per molecule of epoxy compound.

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

In other preferred forms, the epoxy compound (a) is an epoxy resin (a') having two or more epoxy groups in one molecule, a (meth)acrylic monomer having an acid group or an isocyanate group The body (c) is (meth)acryloyl alkyl isocyanate, and has (meth)acryloyl alkyl isocyanate and the reaction product of the epoxy resin (a') and lactic acid or polylactic acid (b) The structure obtained by the reaction of hydroxyl-containing resin.

In another preferred mode, the epoxy compound (a) is an epoxy resin (a') having two or more epoxy groups in one molecule, and has a molecular structure obtained by making the acid anhydride or a molecule obtained by reacting a reactant of a polyisocyanate compound and a hydroxyl-containing (meth)acrylate monomer with a hydroxyl-containing resin that is a reaction product of the epoxy resin (a') and lactic acid or polylactic acid (b) structure.

In addition, the present invention provides a carboxyl group-containing photocurable resin obtained by reacting an acid anhydride (d) with the photocurable resin.

Furthermore, the present invention also provides a photocurable resin composition characterized by containing at least one selected from the group consisting of the photocurable resin (A) and carboxyl group-containing photocurable resin (A'). A photocurable resin and a photopolymerization initiator (B) are essential components.

In a preferred aspect of the photocurable resin composition, another carboxyl group-containing resin (C) other than the above-mentioned carboxyl group-containing photocurable resin (A') is further contained, or a thermosetting component (D) is further contained.

The effect of the invention

The photocurable resin of the present invention is 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. The resulting reaction can be environmentally friendly by using lactic acid as one of the starting materials, and since the structural site represented by the general formula (I) is used as an essential repeating unit, it can form a product with excellent UV curability and heat resistance. , Cured product with excellent adhesion and flexibility.

Description of drawings

FIG. 1 is a graph showing an IR spectrum of a photocurable resin produced in Resin Synthesis Example 1. FIG.

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

FIG. 3 is a graph showing an IR spectrum of a photocurable resin produced in Resin Synthesis Example 2. FIG.

FIG. 4 is a graph showing a nuclear magnetic resonance spectrum of a photocurable resin produced in Resin Synthesis Example 2. FIG.

FIG. 5 is a graph showing an IR spectrum of a photocurable resin produced in Resin Synthesis Example 3. FIG.

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

FIG. 7 is a graph showing an IR spectrum of a photocurable resin produced in Resin Synthesis Example 4. FIG.

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

FIG. 9 is a graph showing an IR spectrum of a photocurable resin produced in Resin Synthesis Example 5. FIG.

10 is a graph showing a nuclear magnetic resonance spectrum of a photocurable resin produced in Resin Synthesis Example 5. FIG.

Detailed ways

By reacting these functional groups of (meth)acrylic monomers (c) having acid groups or isocyanate groups with terminal hydroxyl groups formed by the reaction of epoxy compounds (a) and lactic acid or polylactic acid (b), it is easy to obtain The photocurable resin of the present invention. As a result, the unsaturated double bond of the (meth)acrylic monomer (c) is introduced into a site away from the main chain of the resin through the lactic acid skeleton, thereby exhibiting excellent photoreactivity, and, since the lactic acid skeleton is introduced, A cured product with increased hydrophilicity, adhesiveness and flexibility can be obtained. In addition, depending on the molecular design, the content of lactic acid can be greatly increased, and an environmentally friendly photocurable resin can be obtained. Furthermore, heat resistance can be imparted by selectively reacting the epoxy compound reactive with lactic acid. In addition, at this time, an epoxy resin is easily used as a substance capable of imparting heat resistance by selectively reacting with lactic acid.

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

First, when a polyfunctional cresol-novolac 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), photocuring as shown in the following formula can be obtained: Sexual resin.

In addition, 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), a photoluminescent compound represented by the following formula can be obtained. curable resin.

[chemical formula 5]

Furthermore, when a polyfunctional cresol-novolac epoxy resin is used for the (a) component, lactic acid is used for the (b) component, and 2-acryloxyethyl isocyanate is used for the (c) component, the following formula can be obtained: Indicates the photocurable resin.

Furthermore, it is thought that the reaction of using a polyfunctional cresol-novolak type epoxy resin for (a) component, using lactic acid for (b) component, and using a polyisocyanate compound and a hydroxyl group-containing (meth)acrylate monomer for (c) component In the case of a product (eg, a reaction product of isophorone diisocyanate and hydroxyethyl (meth)acrylate), a photocurable resin represented by the following formula can be obtained.

In addition, the total number of repeating units a and b, the total number of c, d, and e, the total number of f and g, and the total number of h and i shown in each of the above structural formulas are used in the ring used as the (a) component. The epoxy resin has the number of epoxy groups or less, but can be adjusted arbitrarily according to the reaction ratio of (b) component and (c) component with respect to (a) component.

The reaction of the above-mentioned components (a) to (c) can be carried out by any of the following methods. The method is to make lactic acid or polylactic acid (b) and (meth)acrylic monosodium chloride having an acid group or an isocyanate group. A method in which the body (c) reacts with the epoxy compound (a) simultaneously; or first reacts lactic acid or polylactic acid (b) with the epoxy compound (a), and then makes (meth)acrylic acid having an acid group or an isocyanate group A method in which the monomer (c) reacts. Such a reaction is carried out in the presence or absence of an organic solvent as described later, in the presence of a polymerization inhibitor such as hydroquinone or oxygen, at usually about 50 to 150°C. At this time, if necessary, tertiary amines such as triethylamine, quaternary ammonium salts such as triethylbenzyl ammonium chloride, imidazole compounds such as 2-ethyl-4-methylimidazole, and phosphorus compounds such as triphenylphosphine can also be added. etc. as a catalyst.

In addition, the ratio of each component in the above-mentioned reaction (the input ratio of raw materials) is preferably such a ratio that the carboxyl group of the above-mentioned lactic acid or polylactic acid (b) becomes 0.2 to 1.1 equivalents, and when the total of the hydroxyl groups formed by the reaction of the epoxy group of component (a) and the carboxyl group of component (b) and the residual hydroxyl groups of lactic acid or polylactic acid (b) is 1 equivalent, it has an acidic group Or the acidic group or isocyanate group of the (meth)acrylic-type monomer (c) of an isocyanate group becomes 0.05-1.0 equivalent. When the carboxyl group of lactic acid or polylactic acid (b) is less than 0.2 equivalents with respect to 1 equivalent of epoxy groups of the epoxy compound (a), the heat resistance, adhesiveness and flexibility which are the objects of the present invention described above cannot be sufficiently obtained. Conversely, even if it is used in excess of 1.1 equivalents, theoretically only 1 equivalent will react, so these compounds remaining in an unreacted state will increase and become the main cause of the reduction in the physical properties of the cured product. preferred.

The photocurable resin (A) thus obtained preferably has 0.1 to 2.0 equivalents of (meth)acryloyloxy groups relative to 1 equivalent of the final epoxy group.

Moreover, although the weight average molecular weight of the photocurable resin (A) obtained by the said reaction differs with resin skeleton, it is generally preferable that it is the range of 2,000-150,000, and it is more preferable that it is the range of 5,000-100,000. When the weight average molecular weight is less than 2,000, the tack free performance of the coating film may be poor, the moisture resistance of the coating film after exposure may be poor, the film may decrease during development, and the resolution may deteriorate significantly. On the other hand, when the weight average molecular weight exceeds 150,000, handleability may deteriorate and storage stability may deteriorate. In addition, the weight average molecular weight can be measured by GPC etc. of the following conditions, for example.

Measuring device: "HLC-8220 GPC" manufactured by Tosoh Co., Ltd.,

Column: Guard column "H _XL -L" manufactured by Tosoh Co., Ltd.

+ "TSK-GEL G2000HXL" manufactured by Tosoh Co., Ltd.

+ "TSK-GEL G2000HXL" manufactured by Tosoh Co., Ltd.

+ "TSK-GEL G3000HXL" manufactured by Tosoh Co., Ltd.

+ "TSK-GEL G4000HXL" manufactured by Tosoh Co., Ltd.

Detector: RI (differential refractometer)

Determination conditions:

Column temperature: 40°C

Developing solvent: tetrahydrofuran

Flow rate: 1.0ml/min

Moreover, it is preferable that the double bond equivalent of the said photocurable resin (A) is 100 g/equivalent or more and 1000 g/equivalent or less. From the viewpoint of improving photocurability, it is preferably 100 g/equivalent or more and 600 g/equivalent or less. In addition, from the viewpoint of improving flexibility, the double bond equivalent is preferably 500 g/equivalent or more.

Examples of the epoxy compound (a) used in the synthesis of the photocurable resin (A) include (meth)acrylate-2-hydroxyethyl glycidyl ether, (meth)acrylate-2-hydroxypropyl Ester glycidyl ether, (meth)acrylate-3-hydroxypropyl glycidyl ether, (meth)acrylate-2-hydroxybutyl glycidyl ether, (meth)acrylate-4-hydroxybutyl glycidyl ether, Ethylenically unsaturated monomers containing epoxy groups such as (meth)acrylate-2-hydroxypentyl glycidyl ether, (meth)acrylate-6-hydroxyhexyl glycidyl ether or (meth)acrylate glycidyl ether Class, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, brominated bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, biphenol type epoxy resin Resin, bixylenol type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, brominated phenol novolak type epoxy resin, bisphenol A novolac type epoxy resin, etc. Glyceryl ether compounds; glycidyl ester compounds such as diglycidyl terephthalate, diglycidyl hexahydrophthalate, and diglycidyl dimer acid; triglycidyl isocyanurate, N, N , N', N'-tetraglycidyl m-xylylenediamine, N,N,N',N'-tetraglycidylbisaminomethylcyclohexane, N,N-diglycidyl aniline and other shrinkage Glycerylamine compounds, alicyclic epoxy resins such as 3,4-epoxycyclohexane carboxylate, copolymers of glycidyl methacrylate, styrene and methyl methacrylate, glycidyl methacrylate and Copolymerized epoxy resins such as copolymers of cyclohexylmaleimide and other well-known and commonly used epoxy compounds and epoxy resins.

As the above-mentioned lactic acid or polylactic acid (b), for example, Musashino Lactic Acid (registered trademark) F manufactured by Musashino Chemical Research Institute Co., Ltd. can be preferably used. In addition, a lactic acid oligomer having a moderate repeating structure by dehydrating and condensing lactic acid between molecules can also be used.

As the (meth)acrylic monomer (c) having an acid group or an isocyanate group used in the synthesis of the above-mentioned photocurable resin (A), it can be used alone or in combination of two or more. The (meth)acrylic monomer (c-1) and the (meth)acrylic monomer (c-2) having an isocyanate group.

Examples of the (meth)acrylic monomer (c-1) having an acid group include acrylic acid, methacrylic acid, acrylic anhydride, methacrylic anhydride, crotonic acid, cinnamic acid, vinyl acetic acid, sorbic acid, ε - polylactone (meth)acrylate in which butyrolactone reacts with (meth)acrylic acid to elongate its molecule, and (meth)acrylic acid dimer, and these monomers can be used alone or in combination of two or more.

The (meth)acrylic monomer (c-2) having an isocyanate group is not particularly limited as long as it is an isocyanate compound having one isocyanate group and one or more ethylenically unsaturated groups in one molecule. Specific examples include (meth)acryloyloxyethyl isocyanate, (meth)acryloyloxyethoxyethyl isocyanate, bis(acryloyloxymethyl)ethyl isocyanate, or these compounds Modifiers, etc. Commercially available products include "KARENZ MOI" (methacryloxyethyl isocyanate), "KARENZAOI" (acryloyloxyethoxyethyl isocyanate), " KARENZMOI-EG" (methacryloxyethoxyethyl isocyanate), "KARENZMOI-BM" (isocyanate block of KARENZ MOI), "KARENZMOI-BP" (isocyanate block of KARENZ MOI), " KARENZBEI" (1,1-bis(acryloyloxymethyl)ethyl isocyanate). In addition, these product names are registered trademarks. Furthermore, compounds having one hydroxyl group and one or more ethylenically unsaturated groups in one molecule, isophorone diisocyanate, toluene diisocyanate, tetramethylxylene diisocyanate, hexamethylene diisocyanate, etc. can also be used. Half carbamate compound of diisocyanate. These (meth)acrylic monomers (c-2) which have an isocyanate group can be used individually or in combination of 2 or more types.

In addition, it is also possible to prepare a carboxyl group-containing photocurable resin (A') soluble in an aqueous alkali solution by reacting the acid anhydride (d) to the hydroxyl group of the photocurable resin (A) obtained as above to introduce a carboxyl group. . In this reaction, the amount of the acid anhydride (d) used is generally 0.1 to 1.0 mol with respect to 1 mol of the hydroxyl group of the above-mentioned photocurable resin (A). The acid value of (A') is about 20-200 mgKOH/g, More preferably, it is the addition amount of 50-120 mgKOH/g.

The addition reaction of the acid anhydride (d) to the above-mentioned photocurable resin (A) is in the presence or absence of an organic solvent as described later, in the presence or absence of hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechin In the presence of a polymerization inhibitor such as phenol and gallicol, it is usually carried out at about 50 to 150°C. At this time, if necessary, tertiary amines such as triethylamine, quaternary ammonium salts such as triethylbenzyl ammonium chloride, imidazole compounds such as 2-ethyl-4-methylimidazole, phosphorus compounds such as triphenylphosphine, Metal salts of organic acids such as lithium, chromium, zirconium, potassium, and sodium salts of naphthenic acid, lauric acid, stearic acid, oleic acid, or octenic acid are used as catalysts. These catalysts can be used alone or in combination of two or more.

Examples of the acid anhydride (d) include methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic anhydride, 3 , 6-endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, tetrabromophthalic anhydride and other alicyclic dibasic anhydrides; succinic anhydride, maleic anhydride, Itaconic anhydride, octenyl succinic anhydride, penta(dodecenyl) succinic anhydride, phthalic anhydride, trimellitic anhydride and other aliphatic or aromatic dibasic anhydrides, or biphenyl tetracarboxylic dianhydride, diphenyl Aliphatic or aromatic tetracarboxylic dianhydride such as phenylene tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, etc. Anhydrides, one or two or more of these acid anhydrides may be used.

The photocurable resin combination of the present invention can be obtained by further adding a photopolymerization initiator (B) to the photocurable resin (A) and/or carboxyl group-containing photocurable resin (A') of the present invention obtained as above. things. Examples of photopolymerization initiators, photoinitiation aids, and sensitizers that can be suitably used in the photocurable resin composition of the present invention include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, Ketal compounds, benzophenone compounds, xanthone compounds, and the like.

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

When specific examples of the acetophenone compound are given, for example, there are acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-Dichloroacetophenone.

Specific examples of the anthraquinone compound include 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, and 1-chloroanthraquinone.

When specific examples of thioxanthone compounds are given, there are, for example, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone xanthone.

When specific examples of ketal compounds are given, there are, for example, acetophenone dimethyl ketal and benzil dimethyl ketal.

When specific examples of benzophenone compounds are given, for example, benzophenone, 4-benzoyl diphenyl sulfide, 4-benzoyl-4'-methyl diphenyl sulfide, 4-benzoyl- 4'-Ethyl diphenyl sulfide, 4-benzoyl-4'-propyl diphenyl sulfide.

In addition, there are α-aminoacetophenone series, acylphosphine oxide series, and oxime ester series. Specifically, 2-methyl-1-[4-(methylthio)phenyl]-2- Morpholine propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholine phenyl)-butane-1-one, 2-(dimethylamino)-2-[ (4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, N,N-dimethylaminoacetophenone and the like. Commercially available products include IRGACURE 907, IRGACURE 369, and IRGACURE 379 manufactured by Ciba Japan K.K. Examples of commercially available oxime ester initiators include CGI-325 manufactured by Ciba Japan K.K., IRGACURE OXE01, IRGACURE OXE02, N-1919 manufactured by ADEKA CORPORATION, and the like. Examples of the acylphosphine oxide-based initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, etc. Examples of commercially available products include Lucirin TPO manufactured by BASFCORATION, IRGACURE 819 manufactured by Ciba Japan K.K., and the like.

The above mentioned representative photopolymerization initiators are not limited to the above-listed initiators as long as they generate radical active species by light irradiation or contribute to the action of the growing species. In addition, as a sensitizer which does not cause generation of radicals itself but has a sensitizing effect on the above-mentioned photopolymerization initiator, commonly known ones can also be used. The said photoinitiator and sensitizer can be used individually or in combination of 2 or more types.

Moreover, in order to provide alkali developability to the photocurable resin composition of this invention, other well-known and commonly-used carboxyl group-containing resins (C) other than the said carboxyl group-containing photocurable resin (A') can be used.

As a specific example of the carboxyl group-containing resin (C), the compounds listed below (any one of an oligomer and a polymer may be used) can be suitably used.

(1) Copolymer-containing unsaturated group-containing compounds obtained by copolymerization of unsaturated carboxylic acids such as (meth)acrylic acid and unsaturated group-containing compounds such as styrene, α-methylstyrene, lower alkyl (meth)acrylates, and isobutylene. carboxyl resin.

(2) Diisocyanates such as aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate and carboxyl group-containing diol compounds such as dimethylol propionic acid and dimethylol butyric acid And polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A-based alkylene oxide adduct diols, with phenolic hydroxyl groups and alcoholic properties Carboxyl group-containing urethane resin produced by addition polymerization of diol compounds such as hydroxyl compounds.

(3) Through diisocyanate and bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, Carboxyl group-containing photosensitive amino groups produced by addition polymerization of (meth)acrylates of difunctional epoxy resins such as phenolic epoxy resins or partially anhydride-modified products, carboxyl group-containing diol compounds, and diol compounds Formate resin.

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

(5) In the synthesis of the above (2) or (3) resin, equimolar reactants of isophorone diisocyanate and pentaerythritol triacrylate are added to have one isocyanate group and more than one (meth)acrylic acid in the molecule A carboxyl group-containing photosensitive urethane resin obtained by terminal (meth)acrylated compound.

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

(7) Reaction of (meth)acrylic acid with the polyfunctional epoxy resin obtained by further epoxidizing the hydroxyl group of the 2-functional (solid) epoxy resin with epichlorohydrin, and adding the 2-basic acid anhydride to the polyfunctional epoxy resin generated in the above-mentioned reaction A carboxyl-containing photosensitive resin obtained from a hydroxyl group.

(8) A carboxyl group-containing polyester resin obtained by reacting a dicarboxylic acid with a bifunctional oxetane resin and adding a dibasic acid anhydride to the primary hydroxyl group formed by the above reaction.

(9) A carboxyl group-containing photosensitive resin obtained by further adding a compound having one epoxy group and one or more (meth)acrylic groups in one molecule to the above resins (1) to (8).

In order to provide heat resistance, you may add a thermosetting component (D) to the photocurable resin composition of this invention. As the thermosetting component used in the present invention, amine resins such as melamine resins and benzoguanamine resins, blocked isocyanate compounds, cyclocarbonate compounds, polyfunctional epoxy compounds, polyfunctional oxetane compounds, cyclo Well-known and commonly used thermosetting resins such as sulfur resins and melamine derivatives. Particularly preferred is a thermosetting component (D) having two or more cyclic ether groups and/or cyclic thioether groups (hereinafter simply referred to as cyclic (thio)ether groups) in the molecule.

Such a thermosetting component (D) having two or more cyclic (thio)ether groups in the molecule has two or more cyclic ether groups selected from 3, 4 or 5-membered rings in the molecule, or cyclic Compounds of any one or two groups in the thioether group, for example: compounds with at least two or more epoxy groups in the molecule, i.e. polyfunctional epoxy compounds (D-1), have in the molecule Compounds with at least two or more oxetanyl groups, that is, polyfunctional oxetane compounds (D-2), compounds with two or more sulfide groups in the molecule, that is, episulfide resins (D-3), etc. .

Examples of the polyfunctional epoxy compound (D-1) include jER828 manufactured by Japan Epoxy Resins Co. Ltd., jER834, jER1001, jER1004, EPICLON 840 manufactured by DIC CORPORATION, EPICLON 850, EPICLON 1050, EPICLON 2055, Toto EPOTOTE YD-011, YD-013, YD-127, YD-128 manufactured by Kasei Corporation, D.E.R.317, D.E.R.331, D.E.R.661, D.E.R.664 manufactured by Dow Chemical Company, ARALDITE 6071, ARALDITE 6084, ARALDITE manufactured by Ciba Japan K.K. GY250, ARALDITE GY260, SUMI-EPOXYESA-011, ESA-014, ELA-115, ELA-128 manufactured by Sumitomo Chemical Industries, Ltd., A.E.R.330, A.E.R.331, A.E.R.661, A.E.R.664 manufactured by Asahi Kasei Industries, Ltd. (any one) All are trade names) Bisphenol A type epoxy resin; jERYL903 manufactured by Japan Epoxy Resins Co. Ltd., EPICLON 152, EPICLON 165 manufactured by DIC CORPORATION, EPOTOTE YDB-400, YDB-500, Dow manufactured by Tohto Kasei Co., Ltd. D.E.R.542 manufactured by Chemical Company, ARALDITE 8011 manufactured by Ciba Japan K.K., SUMI-EPOXYE SB-400, ESB-700 manufactured by Sumitomo Chemical Industries, Ltd., A.E.R.711, A.E.R.714 manufactured by Asahi Kasei Industries, etc. is a trade name) brominated epoxy resin; jER152, jER154 manufactured by Japan Epoxy Resins Co. Ltd., D.E.N.431, D.E.N.438 manufactured by Dow Chemical Company, EPICLON N-730, EPICLON N-770, EPICLON N-865 manufactured by DICCORPORATION , EPOTOTE YDCN-701, YDCN-704 manufactured by Tohto Chemical Co., Ltd., ARALDITE ECN1235, ARALDITE ECN1273, ARALDITE ECN1299, ARALDITEXPY307 manufactured by Ciba Japan K.K., EPPN-201 and EOCN-1 manufactured by Nippon Kayaku Co., Ltd. 025, EOCN-1020, EOCN-104S, RE-306, SUMI-EPOXY ESCN-195X, ESCN-220 manufactured by Sumitomo Chemical Industries, Ltd., A.E.R.ECN-235, ECN-299 manufactured by Asahi Kasei Industries, etc. (trade name) novolak-type epoxy resin; EPICLON 830 manufactured by DIC CORPORATION, jER807 manufactured by Japan Epoxy Resins Co. Ltd., EPOTOTE YDF-170 manufactured by Tohto Kasei Co., Ltd., YDF-175, YDF-2004, manufactured by Ciba Japan K.K. ARALDITE XPY306, etc. (either is a brand name) bisphenol F-type epoxy resin; EPOTOTE ST-2004, ST-2007, ST-3000 (trade name) and other hydrogenated bisphenol A-type epoxy resins manufactured by Tohto Chemical Co., Ltd. Oxygen resin; jER604 manufactured by Japan Epoxy Resins Co. Ltd., EPOTOTE YH-434 manufactured by Tohto Kasei Co., Ltd., ARALDITE MY720 manufactured by CibaJapan K.K., SUMI-EPOXY ELM-120 manufactured by Sumitomo Chemical Industries, etc. (either (trade name) glycidyl amine type epoxy resin; hydantoin type epoxy resin such as ARALDITE CY-350 (trade name) manufactured by Ciba Japan K.K.; CELLOXIDE 2021 manufactured by DAICEL CHEMICAL INDUSTRIES, LTD., ARALDITE CY175 manufactured by Ciba Japan K.K. , CY179, etc. (all are trade names) alicyclic epoxy resin; YL-933 manufactured by Japan Epoxy Resins Co. Ltd., T.E.N., EPPN-501, EPPN-502 manufactured by Dow Chemical Company, etc. (any one All are trade names) Trishydroxyphenylmethane type epoxy resin; Dicresol type such as YL-6056, YX-4000, YL-6121 (all are trade names) manufactured by Japan Epoxy Resins Co. Ltd. Or biphenol type epoxy resin or their mixture; bisphenol S type epoxy such as EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Denka Kogyo Co., Ltd., EXA-1514 (trade name) manufactured by DIC CORPORATION, etc. Resin: bisphenol A novolak type epoxy resin such as jER157S (trade name) manufactured by Japan Epoxy Resins Co. Ltd.; jERYL-931, CibaJa manufactured by Japan Epoxy Resins Co. Ltd. ARALDITE 163 manufactured by Pan K.K., etc. (either is a trade name) tetraphenol ethane type epoxy resin; ARALDITE PT810 manufactured by Ciba Japan K.K., TEPIC, etc. manufactured by Nissan Chemical Industries, Ltd. (either is a trade name) ) Heterocyclic epoxy resins; diglycidyl phthalate resins such as BLEMMER DGT manufactured by NOF Corporation; tetraglycidyl xylenyl ethane resins such as ZX-1063 manufactured by Tohto Kasei Corporation; Naphthalene group-containing epoxy resins such as ESN-190, ESN-360 manufactured by Iron Chemical Corporation, HP-4032, EXA-4750, EXA-4700 manufactured by DIC Corporation; HP-7200 and HP-7200H manufactured by DIC Corporation have Dicyclopentadiene-based epoxy resins; glycidyl methacrylate copolymer epoxy resins such as CP-50S and CP-50M manufactured by NOF Corporation; cyclohexylmaleimide and glycidyl methacrylate Copolymerized epoxy resin of ester; Epoxy-modified polybutadiene rubber derivatives (such as PB-3600 manufactured by DAICEL CHEMICAL INDUSTRIES, LTD., etc.), CTBN modified epoxy resin (such as YR manufactured by Dongdu Chemical Industry Co., Ltd. -102, YR-450, etc.), etc., but not limited to these. These epoxy resins can be used individually or in combination of 2 or more types. Among them, novolak-type epoxy resins, heterocyclic epoxy resins, bisphenol A-type epoxy resins, or mixtures thereof are particularly preferable.

Examples of the polyfunctional oxetane compound (D-2) include 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)methyl acrylate, (3-ethyl-3-oxetanyl)methyl acrylate, (3-methyl-3-oxetanyl)methyl methacrylate, (3-ethyl-3-oxetanyl)methyl methacrylate, their oligomers or copolymers, etc. Functional oxetanes, in addition, oxetanol and novolac resins, poly(p-hydroxystyrene), Cardo-type bisphenols, calixarenes, resorcinol calixarenes, Or an etherified product of a resin having a hydroxyl group such as silsesquioxane or the like. In addition, copolymers of an unsaturated monomer having an oxetane ring and an alkyl (meth)acrylate, etc. are also mentioned.

Examples of the compound (D-3) having two or more cyclic thioether groups in the molecule include bisphenol A episulfide resin YL7000 manufactured by Japan Epoxy Resins Co. Ltd. and the like. In addition, an episulfide resin obtained by substituting an oxygen atom of an epoxy group of a novolak-type epoxy resin with a sulfur atom by the same synthesis method may also be used.

Regarding the compounding amount of the above-mentioned thermosetting component (D) having two or more cyclic (thio)ether groups in the molecule, relative to the above-mentioned photocurable resin (A) and/or carboxyl group-containing photocurable resin (A') 100 mass parts (when using 2 or more types of resins, the total amount of these 2 or more types of resins), 5-70 mass parts, More preferably, the range of 10-50 mass parts is suitable. When the compounding amount of the thermosetting component (D) having two or more cyclic (thio)ether groups in the molecule is less than the above-mentioned range, the carboxyl group remains in the cured coating film, and the heat resistance, alkali resistance, and electrical insulation are poor. Properties and the like are lowered, so it is not preferable. On the other hand, when exceeding the said range, since the low molecular weight cyclic (thio)ether group remains in a dried coating film, the intensity|strength of a coating film etc. will fall, and it is unpreferable.

When using the thermosetting component (D) which has two or more cyclic (thio) ether groups in a molecule|numerator mentioned above, it is preferable to contain a thermosetting catalyst. Examples of such thermosetting catalysts include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyano Dicyandiamide, benzyldimethylamine, 4-(two Amine compounds such as methylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, hexyl Hydrazine compounds such as diacid dihydrazide and sebacic acid dihydrazide; phosphorus compounds such as triphenylphosphine, etc. In addition, commercially available products include, for example, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, and 2P4MHZ (all of which are trade names of imidazole-based compounds) manufactured by Shikoku Chemical Industry Co., Ltd., and manufactured by San-Apro Ltd. U-CAT (registered trademark) 3503N, U-CAT3502T (all are trade names of blocked isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA 102, U-CAT5002 (all are bicyclic Formula amidine compounds and their salts), etc. It is not particularly limited to these, and it may be a substance that promotes a thermosetting catalyst for an epoxy resin or an oxetane compound, or a substance that promotes a reaction between an epoxy group and/or an oxetane group and a carboxyl group, and may be used alone or Mix two or more to use. In addition, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-s-triazine, 2-vinyl-2,4- Diamino-s-triazine, 2-vinyl-4,6-diamino-s-triazine·isocyanuric acid adduct, 2,4-diamino-6-methacryloxyethyl-sy As a s-triazine derivative such as a triazine/isocyanuric acid adduct, it is preferable to use these compounds functioning as an adhesion-imparting agent in combination with the aforementioned thermosetting catalyst.

It is sufficient that the compounding amount of these thermosetting catalysts is a usual ratio, for example, with respect to at least one photocurable resin selected from the group consisting of the above-mentioned photocurable resin (A) and carboxyl group-containing photocurable resin (A'), 100 parts by mass of curable resin or thermosetting component (D) having two or more cyclic (thio)ether groups in the molecule, preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15.0 parts by mass.

In addition to the above thermosetting compounds, as thermosetting components, isocyanate compounds and block compounds thereof, bismaleimide compounds, oxazine compounds, carbodiimide resins, etc. Sexually reactive substances can be used without particular limitation.

Furthermore, the compound which has one or more ethylenically unsaturated groups in a molecule|numerator can be mix|blended with curable resin composition of this invention. As such a compound, various compounds can be used in order to optimize the hardness and flexibility of the obtained cured product, but it is particularly preferable to have two or more olefinic compounds in one molecule from the viewpoint of photocurability. Compounds with saturated groups. Examples of such compounds include diacrylate esters of diols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, Polyols such as hydroxyethyl isocyanurate or polyacrylic esters such as ethylene oxide adducts or propylene oxide adducts of these polyols; phenoxyacrylate, bisphenol A diacrylate and these Polyacrylic acid esters such as ethylene oxide adducts or propylene oxide adducts of phenols; glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl iso Polyacrylic acid esters of glycidyl ether such as cyanurate; and melamine acrylate, and/or each methacrylate corresponding to the above-mentioned acrylate, and the like.

Furthermore, epoxy acrylate resins obtained by reacting acrylic acid with polyfunctional epoxy resins such as cresol novolac epoxy resins, and further mixtures of hydroxy acrylates such as pentaerythritol triacrylate with isophorone diisocyanate and the like can also be used. An epoxy urethane acrylate compound obtained by reacting a half urethane compound of diisocyanate with the hydroxyl group of the epoxy acrylate resin, and the like.

The photocurable resin composition of the present invention may contain a colorant. Commonly known colorants such as black, white, red, blue, green, and yellow can be used as the colorant, and any of pigments, dyes, and pigments may be used. However, it is preferable not to contain a halogen from the viewpoint of reducing the environmental load and the influence on the human body.

In order to increase the physical strength of the coating film, etc., the photocurable resin composition of this invention may mix|blend a filler as needed. As such a filler, well-known and commonly used inorganic or organic fillers can be used, and barium sulfate, spherical silica, and talc are particularly preferably used. Furthermore, metal hydroxides such as titanium oxide, metal oxides, and aluminum hydroxide can also be used as extender fillers in order to obtain a white appearance and flame retardancy.

According to needs, the photocurable resin composition of the present invention can be further compounded with well-known and commonly used thermal polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, tert-butyl catechol, gallicol, and phenothiazine, micropowder di Silicon oxide, organic bentonite, montmorillonite and other well-known and commonly used tackifiers, silicone-based, fluorine-based, polymer-based and/or antifoaming agents and/or leveling agents, imidazole-based, thiazole-based, triazole-based and other silane coupling agents Commonly used additives such as mixtures, antioxidants, and rust inhibitors.

In addition, in order to dissolve the above-mentioned photocurable resin (A) or carboxyl group-containing photocurable resin (A') and photosensitive (meth)acrylate compound, and adjust the composition to a viscosity suitable for the coating method, the present invention The photocurable resin composition can mix an organic solvent.

Examples of organic solvents include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, and carbitol. , methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether and other glycol ethers; ethyl acetate, butyl acetate, cellosolve Acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate and other acetates; ethanol, propanol, ethylene glycol , propylene glycol and other alcohols; octane, decane and other aliphatic hydrocarbons; petroleum ether, naphtha, hydrogenated naphtha, solvent naphtha and other petroleum-based solvents, etc. These organic solvents may be used alone or in admixture of two or more. In addition, the compounding quantity of an organic solvent can be set to arbitrary quantity according to the coating method.

The photocurable resin composition of the present invention can be adjusted to a viscosity suitable for the coating method using, for example, the above-mentioned organic solvent, and can be coated by dip coating, flow coating, roll coating, rod coater, wire coating, etc. Coating on the substrate by screen printing method, curtain coating method and other methods. Thereafter, by volatilizing and drying the organic solvent contained in the composition at a temperature of about 60 to 100° C. (preliminary drying), a touch-dried coating film can be formed. Alternatively, the above-mentioned composition may be applied on a carrier film, dried, and wound up as a film to obtain a dry film form. A resin insulating layer can be formed by sticking such a dry film on a base material.

Thereafter, by using a conveyor-type exposure machine equipped with a high-pressure mercury lamp or a metal halide lamp and capable of irradiating active energy rays, the coating film of the obtained photocurable resin composition is irradiated with active energy rays to obtain curing easily. things. The exposed portion (portion irradiated with active energy rays) of the coating film is cured. In addition, when patterning the obtained photocurable resin composition, it is selectively exposed with active energy rays through a patterned mask in a contact or non-contact manner, or directly exposed with a laser direct exposure machine. Pattern exposure is performed, and the unexposed part is developed with a dilute alkaline aqueous solution (for example, 0.3 to 3% sodium carbonate aqueous solution) to form a resist pattern. Furthermore, in the case of a composition containing a thermosetting component (D), for example, by heating to a temperature of about 140 to 200° C. to thermally cure it, the hydroxyl group or carboxyl group of the photocurable resin (A) can be photosensitive. The carboxyl group of the curable resin (A') reacts with the thermosetting component (D) having two or more cyclic ether groups and/or cyclic thioether groups in the molecule to form heat resistance, chemical resistance, A cured coating film with excellent properties such as moisture absorption resistance, adhesion, and electrical properties. In addition, when the thermosetting component (D) is not contained, the unreacted ethylenically unsaturated bonds remaining in the unreacted state at the time of exposure can be thermally radically polymerized by heat treatment, and the coating film properties can be improved. Therefore, depending on the purpose , purposes, can also be heat-treated (thermal curing).

As the base material, in addition to printed circuit boards or flexible printed circuit boards with circuits formed in advance, paper-phenolic resin, paper-epoxy resin, glass cloth-epoxy resin, glass-polyimide, All grades of composite materials (FR-4, etc.) ) Copper laminates, polyimide films, PET films, glass substrates, ceramic substrates, silicon wafer boards, etc.

The volatilization drying performed after coating the photocurable resin composition of this invention can be performed using a hot-air circulation type drying oven, an IR oven, a hot plate, a convection oven, etc.

As the exposure machine used in the above-mentioned active energy ray irradiation, a conveyor-type exposure machine capable of irradiating active energy rays can be used. In addition, when performing pattern formation, an ultraviolet exposure device equipped with a high-pressure mercury lamp or a metal halide lamp or a direct exposure device can be used. A drawing device (for example, a laser direct imaging device that draws an image directly with a laser from CAD data from a computer). Any of high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, gas lasers, solid-state lasers, and semiconductor lasers may be used as the active energy rays as long as light with a maximum wavelength in the range of 350 to 410 nm is used. In addition, the exposure amount varies depending on the film thickness and the like, but generally, it can be set within the range of 5 to 800 mJ/cm ² , preferably 10 to 500 mJ/cm ² , and more preferably 10 to 300 mJ/cm ² .

As an image development method at the time of said image development, an appropriate method, such as a dipping method, a shower method, a spray method, and a brush method, can be employ|adopted. In addition, as a developer, aqueous alkali solutions such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, and amines can be used.

Example

Hereinafter, although an Example and a comparative example are given and this invention is demonstrated concretely, this invention is not limited to a following example. In addition, all "parts" and "%" mentioned below are based on mass unless otherwise specified.

Resin Synthesis Example 1

Into a flask equipped with a thermometer, a stirrer, and a reflux condenser, 100 g of diethylene glycol monoethyl ether acetate and cresol novolak-type epoxy resin (manufactured by DIC Corporation, EPICLON N-680, softening point 82°C, ring Oxygen equivalent 211) 211g (1.0 mol), 90% lactic acid (manufactured by Musashino Chemical Research Institute, Musashino lactic acid 90F, purity 90%) 100g (1.0 mol as lactic acid), di-tert-butylhydroxytoluene 1.51 g and 0.15 g of hydroquinone, heated to 100°C to dissolve them uniformly. Next, 1.14 g of triphenylphosphine was added, and the temperature was raised to 110° C. while blowing in nitrogen gas, and the reaction was carried out for 10 hours while removing the contained water to the outside of the system. Next, the inside of the system was replaced with an air atmosphere, and then, 152 g of diethylene glycol monoethyl ether acetate and 2-acryloyloxyethyl isocyanate (manufactured by Showa Denko Co., Ltd., KARENZ AOI, Molecular weight 141) 148g (1.05mol), reacted at 85°C for 3 hours, confirmed the disappearance of the peak (2270cm ^-1 ) of the isocyanate group in the solution by an infrared spectrophotometer, and obtained a solid content acid value of 12.7mgKOH/g, a solid content of 64.0% resin solution. The double bond equivalent of the solid content was 429, and the lactic acid content was 20%. This was used as resin varnish 1. In addition, the infrared absorption spectrum (measured using a Fourier transform infrared spectrophotometer FT-IR) of the obtained photocurable resin is shown in FIG. 1 , and the nuclear magnetic resonance spectrum (solvent CDCl ₃ , reference material TMS (tetramethylsilane )) are shown in Figure 2.

Intermediate Synthesis Example 1 (Synthesis of Lactic Acid Oligomer)

Put 90% lactic acid (manufactured by Musashino Chemical Research Institute, Musashino Lactic Acid 90F, purity 90%) in a flask equipped with a thermometer, a stirrer, and a reflux condenser, 1000 g (10 moles in terms of lactic acid), and blow in nitrogen At the same time, the temperature was raised to 120°C, and the contained water and dehydrated water produced by the intermolecular dehydration esterification of lactic acid were removed from the system at any time, and reacted for 11 hours at the same time to obtain a resin solution with an acid value of 207 mgKOH/g. This was used as the lactic acid oligomer intermediate X-1.

Resin Synthesis Example 2

Into a flask equipped with a thermometer, a stirrer, and a reflux condenser, 147 g of diethylene glycol monoethyl ether acetate and cresol novolak-type epoxy resin (manufactured by DIC Corporation, EPICLON N-680, softening point 82° C., ring Oxygen equivalent 211) 211g (1.0 mol), lactic acid oligomer intermediate (X-1) 216g (0.8 mol), acrylic acid 14.4g (0.2 mol), di-tert-butylhydroxytoluene 2.21g and hydroquinone 0.22g, heating to 100°C to make it dissolve evenly. Next, 1.68 g of triphenylphosphine was added, and the temperature was raised to 110° C. under an air atmosphere, and the mixture was reacted for 8 hours. Next, 188 g of diethylene glycol monoethyl ether acetate and 106 g (0.75 mol) of 2-acryloyloxyethyl isocyanate (manufactured by Showa Denko Co., Ltd., KARENZ AOI, molecular weight 141) were added to the resulting reaction liquid, After reacting at ℃ for 3 hours, the disappearance of the isocyanate group peak (2270 cm ^-1 ) in the solution was confirmed by an infrared spectrophotometer, and a resin solution having a solid acid value of 7.0 mgKOH/g and a solid content of 62.0% was obtained. The double bond equivalent of the solid content was 576, and the lactic acid content was 40%. This was used as resin varnish 2. In addition, the infrared absorption spectrum (measured using a Fourier transform infrared spectrophotometer FT-IR) of the obtained photocurable resin is shown in Figure 3, and the nuclear magnetic resonance spectrum (solvent CDCl ₃ , reference material TMS (tetramethylsilane )) are shown in Figure 4.

Resin Synthesis Example 3

100 g of diethylene glycol monoethyl ether acetate and cresol novolak type epoxy resin (manufactured by DIC Corporation, EPICLON N-680, softening point 82°C, Epoxy equivalent 211) 211g (1.0 mol), 90% lactic acid (manufactured by Musashino Chemical Research Institute, Musashino lactic acid 90F, purity 90%) 100g (1.0 mol as lactic acid), di-tert-butylhydroxytoluene 1.51g and 0.15g of hydroquinone, heated to 100°C to dissolve them uniformly. Next, 1.14 g of triphenylphosphine was added, the temperature was raised to 110° C. while nitrogen gas was blown in, and the reaction was carried out for 10 hours while removing contained water to the outside of the system. Next, after replacing the inside of the system with an air atmosphere, 181 g of diethylene glycol monoethyl ether acetate and 2-acryloyloxyethyl isocyanate (manufactured by Showa Denko Co., Ltd., KARENZ AOI, molecular weight 141) 148 g (1.05 mol) was reacted at 85° C. for 3 hours, and it was confirmed by an infrared spectrophotometer that the peak (2270 cm ⁻¹ ) of the isocyanate group in the solution disappeared. Furthermore, 51.7 g (0.34 mol) of tetrahydrophthalic anhydrides were added, and it was made to react at 110 degreeC for 3 hours, and obtained the resin solution of solid content acid value 49.0 mgKOH/g, and solid content 64%. The double bond equivalent of the solid content was 477, and the lactic acid content was 18%. This was used as resin varnish 3. In addition, the infrared absorption spectrum (measured using a Fourier transform infrared spectrophotometer FT-IR) of the obtained photocurable resin is shown in Fig. 5, and the nuclear magnetic resonance spectrum (solvent CDCl ₃ , reference material TMS (tetramethylsilane )) are shown in Figure 6.

Resin Synthesis Example 4

Add 30.8 g of diethylene glycol monoethyl ether acetate and 187 g (1.0 mol), 90% lactic acid (manufactured by Musashino Chemical Research Institute, Musashino lactic acid 90F, purity 90%) 100g (1.0 mol as lactic acid), di-tert-butylhydroxytoluene 1.39g and hydroquinone 0.14g, Heat to 90°C to make it dissolve evenly. Next, 0.97 g of triphenylphosphine was added, and the temperature was raised to 110° C. while blowing in nitrogen gas, and the reaction was carried out for 11 hours while removing the contained water to the outside of the system. Next, after replacing the inside of the system with an air atmosphere, 91.2 g of diethylene glycol monoethyl ether acetate and 2-acryloyloxyethyl isocyanate (manufactured by Showa Denko Co., Ltd., KARENZ AOI, Molecular weight 141) 141g (1.0 mole), reacted at 85°C for 3 hours, confirmed the disappearance of the peak (2270cm ^-1 ) of the isocyanate group in the solution by an infrared spectrophotometer, and obtained a solid content acid value of 3.5mgKOH/g, a solid content of 76.0% resin solution. The double bond equivalent of the solid content was 418, and the lactic acid content was 22%. This was used as resin varnish 4. In addition, the infrared absorption spectrum (measured using a Fourier transform infrared spectrophotometer FT-IR) of the obtained photocurable resin is shown in FIG. 7, and the nuclear magnetic resonance spectrum (solvent CDCl ₃ , reference material TMS (tetramethylsilane )) are shown in Figure 8.

Resin Synthesis Example 5

Add 30.8 g of diethylene glycol monoethyl ether acetate and 187 g (1.0 mol), 90% lactic acid (manufactured by Musashino Chemical Research Institute, Musashino lactic acid 90F, purity 90%) 100g (1.0 mol as lactic acid), di-tert-butylhydroxytoluene 1.39g and hydroquinone 0.14g, Heat to 90°C to make it dissolve evenly. Next, 0.97 g of triphenylphosphine was added, and the temperature was raised to 110° C. while blowing in nitrogen gas, and the reaction was carried out for 11 hours while removing the contained water to the outside of the system. Next, after replacing the inside of the system with an air atmosphere, 91.2 g of diethylene glycol monoethyl ether acetate and 2-acryloyloxyethyl isocyanate (manufactured by Showa Denko Co., Ltd., KARENZ AOI, Molecular weight 141) 141 g (1.0 mol), reacted at 85° C. for 3 hours, and confirmed the disappearance of the peak (2270 cm ⁻¹ ) of the isocyanate group in the solution by an infrared spectrophotometer. Furthermore, 69.9 g (0.46 mol) of tetrahydrophthalic anhydrides were added, and it was made to react at 115 degreeC for 4 hours, and obtained the resin solution of solid content acid value 57.2 mgKOH/g, and solid content 80.0%. The double bond equivalent of the solid content was 488, and the lactic acid content was 18%. This was used as resin varnish 5 . In addition, the infrared absorption spectrum (measured using a Fourier transform infrared spectrophotometer FT-IR) of the obtained photocurable resin is shown in FIG. 9 , and the nuclear magnetic resonance spectrum (solvent CDCl ₃ , reference material TMS (tetramethylsilane )) are shown in Figure 10.

Resin Varnish 6

Carboxyl group-containing modified cresol novolak type epoxy acrylate (DICLITE UE-9210, solid content acid value 82.9 mgKOH/g, solid content 62%, solid content double bond equivalent 361) manufactured by DIC Co., Ltd. was used.

Examples 1-5 and Comparative Examples 1-3

Each component shown in Table 1 was mixed in the ratio shown in Table 1, stirred and dissolved, and a photocurable resin composition was obtained. As a brief test, the photocurable resin composition was coated on a PET film using an applicator. About Examples 1-5 and the comparative example 1, it dried at 80 degreeC for 20 minutes after coating. After coating, make the PET film and the photocurable resin composition close, and use a metal halide lamp to irradiate UV with a cumulative light intensity of 1000mJ/ ^cm2 , thereby curing the composition to obtain a target film thickness of about 15 to 20μm cured coating film.

[Table 1]

State of cured coating film:

In order to confirm the state of the obtained cured product, the cured coating film after UV irradiation was torn off from the PET film, and the softness and cracking easiness were evaluated. The case where a soft film was obtained without cracking after UV irradiation was rated as ◯, and the case where cracking was evident was rated as x.

Friction test:

In order to test the curability of the cured product, a rubbing test was performed in which the cured product was rubbed 50 times with an acetone-containing waste cloth. Those that did not dissolve on the surface were judged to be sufficiently cured and rated as ◯; those that were slightly dissolved on the surface were rated as x.

Heat resistance test:

Each cured coating film was put into a 200 degreeC hot-air circulation type drying oven, and it heated for 3 minutes. After heating, it was taken out, and the trace of melting was observed visually, and the heat resistance test was performed. The case where melting was not observed at all and a change was evaluated as ◯, and the case where partial melting was confirmed and a change was evaluated as x.

Table 2 summarizes the results of the above tests.

[Table 2]

As can be seen from the results shown in Table 2 above, the cured product obtained by curing the photocurable resin composition of the present invention has the same properties as the cured product from the state of the cured coating film, the results of the friction test, and the heat resistance test. Curability and heat resistance equivalent to ester acrylate and epoxy acrylate. Furthermore, since lactic acid is used as a raw material, an environmentally friendly photocurable resin composition can be provided by increasing the ratio of carbon derived from nature.

Embodiment 6～12 and comparative example 4,5

Using the above-mentioned resin varnishes 1 to 6, it was blended in the ratio shown in Table 3, premixed with a mixer, and then kneaded with a three-roll mill to prepare an alkali-developing photosensitive resin composition.

[table 3]

Performance evaluation:

<best exposure>

The photosensitive resin compositions of Examples 6-12 and Comparative Examples 4 and 5 above were coated on a glass substrate by screen printing method, and dried in a hot air circulation drying oven at 80° C. for 30 minutes. After drying, use an exposure device equipped with a high-pressure mercury lamp, expose through a Step Tablet (Kodak No. 2), and develop for 60 seconds (30°C, 0.2MPa, 1wt% sodium carbonate aqueous solution), The optimal exposure was determined at the moment when the pattern of the remaining step exposure meter was 7 segments.

<Development>

The photosensitive resin compositions of Examples 6 to 12 and Comparative Examples 4 and 5 above were applied to a glass substrate by screen printing so that the film thickness became about 25 μm, and dried in a hot air circulation drying oven at 80°C. 30 minutes. After drying, development was performed with a 1 wt % sodium carbonate aqueous solution, and the time until the dry coating film was removed was measured with a stopwatch.

Characteristic test:

The photosensitive resin composition of the said Example and the comparative example was apply|coated on the glass substrate by the screen printing method so that the film thickness may become about 20 micrometers, and it dried for 60 minutes in the hot-air circulation type drying oven of 80 degreeC. After drying, exposure was carried out at an optimal exposure amount, and a 1 wt% sodium carbonate aqueous solution at 30° C. was developed for 60 seconds under the condition of a spray pressure of 0.2 MPa to obtain a photosensitive pattern. Thereafter, it was heated at 150° C. for 60 minutes to be cured. The following property evaluations were performed on the obtained cured coating film.

<Adhesion>

Using the conventional method, cross-cut the cured coating film present on the glass substrate produced by the above method to make it into a checkerboard pattern, then perform a peel test using a cellophane adhesive tape, and then perform the peel test according to the following criteria. The number of residuals of the checkerboard is evaluated.

○: The number of remaining grids is between 70 and 100

△: The number of remaining checkerboard grids is more than 30 and less than 70

×: The number of remaining checkerboard grids is 0 or more and less than 30

<flexibility>

The cured coating film of about 40 μm formed on PET by the above method instead of glass was peeled off, and the softness and brittleness were evaluated. Among the obtained cured films, those having flexibility were evaluated as ◯, and those which were hard, brittle, and not flexible were evaluated as ×.

Table 4 summarizes the results of the above tests.

[Table 4]

As is clear from the results shown in Table 4 above, the cured product obtained by curing the photocurable resin composition of the present invention has characteristics superior to conventional polyester acrylates and epoxy acrylates. In addition, it was also surprisingly found that the resin into which the lactic acid skeleton was introduced did not significantly deteriorate in developability compared with Comparative Examples 4 and 5. This is considered to be due to the increase in hydrophilicity due to the introduction of the lactic acid skeleton. Furthermore, it turned out that the cured coating film which has excellent photoreactivity, adhesiveness, and flexibility can be obtained. Furthermore, depending on the molecular design, the content of lactic acid can be greatly increased, and an environmentally friendly photocurable resin can be obtained.

Industrial availability

The photocurable resin of the present invention and the photocurable resin composition containing it can be used in various adhesives, printing inks, and coating agents, and can be used advantageously as photoresists and circuits for printed boards. Formation resists, plating resists, and solder resists. In addition, it can also be used in color filters, black matrices, overcoating agents, etc. for flat panel displays.

Claims (11)

1. light-cured resin, it is characterized in that, be make epoxy compounds (a) and lactic acid or poly(lactic acid) (b) and have acidic group or (methyl) acrylic monomer (c) of isocyanate group as necessary monomer component reaction gained, and the molecular structure with following general formula (I) expression

[Chemical formula 1]

In formula, Ac represents (methyl) acryloxy, R ¹Expression contains the residue by this compound (a) of the formed ethylidene of epoxy ring-opening of epoxy compounds (a), R ²Expression contains the connecting portion of carbonyl oxygen base or amino-formate bond, and n represents 1～99 integer, and m represents 0 or 1.

2. light-cured resin according to claim 1, is characterized in that, described light-cured resin with the structure position of following general formula (II) expression as necessary repeating unit,

[Chemical formula 2]

In formula, Ac represents (methyl) acryloxy, R ²Expression contains the connecting portion of carbonyl oxygen base or amino-formate bond, and fc represents hydroxyl or (methyl) acryloxy, R ³Be the alkyl of carbonatoms 1～10, n is 1～99 integer, and m is 0 or 1, and dotted line part represents the key with other structural unit.

3. light-cured resin according to claim 1, is characterized in that, described R ²The connecting portion with carbonyl oxygen base or amino-formate bond of expression is the group that following general formula a1, a2 or a3 represent,

[chemical formula 3]

Above-mentioned various in, R ⁴The alkylidene group of expression carbonatoms 1～10, R ⁵The alkyl of expression carbonatoms 1～20, R ⁶The alkylidene group of expression carbonatoms 1～30, R ⁷The alkylidene group of expression carbonatoms 1～10.

4. light-cured resin according to claim 1, is characterized in that, described light-cured resin is with respect to final epoxy group(ing) 1 equivalent, has (methyl) acryloxy of 0.1～2.0 equivalent.

5. light-cured resin according to claim 1, it is characterized in that, the epoxy resin (a') of described epoxy compounds (a) for have two above epoxy group(ing) in a part, (methyl) acrylic monomer (c) with acidic group or isocyanate group is (methyl) vinylformic acid, and, described light-cured resin has make (methyl) vinylformic acid with as the hydroxy-containing resin reaction of the reaction product of described epoxy resin (a') and lactic acid and must molecular structure.

6. light-cured resin according to claim 1, it is characterized in that, the epoxy resin (a') of described epoxy compounds (a) for have two above epoxy group(ing) in a part, (methyl) acrylic monomer (c) with acidic group or isocyanate group is (methyl) acryl alkyl isocyanate, and, described light-cured resin has make (methyl) acryl alkyl isocyanate with as the hydroxy-containing resin reaction of the reaction product of described epoxy resin (a') and lactic acid or poly(lactic acid) (b) and must structure.

7. light-cured resin according to claim 1, it is characterized in that, the epoxy resin (a') of described epoxy compounds (a) for have two above epoxy group(ing) in a part, and, described light-cured resin has the following molecular structure that obtains, that is, make acid anhydrides or polyisocyanate compound and hydroxyl (methyl) acrylate monomer reactant with as the hydroxy-containing resin reaction of the reaction product of described epoxy resin (a') and lactic acid or poly(lactic acid) (b) and must molecular structure.

8. one kind contains the carboxyl light-cured resin, and acid anhydrides (d) is formed with light-cured resin reaction claimed in claim 1.

9. light-cured resin constituent, it is characterized in that, contain select the described light-cured resin of any one (A) in free claim 1～7 and claimed in claim 8 contain at least a light-cured resin in the group that carboxyl light-cured resin (A') consists of, and Photoepolymerizationinitiater initiater (B) as essential component.

10. light-cured resin constituent according to claim 9, is characterized in that, also contains described in addition other of carboxyl light-cured resin (A') that contain and contain carboxy resin (C).

11. according to claim 9 or 10 described light-cured resin constituents is characterized in that, also contain Thermocurable composition (D).

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