JP2000344889A - Method for producing imide (amide) resin and energy ray-curable resin composition using the resin - Google Patents

Abstract

(57) [Summary] [PROBLEMS] To improve the heat resistance of a resin, improve the curability by an active energy ray while being soluble in a solvent,
Provided is a novel method for producing an energy ray-curable resin which has patterning property by development with a dilute alkaline aqueous solution and is easy to produce. A polyisocyanate compound having three or more functional aromatic carboxylic acids and / or anhydrides thereof (a) and two or more isocyanate groups in one molecule (b) and one or more polymerizations in one molecule A method for producing an imide (amide) resin (A), comprising reacting a compound (c) having a hydroxyl group and / or an epoxy group with an acidic double bond. About

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel energy ray-curable resin composition and a patterning material. More specifically, an imide group or
An object of the present invention is to provide a method for producing a resin which contains an imide group and an amide group, a carboxyl group and / or an acid anhydride group, and a polymerizable double bond, has excellent heat resistance, and is cured by energy rays.

[0002]

2. Description of the Related Art In recent years, active energy ray-curable resins which are cured by ultraviolet rays or electron beams are preferable from the viewpoint of their curing speed and environmental protection. Therefore, alternatives to conventional thermosetting resins and thermoplastic resins are in progress. . Under these circumstances, in various fields, improvement in heat resistance and electrical properties of the active energy ray-curable resin is required.

At present, active energy ray-curable resins are available in a wide variety of types such as ester acrylate, epoxy acrylate and urethane acrylate, but their performance is limited.

[0004] Conventionally, active energy ray-curable resins to be heat-resistant polymers and resins containing imide groups as resin compositions have been studied. For example, a composition in which a compound containing a dimerizable or polymerizable carbon-carbon double bond, an amino group or a quaternized salt thereof is introduced into a polyamic acid which is a polyimide precursor of the component through actinic radiation via an ionic bond. (JP-B-59-52822), a composition in which a photosensitive group is introduced into a carboxyl group of a polyamic acid by an ester bond (JP-B-55-3020).
No. 7, JP-B-55-41422) A composition in which a methacryloyl group is introduced into a carboxyl group of a polyamic acid through an ester bond or an ionic bond (JP-A-56-38).
038, and JP-B-59-52822).

[0005] These techniques all involve cyclization of an imide precursor to imidization by heat treatment after polymerization or reaction by light in order to form an imide bond. However, such a technique has a problem that a portion of a photosensitive group is separated and volatilizes during imidization, and voids and pinholes, a decrease in film thickness, and a lack of flatness can be obtained. In addition, Japanese Unexamined Patent Publication No.
In JP-A-8-13657 and JP-A-57-133108, a dibasic acid containing an imide group and a dibasic acid having a crosslinkable double bond in a molecule are used in combination, and condensation esterification is performed with a polyol compound. A technique for obtaining a composition containing an unsaturated ester imide having a hydroxyl group at a molecular terminal has been disclosed. However, these methods already have an imide group in the molecule and do not need to perform imide ring closure in a subsequent step, so that the above-described problem can be avoided, but a reactive double bond is formed in the molecular main chain. Therefore, it has poor reactivity with light.Because it originally has an imide bond, it has to use a toxic polar solvent such as N-methylpyrrolidone, and the remaining polyol must be removed. Have problems that must be addressed.

JP-A-54-89623 and JP-A-54-91218 disclose compounds having an amide / imide group and having a reactive double bond in the molecule. Since the reactive double bond is derived from glycidyl cinnamate, there are problems in photoreactivity and solubility as described above, and there are also problems in production, such as complicated purification and reaction during production. are doing. JP-A-5-232701 also discloses a compound having an imide group and having a reactive double bond in the molecule, but also has problems in photoreactivity and solubility, In addition, there is a problem that a Michael addition reaction with a double bond occurs and stability is poor because purification at the time of production and an amine are used as a raw material for generating an imide group.

Japanese Patent Application Laid-Open No. 8-283356 discloses that a resin having an amide / imide group and having 20% or more of cyclohexanedicarboxylic acid in a resin, and further having a reactive double bond in a composition and / or a resin. However, this technique requires the use of a special toxic solvent such as γ-butyrolactone or dimethyl imidazolidine in the synthesis. Further, a method of directly introducing a double bond into the resin skeleton has not been clarified, and the diluent is used in the examples of the above specification. Therefore, the amide imide resin hardly contributes to the curing reaction,
When cured, there is a problem that the properties of the cured product are greatly affected by the properties of the diluent. Also, JP-A-10-246958 discloses a composition containing a carboxylic acid-containing photosensitive polyamide-imide resin,
In this technique, a carboxylic acid in a photosensitive polyamideimide resin having a carboxylic acid is present as a side chain on an amideimide-containing resin via an ester bond. Therefore, a cross-linked product obtained by heat-crosslinking an epoxy resin and a carboxylic acid has a problem that the ester group is easily decomposed and hydrolyzed by heat, alkali, and moisture, dissociated from the resin skeleton, and deteriorated.

[0008]

SUMMARY OF THE INVENTION The present invention improves the heat resistance of an active energy ray-curable resin, is soluble in a solvent, and has improved curability by an active energy ray. An object of the present invention is to provide a novel energy ray-curable resin composition and a patterning material which have patterning properties by development and are easy to produce.

[0009]

The present inventors have made intensive studies in view of the above-described problems of the prior art, and as a result, have found that an amide-imide resin having a reactive group or an imide resin [hereinafter referred to as imide (amide)] A resin having a functional group that reacts with the reactive group and a compound having a (meth) acryloyl group, and found that the curable imide (amide) resin obtained can solve the above-mentioned problems. It has been completed.

That is, [I] The present invention relates to an aromatic carboxylic acid having three or more functional groups and / or its anhydride (a) and a polyisocyanate compound (b) having two or more isocyanate groups in one molecule and one molecule. Compound (c) having at least one polymerizable double bond and a hydroxyl group and / or an epoxy group therein
And [II] the present invention provides an imide (amide) resin (A) according to the above [I].
And an energy-curable resin composition comprising an organic solvent and / or a reactive diluent (B).

[III] The present invention comprises the imide (amide) resin (A) according to the above [I], an organic solvent and / or a reactive diluent (B), and an epoxy resin (C). An energy ray-curable resin composition is provided,
[IV] The present invention provides an energy ray-curable resin composition according to [II] or [III], further comprising a photoinitiator (D). (Amide) The energy ray-curable resin composition according to any one of the above [II] to [IV], wherein the polymerizable double bond (b) in the resin (A) is a (meth) acryloyl group. And

[VI] The present invention further relates to an imide (amide)
The present invention provides the energy ray-curable resin composition according to any one of the above [II] to [V], wherein the acid value of the resin (A) is 10 to 300 KOH mg / g. The weight average molecular weight of the (amide) resin (A) is 5
The present invention provides the energy ray-curable resin composition according to any one of the above [II] to [VI], which is from 00 to 50,000. [VIII] The present invention provides the energy ray curable resin composition according to the above [II] to [VII]. An object of the present invention is to provide a patterning material comprising an energy ray-curable resin composition.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The imide (amide) resin according to the present invention is characterized in that (A) has the same aromatic carboxylic acid and / or the same as the imide bond or imidoamide bond at the molecular terminal and / or the side chain. It is characterized by having a carboxyl group and / or an acid anhydride group derived from an anhydride and a polymerizable double bond. Due to such a structure, it is soluble in a solvent, It has become possible to provide a material which has improved curability and has patterning properties by development with a dilute aqueous alkali solution.

The method for producing the imide (amide) resin (A) of the present invention will be specifically described.

The imide (amide) resin (A) in the present invention comprises at least two aromatic carboxylic acids and / or anhydrides thereof, usually tricarboxylic anhydrides and / or tetracarboxylic anhydrides (a). Reaction of compound (b) having two or more compounds having two or more isocyanate groups with (meth) acrylate (c1) having at least one hydroxyl group or (meth) acrylate (c2) having at least one epoxy group Let me get it.

In this case, a compound having three or more functional aromatic carboxylic acids and / or anhydrides thereof, usually tricarboxylic anhydride and / or tetracarboxylic anhydride (a) and at least two or more isocyanate groups (b) ) And a (meth) acrylate having at least one hydroxyl group (c)
1) or (meth) acrylate (c2) having at least one epoxy group may be simultaneously reacted (method I), or a trifunctional or higher functional aromatic carboxylic acid and / or an anhydride thereof, usually tricarboxylic acid Acid anhydride and / or tetracarboxylic anhydride (a) and at least two or more isocyanate groups

And then reacting with a (meth) acrylate (c1) having at least one hydroxyl group or a (meth) acrylate (c2) having at least one epoxy group. Good (method II). At this time, one or more (meth) acrylates (c1) having at least one hydroxyl group or (meth) acrylates (c2) having at least one epoxy group may be reacted.

Unreacted trifunctional or higher functional aromatic carboxylic acid and / or anhydride thereof, usually tricarboxylic anhydride and / or
Alternatively, the method II is not preferred because the tetracarboxylic anhydride (a) and the compound (b) having at least two or more isocyanate groups do not remain, and the imidamide or imidization reaction can be performed at a high temperature. preferable.

By reacting the aromatic tricarboxylic anhydride and / or the aromatic tetracarboxylic anhydride (a) with the compound (b) having at least two isocyanate groups in the present invention, the amide group is converted to the amide group described above. And a carboxyl group of a tricarboxylic anhydride. Further, the imide group can be formed by a reaction between the above-mentioned isocyanate group and an acid anhydride group of a tricarboxylic anhydride and / or a tetracarboxylic anhydride. In this case, the reaction temperature is from 30 ° C. to 200 ° C., and preferably from 50 ° C. to 160 ° C. from the viewpoint of side reaction and reaction rate.

The synthesis of an imide by the reaction of an acid anhydride and an isocyanate is described in RAMeyers (Journal of polyme
r science Part A-1 Vol. 7, 2757-2762 (1969)) and Reters.
Carleton, et al. (Journal of applied polymer science Vo
l.16, PP.2983-2989 (1972)) and NDGhatge et al. (Journal
of polymer science Polymer Chemistry Edition, Vol.
18,1905-1909 (1980)), while being decarboxylated via a 7-membered ring structure as a reaction intermediate.

In addition, tricarboxylic anhydride and / or
Or when an amide group and / or an imide group is formed in the reaction of the tetracarboxylic anhydride (a) with the compound (b) having at least two isocyanate groups,
During the reaction, isocyanate groups and carboxyl groups and / or
Alternatively, a urethane bond or an ester bond is formed by adding a (meth) acrylate compound (c1) having one or more hydroxyl groups and reacting an isocyanate group or an acid anhydride group with a hydroxyl group in a state containing an acid anhydride group. A compound containing the desired (meth) acrylate group can be obtained. At this time, the carboxyl group and / or
Alternatively, the molar ratio of the acid anhydride group and the isocyanate group is (acid anhydride group + carboxyl group) / (isocyanate group) is 0.
The imidamidation reaction is performed in the range of 6 to 2. In this case, the reaction is performed in the range of 0.6 to 0.9 or 1.1 to 2 in that the unreacted isocyanate group or unreacted tricarboxylic anhydride and / or tetracarboxylic anhydride is not left. preferable.

In the course of the reaction, a urethane bond or an ester bond is formed by reacting an isocyanate group or an acid anhydride group with a hydroxyl group of the (meth) acrylate compound (c1) having at least one hydroxyl group to form a reactive double bond. A bond can be introduced. At this time, the molar number of the hydroxyl group of the (meth) acrylate compound (c1) having at least one hydroxyl group in an amount equal to or more than the equivalent of the isocyanate group or the acid anhydride group remaining during the reaction is added, It is desirable to carry out a urethanation or esterification reaction. During the reaction, an epoxy ester bond is formed by reacting the epoxy group of the (meth) acrylate (c2) having at least one epoxy group with a part of the remaining carboxyl group to introduce a reactive double bond. At this time, the carboxyl group / epoxy group molar ratio is preferably less than 1.

In the above-mentioned design, an acid anhydride group or a monocarboxyl group is present at a molecular terminal of an imidoamide resin or an imide resin. An acid may be generated.

In opening the ring of the acid anhydride group, the ring may be opened with a compound having a hydroxyl group. The compound having a hydroxyl group used at this time is not limited as long as it is a compound having one or more alcoholic hydroxyl groups, and is, for example, a monohydric alcohol such as methanol, ethanol, propyl alcohol, or butyl alcohol, or the above. Polyol raw materials,
(Meth) acrylate having at least one hydroxyl group (c
1) etc. can be used.

Further, it is particularly preferable to use (meth) acrylate (c2) having one or more hydroxyl groups when ring-opening the acid anhydride group, since the curability with active energy rays is improved.

When a raw material having three or more functional groups is used as the polyisocyanate compound, a compound having a branched structure can be synthesized.
The polyisocyanate raw material used at this time is preferably an isocyanurate-type polyisocyanate in terms of solubility and physical properties.

In the reaction, a urethanizing catalyst, an imidizing catalyst, or the like may be used, and an antioxidant, a polymerization inhibitor, or the like may be used.

Further, a part of the carboxyl group and / or the acid anhydride group of the imide (amide) resin (A) is reacted with an epoxy compound having two or more epoxy groups or an epoxy group of an epoxy acrylate having an epoxy group. The molecular weight may be increased, solvent solubility may be imparted, or a polymerizable double bond may be introduced.

Examples of the epoxy compound having two or more epoxy groups include bisphenol A epoxy resin, bisphenol S epoxy resin, bisphenol F epoxy resin, phenol novolak epoxy resin, cresol novolak epoxy resin, and dicyclopentadiene. Epoxy products of various dicyclopentadiene-modified phenol resins obtained by reacting with various phenols, aromatic epoxy resins such as 2,2 ′, 6,6′-tetramethylbiphenol, and aliphatic epoxy resins and alicycles Hetero ring-containing epoxy resins such as formula epoxy resins and triglycidyl isocyanurate.

In the above reaction, the carboxyl group / epoxy group molar ratio is preferably less than 1. More preferably 0.8 or less do not leave unreacted epoxy groups,
It is also preferable to leave an aromatic carboxyl group and / or an acid anhydride group in the resin main chain skeleton. If necessary, a compound having an acid anhydride may be reacted with the generated hydroxyl group to introduce a new carboxyl group to adjust the acid value.

In this case, specific examples of the acid anhydride include, but are not necessarily limited to, the following compounds. Acid anhydrides such as phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, succinic acid and trimellitic acid can be mentioned, and these can be used alone or in combination of two or more.

The tri- or more functional aromatic carboxylic acid and / or its anhydride (a), which are essential raw materials of the present invention, include aromatic tricarboxylic acid, aromatic tetracarboxylic acid and the like, and anhydrides thereof.

As the aromatic tricarboxylic acid and its anhydride, for example, trimellitic acid, naphthalene-1,
Examples include 2,4-tricarboxylic acid and anhydrides thereof. Among these various tricarboxylic anhydrides, trimellitic anhydride can be suitably used in terms of solvent solubility and easy synthesis.

Examples of the aromatic tetracarboxylic acid and its anhydride include pyromellitic acid, benzophenone-3,3 ', 4,4'-tetracarboxylic acid and diphenylether-3,3', 4,4'-tetracarboxylic acid. Carboxylic acid, benzene-1,2,3,4-tetracarboxylic acid, biphenyl-3,3 ', 4,4'-tetracarboxylic acid, biphenyl-2,2', 3,3'-tetracarboxylic acid, naphthalene -2,3,6,7-tetracarboxylic acid, naphthalene-
1,2,4,5-tetracarboxylic acid, naphthalene-1,
4,5,8-tetracarboxylic acid, decahydronaphthalene-1,4,5,8-tetracarboxylic acid, 4,8-dimethyl-1,2,3,5,6,7-hexahi

Dronaphthalene-1,2,5,6-tetracarboxylic acid, 2,6-dichloronaphthalene-1,4,4
5,8-tetracarboxylic acid, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic acid, 2,3
6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic acid, phenanthrene-1,3,9,10-
Tetracarboxylic acid, berylen-3,4,9,10-tetracarboxylic acid, bis (2,3-dicarboxyphenyl)
Methane, bis (3,4-dicarboxyphenyl) methane, 1,1-bis (2,3-dicarboxyphenyl) ethane, 1,1-bis (3,4-dicarboxyphenyl)
Ethane, 2,2-bis (2,3-dicarboxyphenyl) propane, 2,3-bis (3,4-dicarboxyphenyl) propane, bis (3,4-dicarboxyphenyl) sulfone, bis (3 4-dicarboxyphenyl)
Examples include ethers and the like, anhydrides thereof, and compounds obtained by opening one anhydride with a compound having one hydroxyl group in the anhydride group.

[0036]

One or more of these tricarboxylic acids and their anhydrides, tetracarboxylic acids and their anhydrides can be used. In addition, an amide bond or an imide bond may be partially formed by using a pentafunctional or higher functional aromatic base anhydride compound or a bifunctional aromatic dicarboxylic acid compound and its anhydride.

The imide (amide) resin (A) of the present invention comprises
It has a structure in which an imide bond or an imidoamide bond is formed in its molecular main chain, and a carboxyl group and / or an acid anhydride group and a polymerizable double bond are formed at a molecular terminal and / or a side chain. Therefore, it is necessary to use a polyisocyanate compound (b) having two or more isocyanate groups in one molecule as a raw material.

As the polyisocyanate compound (b) having two or more isocyanate groups in one molecule, a compound having two or more isocyanate groups in the molecule can be used. Preferred are bifunctional and trifunctional isocyanate compounds.

Examples of the polyisocyanate compound include o-tolidine diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate Diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethyldiphenyl-4,4'-diisocyanate, 3,3'-
Diethyldiphenyl-4,4'-diisocyanate, m
Aromatic isocyanates such as -xylene diisocyanate, p-xylene diisocyanate, and naphthalene diisocyanate; and isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, norbonulene diisocyanate, lysine diisocyanate, and the like. Examples thereof include aliphatic and alicyclic isocyanates. These can be used alone or in combination of two or more.

Polyisocyanate raw materials such as one or more types of burettes or nullates of such isocyanate monomers can be used, and adducts obtained by a urethanization reaction of the above isocyanate compounds with various polyols can be used. . Among these isocyanate compounds, aliphatic or alicyclic isocyanates are preferable in terms of solubility and reactivity.

As the various polyols used in the above-mentioned adduct, those having two or more functional groups can be used. In this case, the molar ratio of the hydroxyl group of the polyol to the isocyanate group is 1.
It is preferred to carry out with an excess of two or more isocyanates.

Representative examples of such polyol raw materials include ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, 2,2,4-
Trimethyl-1,3-pentanediol, 3-methyl-
1,5-pentanediol, dichloroneopentylglycol, dibromoneopentylglycol, neopentylglycol hydroxypivalate, cyclohexanedimethylol, 1,4-cyclohexanediol, spiroglycol, tricyclodecanedimethylol, hydrogenated bisphenol A, Examples thereof include ethylene oxide-added bisphenol A, propylene oxide-added bisphenol A, dimethylolpropionic acid, and dimethylolbutanoic acid.

As the trifunctional or higher functional polyol compound,
Trimethylolethane, trimethylolpropane, ditrimethylolethane, ditrimethylolpropane, glycerin, diglycerol, 3-methylpentane-1,
3,5-triol, pentaerythritol, dipentaerythritol, tripentaerythritol, 2,2
6,6, -tetramethylolcyclohexanol-1,
Tris 2-hydroxyethyl isocyanurate, mannitol, sorbitol, inositol, glucose and the like can be mentioned. As these trifunctional or higher functional polyol compounds, dipentaerythritol is particularly preferably used.

As the polyol compound mentioned here, polyester polyols, polyether polyols, polycarbonate polyols and the like can be used, and they may be used alone or in combination of two or more. Further, the molecular weight of the polyol compound is not limited, but is preferably 100 or more and 5,000 or less.

Such polyester polyols include:
A polyester polyol obtained by reacting the above-mentioned polyol component with a carboxylic acid-containing compound can also be used. As such a carboxylic acid-containing compound, various commonly used carboxylic acids or acid anhydrides thereof can be used. Among them, maleic acid, fumaric acid, maleic acid, Itaconic acid, citraconic acid, tetrahydrophthalic acid, hetonic acid, hymic acid, chlorendic acid, dimer acid, adipic acid, succinic acid, alkenylsuccinic acid, sebacic acid, azelaic acid, 2,2,4-trimethyladipate, 1,4
-Cyclohexanedicarboxylic acid, terephthalic acid, 2-sodium sulfoterephthalic acid, 2-potassium sulfoterephthalic acid, isophthalic acid, 5-sodium sulfoisophthalic acid, 5-potassium sulfoisophthalate

Di-lower alkyl esters of 5-sodium-sulfoisophthalic acid such as sulfonic acid or dimethyl or diethyl ester, or orthophthalic acid, 4-sulfophthalic acid, 1,10-decamethylenedicarboxylic acid, mucon Acid, oxalic acid, malonic acid, glutanic acid, trimellitic acid, hexahydrophthalic acid, tetrabromophthalic acid, methylcyclohexentricarboxylic acid or pyromellitic acid, or acid anhydrides thereof, or alcohol esters such as methanol and ethanol And a lactone polyol obtained by a ring-opening reaction between ε-caprolactone and the above-mentioned polyol component.

As the polyether polyol, known and commonly used polyether polyols can be used. Among them, only typical ones are exemplified, and polytetramethylene glycol, propylene oxide-modified polytetramethylene glycol, Examples thereof include ether glycols such as ethylene oxide-modified polytetramethylene glycol, polypropylene glycol, and polyethylene glycol, and polyether polyols formed by ring-opening polymerization of a cyclic ether using a tri- or higher functional polyol as an initiator.

As the polycarbonate polyol mentioned here, only typical ones are exemplified. Diphenyl carbonate, bischlorophenyl carbonate, dinaphthyl carbonate, phenyl-toluyl-carbonate, phenyl-chlorophenyl-carbonate or Diaryl- or dialkyl carbonates, such as 2-tolyl-4-tolyl-carbonate or dimethyl carbonate or diethyl carbonate; and the reaction products of various polyols, as listed above, and polycarboxylic acids, as described above. Examples thereof include carbonate derivatives obtained by a reaction with a polyol represented by a transesterification reaction with such a polyester diol.

The imide (amide) resin (A) of the present invention comprises
A polyisocyanate compound (b) having two or more isocyanate groups per molecule in the above-mentioned trifunctional or higher functional aromatic carboxylic acid and / or anhydride thereof, and one or more polymerizable double bonds in one molecule; By reacting with a compound (c) having a hydroxyl group and / or an epoxy group, an imide bond or an imidoamide bond is formed in the molecular main chain, and a carboxyl group and / or an acid anhydride is present at a molecular terminal and / or a side chain. And a polymerizable double bond. 1 for that
It is necessary to use a compound (c) having one or more polymerizable double bonds and a hydroxyl group and / or an epoxy group in a molecule as a raw material.

As the compound (c1) having one or more polymerizable double bonds and a hydroxyl group in one molecule, a compound having one or more polymerizable double bonds and a hydroxyl group in the molecule can be used. , Since the polymerizable double bond is excellent in reactivity,
(Meth) acryloyl groups are preferred.

The compound (c1) having one or more (meth) acryloyl groups and one or more hydroxyl groups in one molecule includes, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2
-Hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, trimethylolpropane di (meth) acrylate Having various hydroxyl groups such as trimethylolethanedi (meth) acrylate, pentaerythritol tri (meth) acrylate or glycidyl (meth) acrylate- (meth) acrylic acid adduct, 2-hydroxy-3-phenoxypropyl (meth) acrylate ( A ring-opening reaction product of a (meth) acrylate compound, the above-mentioned (meth) acrylate compound having a hydroxyl group, and ε-caprolactone is exemplified.

Further, a compound having at least one (meth) acryloyl group and at least one hydroxyl group in one molecule (c
As 1), an epoxy (meth) acrylate obtained by reacting various epoxy compounds with (meth) acrylic acid can also be used. The epoxy ring is opened by the reaction between the epoxy group and (meth) acrylic acid, and at this time, a (meth) acrylic acid ester and a hydroxyl group are generated.

Examples of such epoxy compounds include phenylglycidyl ether, bisphenol A type epoxy resin, bisphenol S type epoxy resin, bisphenol F type epoxy resin, phenol novolak epoxy resin, cresol novolak type epoxy resin, dicyclopentadiene and various phenols. Epoxides of various dicyclopentadiene-modified phenolic resins obtained by the reaction, aromatic epoxy resins such as epoxidized 2,2 ', 6,6'-tetramethylbiphenol, aliphatic epoxy resins and alicyclic epoxy resins, Heterocycle-containing epoxy resins such as triglycidyl isocyanurate are also included.

Specific examples of the compound having a compound (c2) having one or more (meth) acrylate groups and one or more hydroxyl groups in one molecule include the following compounds, but are not necessarily limited thereto. Not something. As the compound (c2) having one or more polymerizable double bonds and an epoxy group in one molecule, a compound having one or more polymerizable double bonds and an epoxy group in a molecule can be used. The polymerizable double bond is preferably a (meth) acryloyl group because of its excellent reactivity.

That is, as the compound (c2) having one or more (meth) acryloyl groups and one or more epoxy groups in one molecule, for example, glycidyl acrylate, glycidyl methacrylate, α-methylglycidyl acrylate, α-methylglycidyl Examples thereof include methacrylate and alicyclic epoxy group-containing (meth) acrylate.

Further, acrylic acid and methacrylic acid are added to the epoxy compound and the epoxy group-containing resin in an amount of 30 mol% to 95 mol%, preferably 3 mol% to the epoxy group in one molecule.
0 mol% to 80 mol%, more preferably 50 mol% to
Compounds and resins to which 80 mol% is added, specifically, glycidyl ether-based epoxy resins, for example, bisphenol A-based epoxy resins obtained by reacting bisphenol A with epichlorohydrin in the presence of an alkali, or condensation reaction of bisphenol A with formalin There is a epoxidized resin obtained by using brominated bisphenol A instead of bisphenol A. In addition, a novolak resin is reacted with epichlorohydrin to form a glycidyl etherified novolak epoxy resin, a phenol novolak type, an orthocresol novolak type, a modification of para-tert-butylphenol, and the like.

Further, a bisphenol F epoxy resin obtained by reacting epichlorohydrin with bisphenol F, a brominated epoxy resin derived from tetrahydrobisphenol A, and the like, and a cyclohexene oxide group, a tricyclodecene oxide group, and a cyclopentene oxide group are further added. Having a cycloaliphatic epoxy resin. Glycidyl ester resins such as diglycidyl phthalate, diglycidyl tetrahydrophthalate, diglycidyl hexahydrophthalate, diglycidyl-p-oxybenzoic acid, glycidyl dimer acid, tetraglycidyl diaminodiphenylmethane, triglycidyl para-aminophenol , Diglycidyl aniline, diglycidyl toluidine, tetraglycidyl meta-xylylenediamine, diglycidyl tribromoaniline,
Examples include glycidylamine-based resins such as tetraglycidylbisaminomethylcyclohexane, hydantoin-type epoxy resins in which the hydantoin ring is glycidylated, and triglycidyl isocyanurate having a triazine ring.
These may be used alone or in combination of two or more. Compounds and resins obtained by adding acrylic acid and methacrylic acid to these compounds and resins are mentioned.

Specific examples of the compound having a compound (c2) having one or more (meth) acrylate groups and one or more epoxy groups in one molecule include the following compounds, but are not necessarily limited thereto. It is not something to be done.
Further, the compound (c1) having one or more (meth) acrylate groups and one or more hydroxyl groups in one molecule described above.
One or two or more compounds (c2) having one or more (meth) acrylate groups and one or more epoxy groups in one molecule can also be used.

In the present invention, the imide (amide) resin (A)
In order to further introduce a polymerizable double bond, a polymerizable double bond may be introduced using an isocyanate compound having a polymerizable double bond.

Examples of the isocyanate compound having a polymerizable double bond include isocyanate ethyl acrylate, isocyanato propyl acrylate, isocyanato butyl acrylate, isocyanato pentyl acrylate, isocyanato hexyl acrylate, isocyanato octyl acrylate, and isocyanato decyl acrylate. , Isocyanato octadecyl acrylate, isocyanato propyl acrylate, isocyanato butyl acrylate, isocyanato pentyl acrylate, isocyanato hexyl acrylate,
Isocyanato octyl acrylate, isocyanato decyl acrylate, isocyanato

Examples of butyl methacrylate, isocyanato propyl acrylate, isocyanato butyl acrylate, isocyanato pentyl methacrylate, isocyanato hexyl methacrylate, isocyanato octyl methacrylate, isocyanato decyl methacrylate, isocyanato octadecyl methacrylate, hydroxyethyl vinyl ether and hydroxybutyl vinyl ether Compounds obtained by the reaction of hydroxyalkyl vinyl ethers having a hydroxyl group and an allyl group or a vinyl ether group with diisocyanate (compounds having a double bond such as a vinyl group other than a (meth) acryloyl group) and the like.

As these isocyanate compounds, compounds having a (meth) acryloyl group as a polymerizable double bond are preferable from the viewpoint of a crosslinking reaction by energy rays.

The compound having at least one polymerizable double bond and an isocyanate group includes a reaction between a compound having at least one (meth) acryloyl group and a hydroxyl group and a polyisocyanate having at least two or more isocyanate groups. Can be used.

By reacting at least one compound having a (meth) acryloyl group and a hydroxyl group with a polyisocyanate having at least two isocyanate groups, a compound having a (meth) acryloyl group and an isocyanate group is synthesized. Reacting a polyisocyanate having at least two isocyanate groups with a tricarboxylic acid anhydride, or reacting a polyisocyanate having at least two or more isocyanate groups with a tricarboxylic acid anhydride, and reacting the remaining isocyanate group with at least one tricarboxylic acid anhydride. When two (meth) acryloyl groups and a compound having a hydroxyl group are reacted, a compound having an imide group and an amide group and a urethane bond in the molecule is generated, which is preferable from the viewpoint of solvent solubility. .

As the compound having at least one (meth) acryloyl group and a hydroxyl group, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxy Butyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, trimethylolpropanedi (meth) acrylate,
Trimethylolethanedi (meth) acrylate, pentaerythritol tri (meth) acrylate or glycidyl (meth) acrylate- (meth) acrylic acid adduct, 2-hydroxy-3-phenoxypropyl (meth)
Examples include (meth) acrylate compounds having various hydroxyl groups such as acrylate, and ring-opening products of the above-mentioned (meth) acrylate compounds having a hydroxyl group and ε-caprolactone.

In the present invention, a compound having two or more primary amino groups can be used in combination with the polyisocyanate compound (b) having two or more isocyanate groups in one molecule.

Specific examples of the compound having two or more primary amino groups include, but are not necessarily limited to, the following compounds.

That is, compounds having two or more primary amino groups include, for example, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylethane, 4,4'-
Diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide, 4,4'-di (methaminophenoxy) diphenylsulfone, 4,4'-di (paraaminophenoxy) diphenylsulfone, orthophenylenediamine, metaphenylenediamine, paraphenylene Diamine, benzidine, 3,3′-diaminobenzophenone, 4,4′-diaminobenzophenone, 4,4′-diaminodiphenyl-2,2-propane, 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 4, 4 '
-Bis (4-aminophenoxy) biphenyl, 2,2 '
-Bis {4- (4-aminophenoxy) phenyl} hexafluoropropane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy)
Benzene, 4,4'-diamino-3,3'-diethyl-
5,5'-dimethyldiphenylmethane, 4,4'-dia

Mino-3,3 ', 5,5'-tetramethyldiphenylmethane, 1,4-diaminotoluene, metaxylylenediamine, 2,2'-dimethylbenzidine,
3,4′-diaminobenzanilide, 4,4′-diaminobenzanilide and the like, and examples of the aliphatic diamine include trimethylenediamine, tetramethylenediamine,
Hexamethylenediamine, 2,11-dodecanediamine, and the like. Silicon-based diamines include bis (paraaminophenoxy) dyltylsilane, 1,4-bis (3-aminopropyldimethylsilyl) benzene, and the like. 1,4-diaminocyclohexene,
Examples of guanamines such as bis (4-aminocyclohexyl) methane and isophoronediamine include acetoguanamine and benzoguanamine. These can be used alone or in combination of two or more.

When a compound having two or more primary amino groups is used in combination, it is necessary to carry out an imidation reaction at a high temperature of 150 ° C. or higher after the amidation reaction, and this Is poor, and a sufficient imide group cannot be generated. Further, since the reaction is a high-temperature reaction, there is a problem that crosslinking occurs when a reactive functional group with a double bond is present in the system, and it is preferable to use a compound having at least two or more isocyanate groups.

The imide (amide) resin (A) of the present invention comprises
As described above, an imide (amide) bond and a carboxyl group derived from the same aromatic carboxylic acid and / or an anhydride thereof involved in the imide bond and the imidoamide bond at the molecular terminal and / or the molecular side chain and / or It is characterized by having an acid anhydride group and a polymerizable double bond.
With such a structure, it is possible to provide a material that is soluble in a solvent, has improved curability by active energy rays, and has patterning properties by development with a dilute aqueous alkaline solution.

The imide (amide) resin of the present invention has an acid value in the range of 10 to 300 KOH mg / g, preferably 20 to 200 KOH mg / g. More preferably, it is caused by a carboxylic acid and / or carboxyl group of a trifunctional or higher functional aromatic carboxylic acid and / or an anhydride residue thereof forming an imide bond or an amide bond in the imide (amide) resin (A). Acid value is 10-200KOHmg
/ G. If the acid value is less than 10, sufficient developability with an aqueous alkali solution cannot be obtained, and a sufficient crosslinked product with an epoxy compound cannot be obtained. On the other hand, if it exceeds 300 KOH mg / g, sufficient water resistance cannot be obtained, and it is difficult to use the imidoamide resin of the present invention.

The imide (amide) resin (A) of the present invention
Has a weight average molecular weight in the range of 500 to 50,000, preferably 1,000 to 20,000. If it is less than 500, sufficient heat resistance cannot be obtained.
If it exceeds 000, it becomes insoluble in a solvent, and it becomes difficult to use it as the imidoamide resin of the present invention.

The energy ray-curable resin composition of the present invention contains the imide (amide) resin (A) and an organic solvent and / or a reactive diluent (B). The organic solvent and / or the reactive diluent (B) can be used as long as it does not contain a hydroxyl group or active protons, and examples thereof include ether solvents, ester solvents, and ketone solvents. Dimethylformamide,
Dimethylacetamide, N-methyl-2-pyrrolidone,
A polar solvent such as dimethyl sulfoxide, sulfolane, and γ-butyrolactone may be used in combination.

As the reactive diluent, a known and commonly used photopolymerizable vinyl monomer can be used. Typical examples thereof include dimethylaminoethyl acrylate, diethylaminoethyl acrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, and triethylene glycol diacrylate. Ethylene glycol diacrylate, polyethylene glycol diacrylate, propylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, diacrylate Pentaerythritol pentaacrylate, dipentaerythritol hexaa Relate, acryloyl morpholine, vinyl pyrrolidone, styrene or, tris (2
-Acryloyloxyethyl) isocyanurate, and alkyl (meth) acrylates such as methyl methacrylate and ethyl acrylate

Or methacrylates of the above acrylates, mono-, di-, tri- or higher polyesters of polybasic acids and hydroxyalkyl (meth) acrylates, bisphenol A epoxy acrylates, novolak epoxys Examples include monomers and oligomers having an ethylenically unsaturated double bond such as acrylate or urethane acrylate. One or two or more of these can be used.

Further, an epoxy compound (C) can be used in combination with this composition. By using together
It reacts with the carboxyl group and / or acid anhydride group of the imide (amide) resin (A) by heat or active energy rays, and also reacts with each other with epoxy groups, and further has high heat resistance, high water resistance and alkali resistance. A cured product having the same can be obtained.

Examples of the epoxy compound (C) include phenylglycidyl ether, bisphenol A epoxy resin, bisphenol S epoxy resin, bisphenol F epoxy resin, phenol novolak epoxy resin, cresol novolak epoxy resin, and dicyclopentadiene. Aromatic epoxy resins such as epoxidized products of various dicyclopentadiene-modified phenol resins obtained by reacting with phenols, epoxidized products of 2,2 ', 6,6'-tetramethylbiphenol, aliphatic epoxy resins and alicyclic resins Heterocycle-containing epoxy resins such as epoxy resins and triglycidyl isocyanurate are also mentioned, and one or more of these can be used.

The amount of the epoxy compound (C) used is usually
The epoxy group is used in an amount of 0.5 to 4 equivalents, preferably 0.7 to 2.0 equivalents, relative to the carboxyl group of the imide (amide) resin (A). When the imidoamide resin and / or the imide resin (A) contains an acid anhydride group, the calculation is performed with one mole of the acid anhydride group as 2 moles of the carboxyl group, and the epoxy compound can be used in the above amount. In order to promote the reaction between the epoxy group and the carboxyl group, a reaction promoting catalyst such as an amino compound, a melamine compound, or a metal salt may be used in combination.

When the energy ray-curable resin composition of the present invention further uses ultraviolet rays as energy rays, it uses a polymerizable photoinitiator (D). The polymerization initiator (D) is not particularly limited, and a known and commonly used polymerizable photoinitiator can be used. Typical examples thereof include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether. Benzoin and benzoin alkyl ethers, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, acetophenones such as 1,1-dichloroacetophenone, 2-methylanthraquinone, 2-ethyl Anthraquinone, 2-tert-butylanthraquinone,
1-chloroant

Anthraquinones such as raquinone and 2-aluminanthraquinone; thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthone; bis (2,6 dimethoxy Benzoyl) -2,4,4-trimethylpentylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, such as trimethylbenzoylalkylphosphine oxides, acetophenone dimethyl ketal, ketals such as benzyldimethyl ketal, benzophenone And benzophenones or xanthones. These can be used alone or in combination of two or more.

The amount of the photopolymerization initiator (D) used is usually 0.1 part by weight based on 100 parts by weight of the imide (amide) resin (A).
The range is from 30 to 30 parts by weight, preferably from 0.5 to 10 parts by weight. Such a photopolymerization initiator can be used in combination with one or more known and commonly used photopolymerization accelerators.

Further, if necessary, other curing agents and heat curing accelerators can be used. Further, additives such as a polymerization inhibitor, a thixotropic agent, an antifoaming agent, a leveling agent, and a coupling agent can also be used.

As a method for curing the imidoamide resin or the imide resin of the present invention, active energy ray curing is desirable, but curing by heat is also possible.

In the case of curing with active energy rays, ultraviolet rays and electron beams can be used. Ultraviolet light, high pressure mercury lamp, low pressure mercury lamp, carbon arc,
Black light lamps, metal halide lamps and the like can be used. As the ultraviolet wavelength, a wavelength of 1900 to 3800 angstroms is mainly used.

When curing with an electron beam is performed, an apparatus having an irradiation source such as various electron beam accelerators can be used, and electrons having an energy of 100 to 1000 KeV are irradiated.

In the case of curing by heat, a catalyst for initiating thermal polymerization or an additive can be used. Of course, there is no limitation on the use of both active energy rays and heat for curing.

The energy ray-curable resin composition of the present invention can be widely used for applications such as coatings and paints, but is particularly preferably used for patterning materials.

When used as a patterning material, for example, the energy ray-curable resin composition of the present invention is applied on a substrate, the solvent is dried, and then energy rays are irradiated through a mask having a pattern. A pattern can be formed by developing with an alkaline aqueous solution or a solvent. Further heat treatment at 80 ° C. or higher can form a tougher pattern.

[0091]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described below based on embodiments. Example 1 In a four-necked flask equipped with a stirrer, a thermometer, and a condenser, 103.5 parts of diethylene glycol monoethyl ether acetate and 222.0 parts of isophorone diisocyanate were placed.
And 192.0 parts of trimellitic anhydride, and the mixture was heated to 120 ° C. while stirring. Vigorous bubbling began around 60 ° C., and the contents of the flask gradually became transparent. The reaction was carried out at 120 ° C for 5 hours, and the NCO% in the system was 9.
It cooled to 40 degreeC at the point which became 0%. Further, diethylene glycol monoethyl ether acetate 166.4
And 1.0 parts of methylhydroquinone, and 234.7 of Aronix M-305 (pentaerythritol triacrylate, manufactured by Toagosei Co., Ltd., hydroxyl value 120).
The temperature was raised to 80 ° C. while paying attention to heat generation. 8

After reacting at 0 ° C. for 9 hours, it was confirmed by infrared absorption spectrum (hereinafter referred to as IR) that the absorption of isocyanate at 2270 cm ⁻¹ had disappeared, and a pale yellow transparent liquid was obtained. The IR of this liquid was measured.
Absorption of an imide group in 0 cm ^-1 and 735cm ^-1, 1660c
absorption of amide group m ^-1 further 1850 cm ^-1, 17
Absorption of the acid anhydride in 80 cm ^-1 and 720 cm ^-1 was confirmed further absorption of carboxyl group at 3390 cm ^-1.
In addition, absorption of an acrylate group was confirmed at 1638 cm ⁻¹ and 810 cm ⁻¹ . Furthermore, it was confirmed from C13-NMR that the acrylate was an imide group-amide group-containing acrylate. In the molecular weight distribution measurement by GPC, the number average molecular weight was 1084 in terms of polystyrene, and the weight average molecular weight was 1,524 in terms of polystyrene. The acid value is 9
It was 5.0 KOH-mg / g (solid content conversion). Hereinafter, this resin solution is referred to as a resin solution A.

Example 2 172.4 parts of diethylene glycol monoethyl ether acetate and isophorone diisocyanate were placed in a four-necked flask equipped with a stirrer, a thermometer and a condenser.
Two parts were charged, and the temperature was raised to 60 ° C. while stirring.
There Aronix M-305 (pentaerythritol triacrylate, manufactured by Toagosei Co., Ltd., hydroxyl value 120) 46
7.5 parts was added dropwise over 1 hour, paying attention to heat generation. The mixture was further reacted at 60 ° C. for 2 hours, and when the NCO% became 4.9%, 192.0 parts of trimellitic anhydride and diethylene glycol monoethyl ether acetate 20 were added.
5.4 parts were added and the temperature was raised to 120 ° C. over 2 hours. 60 ° C
Began foaming violently from around

The contents of the flask gradually became transparent.
After reacting at 120 ° C. for 10 hours, 2270 c
m^-1Confirm that the absorption of isocyanate has disappeared.
A pale yellow transparent liquid was obtained. The IR of this liquid was measured.
1780cm^-1And 735cm^-1Absorption of an imide group,
1660cm^-1The absorption of the amide group further increases 1850c
m^-1, 1780cm^-1And 720cm^-1Absorption of acid anhydride
But another 3380cm ^-1Carboxyl group absorption
It has been certified. Also 1638cm^-1, 810cm^-1Acrylic
The absorption of the rate group was confirmed. Further C13-NMR
Also confirmed to be imide group amide group containing acrylate
Was done. In the molecular weight distribution measurement by GPC,
Equivalent molecular weight is 863 in terms of polystyrene, weight average molecular weight
Was 1040 in terms of polystyrene. The acid value is
It was 146.9 KOH-mg / g (solid content conversion).
Hereinafter, this resin solution is referred to as a resin solution B.

Example 3 A four-necked flask equipped with a stirrer, a thermometer and a condenser was charged with 292.0 parts of diethylene glycol monoethyl ether acetate, 172.8 parts of trimellitic anhydride, and 65.4 parts of pyromellitic anhydride. Charge and add 199.8 parts of isophorone diisocyanate while stirring 13
The temperature was raised to 0 ° C over 4 hours. Vigorous bubbling began around 60 ° C., and the contents of the flask gradually became transparent. 1
After reacting at 30 ° C. for 10 hours and confirming that the absorption of isocyanate at 2270 cm ⁻¹ has disappeared by IR, 8
After cooling to 0 ° C., 116.4 parts of diethylene glycol monoethyl ether acetate, 1.0 part of methylhydroquinone, and Aronix M-

140.3 of 305 (pentaerythritol triacrylate, manufactured by Toagosei Co., Ltd., hydroxyl value 120) was charged, and the temperature was raised to 80 ° C. while stirring. The reaction was carried out at 80 ° C. for 5 hours to obtain a yellow transparent liquid. IR of this liquid
It was measured, the absorption of the imide group in 1785 cm ^-1 and 735cm ^-1, the absorption of amide group 1660 cm ^-1, further 1850 cm ^-1, absorption of acid anhydride to 1780 cm ^-1 and 725 cm ^-1, further 3390cm ^{At -1} , absorption of a carboxyl group was confirmed. 1638 cm ^-1 , 81
Absorption of an acrylate group was confirmed at 0 cm ^-1 . Furthermore, it was confirmed from C13-NMR that the acrylate was an imide group-amide group-containing acrylate. In the molecular weight distribution measurement by GPC, the number average molecular weight was 160 in terms of polystyrene.
0, and the weight average molecular weight was 5,100 in terms of polystyrene. Further, the acid value was 100.9 KOH-mg / g (in terms of solid content). Hereinafter, this resin solution is referred to as a resin solution C.

Example 4 A 4-necked flask equipped with a stirrer, a thermometer and a condenser was charged with 128.8 parts of dimethylformamide and 97.1 parts of 1,3-bis (isocyanatomethyl) cyclohexane.
91.1 parts of trimellitic anhydride was charged, and the temperature was raised to 80 ° C. while stirring. Vigorous bubbling began around 60 ° C., and the contents of the flask gradually became transparent. 80
Reaction at 2 ℃ for 2 hours, then about 1 hour at 120 ℃
Temperature. After reacting at 120 ° C for 10 hours,
When the CO% became 0.6%, it was cooled to 60 ° C. Further, 50.3 parts of dimethylformamide and 0.7 parts of methylhydroquinone were added, and Aronix M-3 was added thereto.
05 (pentaerythritol)

Reacrylate, Toagosei Co., Ltd., hydroxyl value 1
20), and add 25.7 parts, and pay attention to the heat generation at 80 ° C.
The temperature rose. After reacting at 80 ° C for 3 hours, 2270 by IR
It was confirmed that the absorption of isocyanate at cm ^-1 had disappeared, and a yellowish white liquid was obtained. When the IR of this liquid was measured, absorption of an imide group was observed at 1785 cm ^-1 and 735 cm ^-1 .
At 1660 cm ⁻¹ , the absorption of the amide group was further increased by 1780 c.
The absorption of the acid anhydride at m ^-1 and 725 cm ^-1 was further increased by 339.
At 0 cm ^-1 , absorption of a carboxyl group was confirmed. Also,
Absorption of an acrylate group was confirmed at 1638 cm ^-1 and 810 cm ^-1 . Furthermore, it was confirmed from C13-NMR that the acrylate was an imide group-amide group-containing acrylate. Note that G
In the molecular weight distribution measurement by PC, the number average molecular weight was 1600 in terms of polystyrene and the weight average molecular weight was 2100 in terms of polystyrene. The acid value is 40.0 KOH
-mg / g (in terms of solid content). Hereinafter, this resin solution is referred to as a resin solution D.

Example 5 163.2 parts of diethylene glycol monoethyl ether acetate and 111.0 parts of isophorone diisocyanate were placed in a four-necked flask equipped with a stirrer, a thermometer and a condenser.
And 192 parts of trimellitic anhydride, and the mixture was heated to 80 ° C. while stirring. Vigorous bubbling began around 60 ° C., and the contents of the flask gradually became transparent. 80
After reacting at 5 ° C. for 5 hours, the temperature was raised to 130 ° C. Further, the reaction was performed at 120 ° C. for 10 hours, and the IR was 2,270 cm.
^It was confirmed that the absorption of isocyanate- ¹ disappeared. At this time, the acid value was 186.0 KOHmg / g. 134.1 parts of diethylene glycol monoethyl ether acetate and 0.22 parts of methylhydroquinone were added, and the mixture was cooled to 80 ° C., and Aronix M-305 (Toa) was added.

Synthetic product, hydroxyl value 120) 187.0 parts,
0.5 part of triphenylphosphine was charged and reacted at 80 ° C. for 5 hours. By IR, it was confirmed that the absorption of anhydride at 1780 cm ⁻¹ had disappeared, and a brown liquid was obtained. When the IR of this liquid was measured, it was 1785 cm ^-1 and 735 cm ^-1.
absorption of an imide group in cm ^-1, absorption of amide group 1660 cm ^-1, further absorption of carboxyl group at 3390 cm ^-1 was confirmed. In addition, absorption of an acrylate group was confirmed at 1638 cm ⁻¹ and 810 cm ⁻¹ . In the molecular weight distribution measurement by GPC, the number average molecular weight was 710 in terms of polystyrene, and the weight average molecular weight was 98 in terms of polystyrene.
It was 0. The acid value is 126.0 KOH-mg / g.
(In terms of solid content). Hereinafter, this resin solution is referred to as a resin solution E.

Example 6 609.2 parts of the resin solution E obtained in Example 5 was charged into a four-necked flask equipped with a stirrer, a thermometer and a condenser, and the temperature was raised to 110 ° C. while stirring, and diethylene glycol monoethyl was added. Ether acetate 132.5
Part, Epicron 830 [Dainippon Ink Chemical Industry Co., Ltd.
103.2 parts of an epoxy resin having an epoxy equivalent of 172] and 0.4 parts of triphenylphosphine. 1 at 110 ° C
0 hours, epoxy equivalent 12000, acid value 2
A light brown liquid of 6.7 KOH mg / g was obtained. Further, 83.6 parts of tetrahydrophthalic anhydride and 45.0 parts of diethylene glycol monoethyl ether acetate were added, and 1
Reaction at 00 ° C for 5 hours, acid value 84.7KOHmg / g
A light brown liquid (in terms of solid content) was obtained. GPC of this liquid
The number average molecular weight was 3,350 in terms of polystyrene, and the weight average molecular weight was 9,800 in terms of polystyrene. Hereinafter, this resin solution is referred to as a resin solution F.

Example 7 Four-necked flask equipped with a stirrer, a thermometer and a condenser
To diethylene glycol monoethyl ether acetate
195.4 parts and isophorone diisocyanate 111.0
And 114.4 parts of trimellitic anhydride in a nitrogen atmosphere.
The temperature was raised to 80 ° C. while stirring in an atmosphere. With 60 ° C
Vigorous bubbling began in the near future, and the contents of the flask gradually became transparent.
It became clear. After reacting at 80 ° C for 1 hour,
The temperature rose. Further react at 150 ° C for 7 hours to IR
2270cm^-1Isocyanate absorption has disappeared
I confirmed that The acid value at this time was 58.9 KOHmg /
g. Change from nitrogen atmosphere to air atmosphere, methyl
Add 0.22 parts of hydroquinone and cool to 100 ° C
Aronix M-305 (pentaerythritol tote)
Acrylate, Toa Gosei, hydroxyl value 120) 37.
Charge 4 parts and react at 100 ° C for 3 hours.
1780cm^-1Confirm that the absorption of anhydrous acid has disappeared
To give a brown liquid. The IR of this liquid was measured.
1785cm ^-1And 735cm^-1Absorption of an imide group,
1660cm^-1The absorption of the amide group further increases to 3390c.
m^-1In addition, absorption of a carboxyl group was confirmed. Also, 16
38cm^-1, 810cm^-1Acrylate group absorption
It has been certified. In the molecular weight distribution measurement by GPC,
Average molecular weight is 1780 in terms of polystyrene, weight average
The molecular weight was 2050 in terms of polystyrene. Also acid
The value is 100.9 KOH-mg / g (solid content conversion).
Was. Hereinafter, this resin solution is referred to as a resin solution G.

Comparative Example 1 In a flask equipped with a thermometer, a stirrer, and a reflux condenser,
322.2 parts of ethyl carbitol acetate was added, and 963.0 parts of orthocresol novolak type epoxy resin Epicron N-680 (epoxy resin having an epoxy equivalent of 214, manufactured by Dainippon Ink and Chemicals, Inc.) was dissolved.
After adding 1.3 parts of hydroquinone as a thermal polymerization inhibitor,
325.8 parts of acrylic acid and 4.25 parts of N, N-dimethylbenzylamine were added, and while blowing air, 11
The esterification reaction was performed at 5 ° C. The reaction end point has an acid value of 1
The following points were considered. Thereafter, 611.2 parts of ethyl carbitol acetate, tetrahydrophthalic anhydride 44
4.6 parts were added and reacted at 90 ° C. for 5 hours to obtain an acid value of 82.4.
A pale yellow liquid having a KOH mg / g (in terms of solid content) was obtained. In the molecular weight distribution measurement of this liquid by GPC, an acid pendant epoxy acrylate having a number average molecular weight of 3,500 in terms of polystyrene and a weight average molecular weight of 9,800 in terms of polystyrene was synthesized. Hereinafter, this resin solution is referred to as resin solution I.
Abbreviated. Examples 8 to 14, Comparative Example 2 Inks were blended according to Table 1 below and kneaded with a homodisper to prepare inks.

[0104]

[Table 1] Table 1 Ink formulation

*: Bisphenol A type epoxy resin (manufactured by Dainippon Ink and Chemicals, epoxy equivalent: 188) Next, this ink was applied on a tin plate using an applicator 0.254 mil to prepare a test piece.

Application Example 1 (Resolubility Test) The test pieces obtained in Examples 9 to 16 and Comparative Example 2 were left in a dryer at 80 ° C. for 30 minutes to evaporate the solvent.
It was immersed and shaken in a 1% aqueous sodium carbonate solution and a 1% aqueous sodium hydroxide solution for 120 seconds to be redissolved, and the thickness of the coating film was measured. Table 2 shows the obtained test results. The numbers in the table indicate the film-thinning speed, and the larger the number, the better the resolubility.

Application Example 2 (Ultraviolet Curability and Patterning Property) The test pieces obtained in Examples 9 to 16 and Comparative Example 2 were left in a dryer at 80 ° C. for 30 minutes to evaporate the solvent. Step tablet No. on the coating film 2 (manufactured by Kodak Co., Ltd.).
/ Cm ² , 300 mJ / cm ² and then 1%
It was immersed and shaken in an aqueous sodium carbonate solution for 120 seconds and evaluated by the step tablet method. Table 2 shows the obtained test results.
Shown in The numbers in the table indicate the number of steps of the step tablet, and the larger the number, the better the ultraviolet curability and patterning properties.

Application Example 3 (Tg Measurement) The test pipes obtained in Examples 9 to 16 and Comparative Example 2
Solvent in a drying oven at 80 ° C for 30 minutes to evaporate the solvent.
500mJ / cm using an ultra-high pressure mercury lamp ^TwoUltraviolet
After irradiating with a ray, place in a dryer at 150 ° C or 170 ° C for 60
After leaving for a minute, a cured coating film was obtained. Using TMA, the resulting coating
Tg. (Glass transition temperature) and linear expansion coefficients α1, α2
Was measured. Table 2 shows the obtained test results. T in the table
g. Indicates that the higher the temperature, the better the heat resistance. Ma
The linear expansion coefficient α1 is determined by Tg. The dimensional stability at the pre-temperature is α
2 is Tg. Shows the dimensional stability of the post-temperature.
It shows that it has excellent thermal dimensional stability.

[0109]

[Table 2] Table 2 Results of application examples 1 and 2

[0110]

[Table 3] Table 3 Results of Application Example 3

[0111]

The energy ray-curable resin composition of the present invention contains an imidoamide resin or an imide resin which is soluble in a solvent, can be developed with a dilute aqueous alkali solution, and has excellent energy ray curability and heat resistance. It is useful for various applications such as resist inks and coatings, and is particularly suitable for patterning materials.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 5/00 C09D 5/00 Z 179/00 179/00 179/08 179/08 ZF term (reference) 4J011 QB17 SA01 SA21 SA31 SA51 SA62 SA64 SA84 UA01 UA03 VA01 WA01 4J027 AD05 4J036 AA01 FB14 JA09 4J038 DB052 DB062 DB072 DB082 DB262 DB272 DB282 DJ021 DJ051 FA012 FA042 FA122 FA152 FA162 FA172 PA04 MA03 PA04 MA03 PA04 PC016 PC135 PC136 QB21 QB26 QB58 RA05 RA34 SA11 SB01 SB02 TA13 TA14 TA21 TA22 TA43 TA44 TB01 TB02 UA041 UA051 UA052 UA121 UA122 UA131 UA132 UA252 UA261 UA262 UA761 UB012 UB122 UB152 UB302 X02A19B12A02B12A02B12A02A ZB03 ZB21

Claims (8)

[Claims] 1. A polyisocyanate compound having three or more functional aromatic carboxylic acids and / or anhydrides thereof (a), a polyisocyanate compound having two or more isocyanate groups in one molecule (b), and one or more aromatic carboxylic acids in one molecule. A method for producing an imide (amide) resin (A), comprising reacting a polymerizable double bond with a compound (c) having a hydroxyl group and / or an epoxy group. 2. An energy ray-curable resin composition comprising the imide (amide) resin (A) according to claim 1 and an organic solvent and / or a reactive diluent (B). 3. An energy ray-curable resin composition comprising the imide (amide) resin (A) according to claim 1, an organic solvent and / or a reactive diluent (B), and an epoxy resin (C). object. 4. The energy ray-curable resin composition according to claim 2, further comprising a photoinitiator (D). 5. The polymerizable double bond in the imide (amide) resin (A) is a (meth) acryloyl group.
The energy ray-curable resin composition according to any one of the above. 6. An imide (amide) resin (A) having an acid value of 10
The energy ray-curable resin composition according to any one of claims 2 to 5, wherein the amount is from 300 to 300 KOHmg / g. 7. The energy ray-curable resin composition according to claim 2, wherein the imide (amide) resin (A) has a weight average molecular weight of 500 to 50,000. 8. A patterning material comprising the energy ray-curable resin composition according to claim 2.