JP2003195497A - Photocuring composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photocuring composition and an inorganic powder- containing photocuring composition having sufficient photocuring property, giving a pattern of high resolution when a photolithographic method is used, and showing excellent pyrolytic property during calcination. <P>SOLUTION: The photocuring composition comprises a compound (A1) having a group having a (meth)acryloyl group and a photopolymerization initiator (B). The group having a (meth)acryloyl group is expressed by general formula (1) and/or general formula (2). In formula (1), R<SP>1</SP>represents a hydrogen atom or a methyl group, R<SP>2</SP>represents an organic residue and R<SP>3</SP>represents a hydrogen atom or an organic residue. In formula (2), R<SP>4</SP>represents a hydrogen atom or a methyl group, R<SP>5</SP>represents an organic residue and R<SP>6</SP>represents a hydrogen atom or an organic residue. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a photocurable composition. Specifically, the photocurable composition obtained by photocuring has a heat-decomposable property, and the inorganic component containing a photocurable inorganic powder-containing cured product has a heat-decomposable inorganic property. It relates to a powder-containing photocurable composition.

[0002]

2. Description of the Related Art A molded article made of an inorganic material and a pattern formed by it are useful in the field of electronic materials and the like. As a method for forming such a molded article or pattern, a metal powder has hitherto been used. Body, metal oxide powder, fluorescent powder, inorganic powder such as glass frit is mixed with a binder resin to prepare a paste-like composition, and a predetermined shape or pattern is formed from this composition, followed by firing. Then, a method of forming the organic substance by thermally decomposing it is known.

In order to obtain a dense pattern, a paste-like composition is prepared by using a photo-curable and developable resin as a binder resin, and a predetermined pattern is formed by a photolithography method. Also known is a method of forming a pattern of an inorganic material by firing and then thermally decomposing the organic material.

As a technique of using a binder resin having photo-curing property, for example, in Japanese Patent Laid-Open No. 2000-298336, (A) inorganic powder, (B) cellulose-based carboxylic acid-modified photosensitive binder resin, and An alkaline developable photosensitive paste composition containing C) a photoreactive monomer and (D) a photopolymerization initiator is disclosed. Further, JP-A-10-306101 discloses a photopolymerizable composition containing (a) a modified cellulose compound, (b) a photopolymerization initiator, (c) an ethylenic compound, and (d) an inorganic and / or metal powder. Resin compositions are disclosed.

However, in these technologies,
In order to completely remove the binder resin by thermal decomposition, it is necessary to perform firing under a fairly high temperature condition for a long time. Moreover, thermal decomposition tends to be incomplete, so that it is possible to heat organic substances by firing. Since organic substances derived from the binder resin are likely to remain in the inorganic molded body and inorganic pattern formed by decomposition, there is room for improvement in this respect. Further, in the pattern formation by the photolithography method, the photocurability of these binder resins is not sufficient and the resolution of the pattern is not sufficient, so there is room for improvement in this respect as well.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances and has a sufficient photo-curing property and a high-resolution pattern can be obtained when a photolithography method is used. Moreover, it is an object of the present invention to provide a photocurable composition and an inorganic powder-containing photocurable composition having excellent thermal decomposability during firing.

[0007]

As a result of various studies on the composition capable of forming a molded article or a pattern made of an inorganic material, the present inventors have found that a photocurable compound containing a photocurable compound and a photopolymerization initiator. Focusing on the fact that the composition is useful because it can form a dense pattern, examples of the compound having photocurability include a (meth) acryloyl group and —O—C.
A compound having a specific group having an acetal group or a hemiacetal ester group represented by HR-O- or -O-CHR-O-CO- has sufficient photocurability due to a (meth) acryloyl group, In addition, -O-CHR-O- or-
O-CHR-O-CO- represents an acetal group or hemiacetal ester group represented by O-CHR-O-CO-. I found it. Further, when a compound having both such a specific group and a carboxyl group is used,
It was also found that when a photolithography method is used, it exhibits excellent performance in alkali developability due to a carboxyl group, and that a high-resolution pattern can be obtained as in the case of using solvent development. I realized that I could solve it. Furthermore, an inorganic powder-containing photocurable composition obtained by mixing such a photocurable composition with an inorganic powder is capable of sufficiently exerting the performance of the photocurable composition to form a molded article or a dense body made of an inorganic material. Since it is possible to form various patterns, it has been found that it can be suitably applied to various uses such as electronic materials, and the present invention has been achieved.

That is, the present invention is a photocurable composition containing a compound (A1) having a group having a (meth) acryloyl group and a photopolymerization initiator (B), which has the above-mentioned (meth) acryloyl group. The group is represented by the following general formula (1);

[0009]

[Chemical 6]

(Wherein R ¹ represents a hydrogen atom or a methyl group, R ² represents an organic residue, R ³ represents a hydrogen atom or an organic residue) and / or the following general formula ( 2);

[0011]

[Chemical 7]

(Wherein R ⁴ represents a hydrogen atom or a methyl group, R ⁵ represents an organic residue, and R ⁶ represents a hydrogen atom or an organic residue). It is a composition.

The present invention also provides a compound (A2) having both a group having a (meth) acryloyl group and a carboxyl group.
And a photopolymerization initiator (B), which is a photocurable composition, and the group having the (meth) acryloyl group is represented by the general formula (1) and / or the general formula (2). It is also a photocurable composition.

The present invention also provides an inorganic powder-containing photocurable composition obtained by mixing the above photocurable composition with an inorganic powder (C). The present invention is described in detail below.

The photocurable composition of the present invention comprises a compound (A1) having a group having a (meth) acryloyl group and / or a compound (A2) having a group having a (meth) acryloyl group and a carboxyl group, It also contains a photopolymerization initiator (B). The group having the (meth) acryloyl group is represented by the general formula (1) and / or the general formula (2). In these groups,
(Meth) acryloyl group and ^{_{-O-CH (CH 2 R 3}} ) -O
- or it will have a ^{_{-O-CH (CH 2 R 6}} ) acetal or hemiacetal ester group represented by -O-CO-.

In the above general formulas (1) and (2), the organic residue represented by R ² and R ⁵ is, for example,
A linear, branched or cyclic alkylene group having 2 to 18 carbon atoms, an alkoxyalkylene group having 2 to 20 carbon atoms, a halogenated (eg chlorinated, brominated or fluorinated) alkylene group having 2 to 8 carbon atoms, Examples thereof include a polyethylene glycol skeleton excluding terminal hydroxyl groups, a polypropylene glycol skeleton excluding terminal hydroxyl groups, a polybutylene glycol skeleton excluding terminal hydroxyl groups, and an aryl group. Among these, a polyethylene glycol skeleton having a degree of polymerization of 1 to 10,000, a polypropylene glycol skeleton, a polybutylene glycol skeleton,
An alkyl group having 1 to 4 carbon atoms is preferable. More preferably, a polyethylene glycol skeleton having a degree of polymerization of 1 to 100, a polypropylene glycol skeleton, a polybutylene glycol skeleton, and an alkylene group having 2 carbon atoms (—CH ₂ CH
₂₋ ), an alkylene group having 3 carbon atoms (—CH ₂ CH ₂ CH
_2- ), and more preferably a polyethylene glycol skeleton, a polypropylene glycol skeleton, or a polybutylene glycol skeleton having a degree of polymerization of 1 to 15. In addition, in this specification, an organic residue means the organic group couple | bonded with the basic structure which comprises a group or a compound.

The organic residue represented by R ³ and R ⁶ may be, for example, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms or substituted with 6 to 11 carbon atoms. Examples include good aromatic groups. Among these, carbon number 1
2 alkyl groups are preferred. When one molecule of the above compound has a plurality of groups having a (meth) acryloyl group, the above organic residues may be the same or different.

The group having a (meth) acryloyl group is the compound (a) having both a (meth) acryloyl group and a vinyl ether group, and the compound (b) having a hydroxyl group and / or a carboxyl group. It is preferably a group formed by an addition reaction with a hydroxyl group and / or a carboxyl group. In this case, the compound (A1) having a group having a (meth) acryloyl group and / or the compound (A2) having a group having a (meth) acryloyl group and a carboxyl group in the present invention.
Has a structure in which a group having a (meth) acryloyl group is bonded to an organic residue formed by the compound (b) having a hydroxyl group and / or a carboxyl group.

When the compound (a) having both a (meth) acryloyl group and a vinyl ether group is used for forming the group having a (meth) acryloyl group, the vinyl ether group in the compound (a) and the compound (b) in the compound (b) are used. Since the addition reaction with the hydroxyl group and / or the carboxyl group can be performed under mild conditions, the group having a (meth) acryloyl group can be easily formed without coloring the product. The hydroxyl group and / or the carboxyl group in the compound (b) may be wholly added to the vinyl ether group in the compound (a) or a part thereof may be added. These compounds may be used alone or in combination of two or more.

The above general formula (1) and / or general formula (2)
In the formation of a group having a (meth) acryloyl group represented by, a reaction of the compound (a) having both the (meth) acryloyl group and the vinyl ether group with the compound (b) having the above hydroxyl group and / or carboxyl group The molar ratio may be appropriately set depending on the use of the photocurable composition of the present invention, desired physical properties, and the like. For example, the compound (b)
The compound (a) is preferably 0.02 mol or more per 1 mol of the hydroxyl group and / or the carboxyl group in. It is more preferably at least 0.1 mol, and even more preferably at 0.1.
It is 2 mol or more. Further, it is preferably 10 mol or less. The amount is more preferably 5 mol or less, still more preferably 1.5.
It is less than or equal to mol.

As a method of addition reaction between the compound (a) and the compound (b), for example, as an addition method at the time of addition reaction, they may be charged all at once at the initial stage of the reaction, or either or both of them may be continuously added. Alternatively, it may be intermittently added to the reaction system. The addition reaction is preferably carried out in the presence of a catalyst.

Examples of the compound (a) having both the (meth) acryloyl group and the vinyl ether group are:
The following general formula (3):

[0023]

[Chemical 8]

(In the formula, R⁷Is a hydrogen atom or a methyl group
Represent R⁸Represents an organic residue. R⁹Is a hydrogen atom or
Represents a machine residue. ) (Meth) acrylic acid ester
It is preferable that they are Smell of the above general formula (3)
And R⁸The organic residue represented by²And above
R^FiveIs the same as the organic residue represented by⁹Represented by
As the machine residue, the above R ³And the above R⁶Organic residue represented by
It is the same as the group.

Examples of the (meth) acrylic acid esters represented by the above general formula (3) include the compounds exemplified below. These may be used alone or in combination of two or more. 2-vinyloxyethyl (meth) acrylate, 3-vinyloxypropyl (meth) acrylate,
1-Methyl-2-vinyloxyethyl (meth) acrylate, 2-vinyloxypropyl (meth) acrylate, 4-vinyloxybutyl (meth) acrylate, 1-methyl-3-vinyloxypropyl (meth) acrylate, (meth ) 1-vinyloxymethylpropyl acrylate, 2-methyl-3-vinyloxypropyl (meth) acrylate, (meth)
1,1-dimethyl-2-vinyloxyethyl acrylate,
3-Vinyloxybutyl (meth) acrylate, 1-methyl-2-vinyloxypropyl (meth) acrylate, 2-vinyloxybutyl (meth) acrylate, 4-vinyloxycyclohexyl (meth) acrylate, (meth) acrylic acid 6 -Vinyloxyhexyl, 4-vinyloxymethylcyclohexylmethyl (meth) acrylate, 3-vinyloxymethylcyclohexylmethyl (meth) acrylate, 2-vinyloxymethylcyclohexylmethyl (meth) acrylate, p (meth) acrylate -Vinyloxymethylphenylmethyl, m-vinyloxymethylphenylmethyl (meth) acrylate, o-vinyloxymethylphenylmethyl (meth) acrylate.

2- (vinyloxyethoxy) ethyl (meth) acrylate, 2- (vinyloxyisopropoxy) ethyl (meth) acrylate, 2- (vinyloxyethoxy) propyl (meth) acrylate, (meth) acrylic Acid 2-
(Vinyloxyethoxy) isopropyl, 2- (vinyloxyisopropoxy) propyl (meth) acrylate, 2- (vinyloxyisopropoxy) isopropyl (meth) acrylate, 2- (vinyloxyethoxyethoxy) (meth) acrylate Ethyl, 2- (vinyloxyethoxyisopropoxy) ethyl (meth) acrylate, 2- (vinyloxyisopropoxyethoxy) ethyl (meth) acrylate, 2- (vinyloxyisopropoxyisopropoxy) ethyl (meth) acrylate , (Meth) acrylic acid 2-
(Vinyloxyethoxyethoxy) propyl, 2- (vinyloxyethoxyisopropoxy) propyl (meth) acrylate, 2- (vinyloxyisopropoxyethoxy) propyl (meth) acrylate, 2- (meth) acrylic acid
(Vinyloxyisopropoxyisopropoxy) propyl, 2- (vinyloxyethoxyethoxy) isopropyl (meth) acrylate, 2- (vinyloxyethoxyisopropoxy) isopropyl (meth) acrylate, (meth)
Acrylic acid 2- (vinyloxyisopropoxyethoxy)
Isopropyl, 2- (vinyloxyisopropoxyisopropoxy) isopropyl (meth) acrylate, (meth)
2- (vinyloxyethoxyethoxyethoxy) ethyl acrylate, 2- (vinyloxyethoxyethoxyethoxyethoxy) ethyl (meth) acrylate, 2- (isopropenoxyethoxy) ethyl (meth) acrylate, (meth) acrylic acid 2- (isopropenoxyethoxyethoxy) ethoxy, 2- (isopropenoxyethoxyethoxyethoxy) ethyl (meth) acrylate, 2- (isopropenoxyethoxyethoxyethoxyethoxy) ethyl (meth) acrylate, (meth) acrylic Acid polyethylene glycol monovinyl ether, (meth) acrylic acid polypropylene glycol monovinyl ether.

The compound (b) having a hydroxyl group and / or a carboxyl group may be in the form of a low molecular weight compound, an oligomer or a polymer. For example, the following (1) to (3) are described. And the like.
These may be used alone or in combination of two or more. (1) Compound having a hydroxyl group; methanol,
Monohydric alcohols such as ethanol, propanol, butanol, hexanol, polyethylene glycol monoalkyl ether, polypropylene glycol monoalkyl ether; ethylene glycol, diethylene glycol, 1,3-propanediol, 2-methyl-1,3
-Propanediol, 1,4-butanediol, 1,3
-Butanediol, 2,3-butanediol, dipropylene glycol, 1,5-pentanediol, 1,6-
Hexanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2-ethyl-
1,4-butanediol, 1,7-heptanediol,
1,8-octanediol, 1,9-nonanediol,
1,10-decanediol, 1,4-cyclohexanediol, 1,4-dimethylolcyclohexane, 2,2
-Diethyl-1,3-propanediol, 3-methyl-
1,4-pentanediol, 2,2-diethyl-1,3
-Butanediol, 4,5-nonanediol, triethylene glycol, hydrogenated bisphenol A, alkylene oxide adduct of hydrogenated bisphenol A, alkylene oxide adduct of bisphenol A, polyethylene glycol, polypropylene glycol, trimethylolethane, trimethylol Polyhydric alcohols such as propane, glycerin, polyglycerin, pentaerythritol, dipentaerythritol; saccharides such as sorbitol, xylitol, xylylose, glucose, fructose, and mannitol; unsaturated polyester, saturated polyester, hydroxyl group-containing weights such as epoxy acrylate Condensate; Polymer having hydroxyl group; Cellulose, starch, dextran; Phenol compounds such as phenol, cresol and bisphenol.

(2) Compounds having a carboxyl group; monovalent carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid and glutamic acid; adipic acid, pimelic acid, azelaic acid,
Polybasic carboxylic acids such as sebacic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, hexahydrophthalic acid, dimer acid and butanetetracarboxylic acid; Carboxyl group-containing epoxy acrylate, unsaturated polyester, saturated polyester, etc. Polycondensate; Polymer having carboxyl group; Carboxymethyl cellulose. (3) Compounds having both a hydroxyl group and a carboxyl group; hydroxy acids such as hydroxyacetic acid, lactic acid, glyceric acid, tartaric acid, citric acid and dimethylolpropionic acid; hydroxybenzoic acid, hydroxynaphthoic acid; unsaturated polyesters, saturated polyesters, etc. Polycondensate having a hydroxyl group and a carboxyl group; a polymer having a hydroxyl group and a carboxyl group.

Among the above-mentioned compound (b) having a hydroxyl group and / or a carboxyl group, a compound containing two or more hydroxyl groups and / or carboxyl groups in one molecule, epoxy acrylate, epoxy acrylate having a carboxyl group, unsaturated polyester Preferred are polycondensates containing two or more hydroxyl groups and / or carboxyl groups such as saturated polyesters, and polymers having hydroxyl groups and / or carboxyl groups.

The above-mentioned epoxy acrylate can be obtained by subjecting an epoxy compound having two or more epoxy groups in one molecule to an unsaturated monobasic acid for ring-opening addition reaction. A hydroxyl group is generated by this ring-opening addition.

Examples of the epoxy compound which is a raw material for producing the above-mentioned epoxy acrylate include propylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether and hydrogenated bisphenol A. Diglycidyl ether,
Glycidyl etherification products of polyhydric alcohols such as polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyglycerin polyglycidyl ether; adipic acid diglycidyl ester, Glycidyl ester compound of polycarboxylic acid such as sebacic acid diglycidyl ester, azelaic acid diglycidyl ester, terephthalic acid diglycidyl ester, dimer acid diglycidyl ester; bis (2,
3-epoxycyclopentyl) ether, dicyclopentadiene dioxide, 2,2-bis (3,4-epoxycyclohexyl) propane, 3,4-epoxycyclohexylmethyl- (3,4-epoxy) cyclohexanecarboxylate, 3,4 -Epoxy-6-methylcyclohexylmethyl-4-epoxy-6-methylcyclohexanecarboxylate, bis (3,4-epoxy-6)
Alicyclic epoxy compounds such as -methylcyclohexylmethyl) adipate; and bisphenol type epoxy resins.

It is also possible to use two or more molecules of these epoxy resins, which are chain-extended by reaction with a chain extender such as a polybasic acid, a polyphenol compound, a polyfunctional amino compound or a polyvalent thiol. it can. These may be used alone or in combination of two or more.

Examples of the unsaturated monobasic acid used as a raw material for producing the epoxy acrylate include acrylic acid, methacrylic acid, and derivatives of these carboxylic acids. These may be used alone or in combination of two or more.

As the epoxy acrylate, an epoxy acrylate obtained by partially reacting an alcoholic hydroxyl group contained in the epoxy acrylate with a polyvalent isocyanate compound, or an acid anhydride partially contained in the alcoholic hydroxyl group contained in the epoxy acrylate is used. It is also possible to use an epoxy acrylate having a high molecular weight obtained by reacting a carboxyl group formed by addition of a substance with a polyfunctional epoxy compound.

The unsaturated polyester is a polymer obtained by polycondensing an acid component containing an unsaturated polybasic acid as a main component and a polyhydric alcohol component containing a polyhydric alcohol and / or an epoxy compound as a main component. Is.

The acid component used as a raw material for producing the unsaturated polyester may contain a saturated polybasic acid such as an aliphatic saturated polybasic acid or an aromatic saturated polybasic acid, or an acrylic resin, if necessary. It may contain unsaturated monobasic acids such as acids, methacrylic acid, cinnamic acid, and derivatives of these carboxylic acids, and monobasic acids such as saturated monobasic acids. In addition, the polyhydric alcohol component may contain a monohydric alcohol such as hydroxydicyclopentadiene, benzyl alcohol, and allyl alcohol, if necessary.

As the unsaturated polyester, a (meth) acrylate-modified unsaturated polyester obtained by ring-opening addition of glycidyl (meth) acrylate to a terminal carboxyl group of the unsaturated polyester can be used.

Examples of the unsaturated polybasic acid which is the main component of the above acid component include α, β-unsaturated polybasic acids such as maleic acid, fumaric acid, aconitic acid and itaconic acid; β, such as dihydromuconic acid. γ-unsaturated polybasic acid and the like can be mentioned.
Further, a derivative of an unsaturated polybasic acid can be used instead of the unsaturated polybasic acid. Examples of such derivatives include anhydrides of the unsaturated polybasic acids; halides of the unsaturated polybasic acids; alkyl esters of the unsaturated polybasic acids. These unsaturated polybasic acids and derivatives may be used alone or in combination of two or more.

Examples of the saturated polybasic acid include malonic acid, succinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, hexylsuccinic acid, glutaric acid, and 2-methylglutaric acid. Saturated aliphatic such as 3-methyl glutaric acid, 2,2-dimethyl glutaric acid, 3,3-dimethyl glutaric acid, 3,3-diethyl glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid Polybasic acids; aromatic saturated polybasic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid; het acid, 1,2-tetrahydrophthalic acid, 1,2-hexahydrophthalic acid, 1 , 1-
Cyclobutanedicarboxylic acid, 5-norbornene-2,3
Alicyclic saturated polybasic acids such as dicarboxylic acid and trans-1,4-cyclohexanedicarboxylic acid.
Further, a derivative of a saturated polybasic acid can be used instead of the saturated polybasic acid. Examples of such a derivative include an anhydride of the saturated polybasic acid; a halide of the saturated polybasic acid; an alkyl ester of the saturated polybasic acid. These saturated polybasic acids and derivatives may be used alone or in combination of two or more.

Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,3-butanediol, and 2 , 3-butanediol, dipropylene glycol, 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2-ethyl-1,4- Butanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-
Decanediol, 1,4-cyclohexanediol,
1,4-dimethylolcyclohexane, 2,2-diethyl-1,3-propanediol, 3-methyl-1,4-
Of pentanediol, 2,2-diethyl-1,3-butanediol, 4,5-nonanediol, triethylene glycol, glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, hydrogenated bisphenol A, hydrogenated bisphenol A Examples thereof include alkylene oxide adducts and bisphenol A alkylene oxide adducts. These may be used alone or in combination of two or more.

Examples of the epoxy compound include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, glycidyl acrylate, glycidyl methacrylate, and diglycidyl ether of bisphenol A. These may be used alone or in combination of two or more.

The above saturated polyester can be obtained in exactly the same manner as the above unsaturated polyester except that the unsaturated polybasic acid is not used. The polymer having a hydroxyl group may be obtained, for example, by (1) a method of homopolymerizing or copolymerizing a monomer having a hydroxyl group, and (2) after homopolymerizing or copolymerizing a monomer having a carboxyl group. A method of adding a compound having a glycidyl group to the carboxyl group to form a hydroxyl group, (3) homopolymerizing or copolymerizing a monomer having a glycidyl group, and then adding a compound having a carboxyl group to the glycidyl group. A method of producing a hydroxyl group by an addition reaction, (4) a method of saponifying all or part of a polymer obtained by homopolymerization or copolymerization of a vinyl ester compound such as vinyl acetate,
(5) A method using a polymerization initiator having a hydroxyl group or a chain transfer agent may be mentioned, but the method is not limited to these methods. These methods may be used alone,
It is also possible to use a combination of two or more methods.

As a method for obtaining the above-mentioned polymer having a carboxyl group, for example, (1) a method of homopolymerizing or copolymerizing a monomer having a carboxyl group, and (2) a monomer having an acid anhydride group A method in which a compound having a hydroxyl group is added to the acid anhydride group to form a carboxyl group after homopolymerization or copolymerization, (3) a monomer having a hydroxyl group is homopolymerized or copolymerized, and then the hydroxyl group is formed. Examples of the method include, but are not limited to, a method of adding a compound having an acid anhydride group to produce a carboxyl group and (4) a method of using a polymerization initiator or a chain transfer agent having a carboxyl group. Not something. These methods may be used alone or in combination of two or more.

In order to obtain the above-mentioned polymer containing a hydroxyl group and a carboxyl group, for example, a method of appropriately combining the method for obtaining a polymer having a hydroxyl group with the method for obtaining a polymer having a carboxyl group is used. is there. Examples of the monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, diethylene glycol mono (meth) acrylate, Propylene glycol mono (meth) acrylate,
Allyl alcohol, hydroxyethyl vinyl ether,
Examples thereof include hydroxybutyl vinyl ether, p-hydroxystyrene, butene-2-diol-1,4 and the like.
Examples of the monomer having a carboxyl group include, but are not limited to, acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, and citraconic acid.

Further, examples of the monomer to be copolymerized with the monomer having a hydroxyl group or the monomer having a carboxyl group include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, and (meth) acrylic acid. Propyl, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate,
(Meth) acrylic acid esters such as cyclohexyl (meth) acrylate and glycidyl (meth) acrylate; styrenes such as styrene, p-methylstyrene, α-methylstyrene; vinyl acetate, vinyl propionate, butyric acid Vinyl ester monomers such as vinyl; N
-Vinylacetamide, N-vinylformamide, N-
N-vinyl compounds such as vinylpyrrolidone and N-vinylcaprolactam; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, and butyl vinyl ether; olefins such as ethylene, propylene, and butylene. Combinations of more than one species are possible.

An acid is suitable as a catalyst used in the addition reaction of the compound (a) having both the (meth) acryloyl group and the vinyl ether group with the compound (b) having a hydroxyl group and / or a carboxyl group. As an acid,
For example, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butanoic acid, trichloroacetic acid, dichloroacetic acid, pyruvic acid, glycolic acid; oxalic acid, maleic acid, oxaloacetic acid, malonic acid, fumaric acid, tartaric acid, citric acid And other aliphatic polycarboxylic acids; benzoic acid, terephthalic acid, and other aromatic carboxylic acids; benzenesulfonic acid, p-toluenesulfonic acid, p-toluenesulfonic acid pyridinium salt, p
-Aromatic sulfonic acids such as quinolinium toluenesulfonate or salts thereof; sulfates such as sodium sulfate, potassium sulfate, magnesium sulfate, calcium sulfate, nickel sulfate, copper sulfate, zirconium sulfate; sodium hydrogen sulfate, potassium hydrogen sulfate, etc. Hydrogen sulfate; mineral acids such as sulfuric acid, hydrochloric acid, phosphoric acid, polyphosphoric acid; molybdic acid such as limba,
Heteropolyacids such as phosphorus tungstomolybdic acid and silicate tungstomolybdic acid; acidic zeolite; phenol resin or styrene resin as the base resin, exhibiting any form of gel type, porous type or macroporous type, and sulfone Examples thereof include acidic ion exchange resins having at least one type of ion exchange group selected from the group consisting of acid groups and alkylsulfonic acid groups. These catalysts may be used alone or in combination of two or more. Among these, oxalic acid, maleic acid, potassium hydrogen sulfate and hydrochloric acid are preferable. In the case of other acid catalysts, in addition to acting as a catalyst for addition reaction, it may act as a cationic polymerization initiator of vinyl ether. Therefore, it is necessary to strictly control the temperature, but among them, hydrochloric acid does not act as a cationic polymerization initiator and selectively acts only on the addition reaction, so that the temperature control range is wide and it is very advantageous in manufacturing. Is a particularly preferred catalyst.

The amount of the above catalyst used may be appropriately set depending on the kind and combination of the compound (a) and the compound (b) used in the addition reaction, but the yield, the stability of the butterfly, the productivity and the economy. From the viewpoint of sex, for example, compound (a) 100
It is preferably 0.0005 parts by weight or more with respect to parts by weight.
It is more preferably 0.001 part by weight or more. Also, 1
It is preferably less than or equal to parts by weight. It is more preferably 0.5 part by weight or less.

Further, a photocurable composition containing a compound (A2) having both a group having a (meth) acryloyl group and a carboxyl group and a photopolymerization initiator (B) is also one aspect of the present invention. By having both a group having the above (meth) acryloyl group and a carboxyl group, photocurability and alkali developability sufficient for forming a dense pattern can be exhibited, and excellent photolithographic properties are exhibited, and at the same time excellent at the time of firing. It is possible to exhibit easy thermal decomposition.

As the method for obtaining the compound (A2) having both the group having the (meth) acryloyl group and the carboxyl group, for example, (1) when obtaining the compound (A1) having the group having the (meth) acryloyl group A method of reacting a ratio of the compound (a) and the compound (b) so that a hydroxyl group remains, and ring-opening addition of an acid anhydride to the remaining hydroxyl group to introduce a carboxyl group, (2) a (meth) acryloyl group When obtaining the compound (A1) having a group having the compound (a)
Examples thereof include a method of reacting the ratio of the compound (b) with the compound (b) so that the carboxyl group remains, and leaving the carboxyl group. However, the method is not limited to these methods.

The concentration of the carboxyl group in the compound (A2) having both the group having the (meth) acryloyl group and the carboxyl group is 20 to 200 mgKOH / g as an acid value.
Is preferred, more preferably 30-150 mg
It is in the range of KOH / g. When the acid value is 20 mgKOH / g or less, it is difficult to remove the uncured portion quickly with an alkali developer after light irradiation, and it may be difficult to form a pattern with high reproducibility and high accuracy.
If it is H / g or more, the photo-cured portion is likely to be corroded during alkali development, and similarly, it may be difficult to form a pattern with high reproducibility and high precision.

Examples of the acid anhydride used to introduce a carboxyl group by ring-opening addition to the hydroxyl group contained in the compound (A1) having a group having a (meth) acryloyl group are succinic anhydride and anhydride. Maleic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic acid anhydride, methylnadic acid anhydride, etc. are available, either alone or in combination of two or more. It can be mixed and used.

Further, as a developing solution used for the alkali developing, a metal alkali aqueous solution of sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, sodium silicate, calcium hydroxide, etc .; ammonia aqueous solution; monomethylamine, dimethylamine, trimethylamine An aqueous solution of water-soluble organic amines such as monoethylamine, diethylamine, triethylamine, monopropylamine, dimethylpropylamine, monoethanolamine, diethanolamine, triethanolamine, ethylenediamine, diethylenetriamine, dimethylaminoethylmethacrylate, and polyethyleneimine are preferable. Yes, these 1 type, or 2 or more types can be mixed and used. In particular, a dilute alkaline aqueous solution having a concentration of 1.5% by weight or less is preferably used.

In the photocurable composition of the present invention, a usual photocurable cross-linking agent can be used in combination within the range that the heat-decomposability is not impaired. For example, C ₁ -C ₁₈ alkyl (meth) acrylate, C ₁ -C ₈ alcohol ethylene oxide derivative (meth) acrylate, C ₁ -C ₁₈ (alkyl) phenol ethylene oxide derivative (meth)
Acrylate, diol di (meth) acrylates of C ₂ -C _9, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, bisphenol A ethylene oxide derivative di (meth) acrylate, trimethylolpropane tri (meth) acrylate, There are pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin ethylene oxide derivative tri (meth) acrylate and the like, and these can be used alone or in combination of two or more kinds.

Examples of the photopolymerization initiator (B) in the present invention include 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one and 2-methyl-1- [4. -(Methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-hydroxy-2-methyl-1- Phenylpropan-1-one, 2,4,6-
Trimethylbenzoyldiphenylphosphine oxide,
1- [4- (2-hydroxyethoxy) phenyl] -2
-Hydroxy-2-methyl-1-propan-1-one,
2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 3,3-dimethyl-4-methoxybenzophenone, benzophenone, 1-chloro-4-propoxythioxanthone, 1-
(4-Isopropylphenyl) -2-hydroxy-2-
Methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4-benzoyl-4'-methyldimethylsulfide, 4-dimethylaminobenzoic acid, 4-dimethyl Methyl aminobenzoate, ethyl 4-dimethylaminobenzoate,
Butyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-isoamyl 4-dimethylaminobenzoate, 2,2-diethoxyacetophenone, benzyldimethylketal, benzyl-β-
Methoxyethyl acetal, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, methyl o-benzoylbenzoate, bis (4-dimethylaminophenyl) ketone, 4,4'-bisdiethylaminobenzophenone , 4,4'-dichlorobenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzoin butyl ether,
p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, α, α-dichloro-4-phenoxyacetophenone, pentyl -4-Dimethylaminobenzoate and the like can be mentioned. These may be used alone or 2
You may use together 1 or more types.

The amount of the photopolymerization initiator (B) used is 100% by weight of the photocurable composition of the present invention.
It is preferably 0.1% by weight or more, and 25% by weight or less. If it is less than 0.1% by weight, defective exposure and curing may occur, and if it exceeds 25% by weight, the coating property and the abrasion resistance and chemical resistance of the coating film after exposure and curing may be deteriorated. More preferably, it is 0.5% by weight or more and 15% by weight or less.

The inorganic powder-containing photocurable composition obtained by mixing the photocurable composition of the present invention with the inorganic powder (C) sufficiently exhibits the performance of the photocurable composition of the present invention. Since it is possible to form a molded body or a dense pattern made of an inorganic material, various uses such as electronic materials, for example, partition walls of plasma display panels (PDP), electrodes, resistors, phosphors, color filters, black matrix Etc., LCDs, organic EL devices, printed circuit boards, multi-layer circuit boards, multi-chip modules and L
It can be suitably applied to the production of electrode patterns constituting SI or the like, the production of conductor patterns on a ceramic substrate, and the like. Such an inorganic powder-containing photocurable composition is also one aspect of the present invention.

As the above-mentioned inorganic powder (C), for example, P
bO-SiO _{2 system, PbO-B 2 O 3 -SiO} 2 system, ZnO
-SiO _{2 system, ZnO-B 2 O 3 -SiO} 2 system, BiO-S
Glass frit such as io ₂ -based, BiO-B ₂ O ₃ -SiO ₂ -based lead borosilicate glass, zinc borosilicate glass, bismuth borosilicate glass; cobalt oxide, iron oxide, chromium oxide,
Nickel oxide, copper oxide, manganese oxide, neodymium oxide, vanadium oxide, cerium oxide chip yellow,
Cadmium oxide, alumina, silica, macnesia, spinel, etc. Na, K, Mg, Ca, Ba, Ti, Zr, Al
Oxides such as ZnO: Zn, Zn ₃ (PO ₄ ) ₂ : M
n, Y ₂ SiO ₅ : Ce, CaWO ₄ : Pb, BaMgA
l ₁₄ O ₂₃ : Eu, ZnS: (Ag, Cd), Y ₂ O ₃ : E
u, Y ₂ SiO ₅ : Eu, Y ₃ Al ₅ O ₁₂ : Eu, YB
O ₃ : Eu, (Y, Gd) BO ₃ : Eu, GdBO ₃ : E
u, ScBO ₃ : Eu, LuBO ₃ : Eu, Zn ₂ Si
_{O 4: Mn, BaAl 12 O} 19: Mn, SrAl 13 O 19:
Mn, CaAl ₁₂ O ₁₉ : Mn, YBO ₃ : Tb, BaM
gAl ₁₄ O ₂₃ : Mn, LuBO ₃ : Tb, GdBO ₃ : T
b, ScBO ₃ : Tb, Sr ₆ Si ₃ O ₃ Cl ₄ : Eu, Z
nS: (Cu, Al), ZnS: Ag, Y ₂ O ₂ S: E
u, ZnS: Zn, (Y, Cd) BO ₃ : Eu, BaM
gAl _{1 2} O _23: phosphor powder such as Eu and the like. These may be used alone or in combination of two or more. When the inorganic powder-containing photocurable composition of the present invention is used for forming a conductive pattern or the like, by adding conductive particles such as iron, nickel, copper, aluminum, silver and gold, Can be reached.

The amount of the inorganic powder (C) used is preferably 30% by weight or more and 95% by weight or less when the inorganic powder-containing photocurable composition of the present invention is 100% by weight. . If it is less than 30% by weight, problems such as deterioration in coating property and printability and shrinking after firing may occur, and if it exceeds 95% by weight, photocurability may decrease.

The inorganic powder-containing photocurable composition of the present invention can be used, for example, by applying it to the entire surface or a part of the base material, forming a pattern by printing or the like, or molding it into a predetermined shape. After that, it is preferable to obtain a cured pattern and shape by a method of curing by irradiating light such as ultraviolet rays or a photolithography method, and then to bake. By curing and baking the inorganic powder-containing photocurable composition of the present invention, the compound (A1) or the compound (A
Inorganic powder (C)
Since the two are fused to each other, a strong coating film made of an inorganic component such as the inorganic powder (C) or a molded product such as a pattern can be obtained.

Further, the photocurable composition and the inorganic powder-containing photocurable composition of the present invention may use a solvent as exemplified below in order to improve the coating property and the printability. These may be used alone or in combination of two or more. Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol Monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monophenyl ether, diethylene glycol dimethyl ether, die Glycol diethyl ether.

Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl Ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monophenyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2- Butoxy butyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 2-methyl-3-methoxybutyl acetate, 3-
Methyl-3-methoxybutyl acetate, 3-ethyl-
3-methoxybutyl acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate Acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate,
4-Methyl-4-methoxypentyl acetate.

Acetone, methyl ethyl ketone, diethyl ketone, methyl persobutyl ketone, ethyl isobutyl ketone, tetrahydrofuran, cyclohexanone, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, 2-hydroxypropione. Ethyl acid,
2-hydroxy-2-methyl, methyl-3-methoxypropionate, ethyl-3-methoxypropionate,
Ethyl-3-ethoxypropionate, ethyl-3-propoxypropionate, propyl-3-methoxypropionate, isopropyl-3-methoxypropionate, methyl lactate, ethyl lactate, propyl lactate, isopropyl lactate, butyl lactate , Amyl lactate, ethyl ethoxyacetate, ethyl oxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isoamyl acetate,
Methyl carbonate, ethyl carbonate, propyl carbonate, butyl carbonate,
Methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, benzyl methyl ether, benzyl ethyl ether, dihexyl ether, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ−
Butyrolactone, benzene, toluene, xylene, cyclohexanone, methanol, ethanol, propanol, butanol, hexanol, cyclohexanol,
Ethylene glycol, diethylene glycol, glycerin.

The solvent may be used in an amount of 1000 parts by weight or less, preferably 500 parts by weight or less, based on 100 parts by weight of the photocurable composition or the inorganic powder-containing photocurable composition.

In the present invention, a sensitizer, a thermal polymerization inhibitor, a plasticizer, a surfactant, a wetting agent, a defoaming agent, a leveling agent, and other additives may be used, if necessary. These may be used alone or in combination of two or more.

The photocurable composition of the present invention has sufficient photocurability, and when the photolithography method is used,
A high-resolution pattern is obtained, and moreover, it is excellent in thermal decomposability during firing, and the inorganic powder-containing photocurable composition of the present invention is excellent in thermal decomposability of organic components during firing. Since it is possible to obtain an inorganic molded body, an inorganic pattern, or the like in which an organic component remains extremely little, a partition wall, an electrode, a resistor, a phosphor, a color of a plasma display panel (PDP) can be obtained by a printing method, a photolithography method, or the like. Suitable for manufacturing filters, black matrices, LCDs, organic EL devices, printed circuit boards, multi-layer circuit boards, multi-chip modules, LSI, and other electrode patterns, and conductor patterns on ceramic substrates. be able to.

[0066]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "part" is
"Parts by weight" and "%" mean "% by weight".

Synthesis Example 1 In a 1 liter flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen gas introducing tube, 134 g of trimethylolpropane (hydroxyl group = 3 mol) and 2- (vinyloxyethoxy) ethyl methacrylate (hereinafter, Called "VEEM") 600 g (3 mol) was added, stirred and heated to 60 ° C to form a uniform mixture. Subsequently, this was cooled to 25 ° C., and a solution prepared by diluting 0.104 g of hydrochloric acid (35% aqueous solution, 0.01 mol as an HCl component) with 10 g of bis (2-methoxyethyl) ether was slowly added dropwise while paying attention to heat generation. When the exotherm became mild, the temperature was raised to 60 ° C. and the reaction was carried out for 4 hours. When the thus obtained reaction product (1) was analyzed by IR, the peak at around 3500 cm ^-1 due to the hydroxyl group almost disappeared.

Synthesis Example 2 In a 1 liter flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen gas introducing tube, 263 g of fully dehydrated polyglycerin (trade name: polyglycerin # 750, manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.) = About 3.5 mol) and VEEM
Add 700 g (3.5 mol) and stir at 25 ° C.
Hydrochloric acid 1.1 g (35% aqueous solution, 0.0 as HCl component)
11 mol) to bis (2-methoxyethyl) ether 1
The solution diluted with 0 g was slowly added dropwise while paying attention to heat generation. When the exotherm slowed down, the temperature rose to 60 ° C,
The reaction was carried out for 4 hours. When the thus obtained reaction product (2) was analyzed by IR, the peak at around 3500 cm ^-1 due to the hydroxyl group almost disappeared.

Synthesis Example 3 In a 1 liter flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen gas inlet tube, 263 g of fully dehydrated polyglycerin (trade name: polyglycerin # 750, manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.) = About 3.5 mol), VEEM
420 g (2.1 mol) and 141.6 g (0.7 mol) of triethylene glycol divinyl ether were added and stirred, and at 25 ° C., 1.1 g of hydrochloric acid (35% aqueous solution, HC
A solution prepared by diluting 0.011 mol) of the 1 component with 10 g of bis (2-methoxyethyl) ether was slowly added dropwise while paying attention to heat generation. When the exotherm became mild, the temperature was raised to 60 ° C. and the reaction was carried out for 4 hours. When the reaction product (3) thus obtained was analyzed by IR,
The peak near 3500 cm ^-1 due to the hydroxyl group almost disappeared.

Synthesis Example 4 In a 0.5 liter flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen gas inlet tube, 50 g (0.5 mol) of methyl methacrylate and 65.1 g (0. 0.5 mol) and 173.5 g of bis (2-methoxyethyl) ether were added, and the atmosphere was sufficiently replaced with nitrogen, and then the temperature was raised to 70 ° C. Subsequently, 0.61 g of n-dodecyl mercaptan was added, and then 0.58 g of 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved in bis (2-methoxyethyl) ether and the system was added over 1 hour. The mixture was placed in a container and polymerized at 70 ° C. for 5 hours.
4-hydroxy-2,2,6,6-tetramethylpiperidinooxyl (0.17 g) and VEEM (50 g) as an inhibitor are added to 289 g of a mixed solution of the obtained methacrylic polymer and bis (2-methoxyethyl) ether. (0.25m
ol) and stir, and at 25 ° C., hydrochloric acid 0.078 g
(35% aqueous solution, 7.5 × 10 ⁻⁴ mo as HCl component)
A solution obtained by diluting 1) with 10 g of bis (2-methoxyethyl) ether was slowly added dropwise while paying attention to heat generation. When the exotherm became mild, the temperature was raised to 60 ° C. and the reaction was carried out for 6 hours. When the curable resin solution (4) thus obtained was analyzed by IR, it was confirmed that the peak near 3500 cm ⁻¹ due to the hydroxyl group was reduced.

Synthesis Example 5 60 g (0.6 mol) of methyl methacrylate and 28.8 g of methacrylic acid were placed in a 0.5 liter flask equipped with a stirrer, a thermometer, a condenser and a nitrogen gas inlet tube.
(0.4 mol) and 134.1 g of bis (2-methoxyethyl) ether were added, the atmosphere was sufficiently replaced with nitrogen, and the temperature was raised to 70 ° C. Then 0.61 g of n-dodecyl mercaptan
Was added, and then 0.45 g of 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved in bis (2-methoxyethyl) ether and charged into the system over 1 hour.
Polymerization was carried out at 0 ° C. for 5 hours. 4-hydroxy-inhibitor was added to 224 g of a mixed solution of the obtained methacrylic polymer and bis (2-methoxyethyl) ether.
2,2,6,6-tetramethylpiperidinooxyl 0.
13 g and VEEM 40 g (0.2 mol) were added and stirred, and at 25 ° C., 0.063 g of hydrochloric acid (35% aqueous solution, HC
A solution prepared by diluting 6 × 10 ⁻⁴ mol) as the 1-component with 10 g of bis (2-methoxyethyl) ether was slowly added dropwise while paying attention to heat generation. When the exotherm became mild, the temperature was raised to 60 ° C. and the reaction was carried out for 3 hours. The acid value of the curable resin solution (5) thus obtained was measured and found to be 43 mgKOH / g.

Synthesis Example 6 In a 0.5 liter flask equipped with a stirrer, a thermometer, a condenser and a nitrogen gas introducing tube, 339 g of a mixed solution of the polymer synthesized in Synthesis Example 3 and bis (2-methoxyethyl) ether. , Tetrahydrophthalic anhydride 38 g (0.25
mol) and tetraphenylphosphonium bromide 1.5
1 g was added, and an acid anhydride addition reaction to a hydroxyl group was performed at 100 ° C. for 4 hours in a mixed gas atmosphere. The acid value of the curable resin solution (6) thus obtained was 37 m.
It was gKOH / g.

Synthesis Example 7 In a 1 liter flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen gas inlet tube, 263 g of fully dehydrated polyglycerin (trade name: polyglycerin # 750, manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.) = About 3.5 mol) and 2- (vinyloxyethoxy) ethyl acrylate (hereinafter referred to as “VEE
(Hereinafter referred to as "A") 651 g (3.5 mol) was added and stirred, and at 25 ° C., 1.1 g of hydrochloric acid (35% aqueous solution, 0.011 mol as an HCl component) was diluted with 10 g of bis (2-methoxyethyl) ether. The solution was slowly added dropwise while paying attention to the exotherm. Where the fever has eased 6
The temperature was raised to 0 ° C. and the reaction was carried out for 4 hours. When the thus obtained reaction product (7) was analyzed by IR, the peak at around 3500 cm ^-1 due to the hydroxyl group almost disappeared.

Synthesis Example 8 In a 0.5-liter flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen gas introducing tube, 50 g (0.5 mol) of methyl methacrylate and 65.1 g (0. 0.5 mol) and 173.5 g of bis (2-methoxyethyl) ether were added, and the atmosphere was sufficiently replaced with nitrogen, and then the temperature was raised to 70 ° C. Subsequently, 0.61 g of n-dodecyl mercaptan was added, and then 0.58 g of 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved in bis (2-methoxyethyl) ether and the system was added over 1 hour. The mixture was placed in a container and polymerized at 70 ° C. for 5 hours.
To 289 g of the obtained mixed solution of methacrylic polymer and bis (2-methoxyethyl) ether, 0.17 g of 4-hydroxy-2,2,6,6-tetramethylpiperidinooxyl as an inhibitor and VEEA46 0.5 g (0.2
5 mol) and stirred at 25 ° C. with hydrochloric acid 0.078
g (35% aqueous solution, 7.5 × 10 ⁻⁴ m as HCl component)
solution) diluted with 10 g of bis (2-methoxyethyl) ether was slowly added dropwise while paying attention to heat generation.
When the exotherm became mild, the temperature was raised to 60 ° C. and the reaction was carried out for 6 hours. When the curable resin solution thus obtained was analyzed by IR, it was found to be 350
It was confirmed that the peak around 0 cm ^-1 was reduced. 38 g of tetrahydrophthalic anhydride was added to the obtained curable resin solution.
(0.25 mol) and tetraphenylphosphonium bromide (1.50 g) were added, and the mixture was mixed under an atmosphere of 10
The acid anhydride addition reaction to the hydroxyl group was carried out at 0 ° C. for 4 hours. The acid value of the curable resin solution (8) thus obtained was 38 mgKOH / g.

Synthesis Example 9 60 g (0.6 mol) of methyl methacrylate and 28.8 g of methacrylic acid were placed in a 0.5 liter flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen gas inlet tube.
(0.4 mol) and 134.1 g of bis (2-methoxyethyl) ether were added, the atmosphere was sufficiently replaced with nitrogen, and the temperature was raised to 70 ° C. Then 0.61 g of n-dodecyl mercaptan
Was added, and then 0.45 g of 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved in bis (2-methoxyethyl) ether and charged into the system over 1 hour.
Polymerization was carried out at 0 ° C. for 5 hours. 4-hydroxy-inhibitor was added to 224 g of a mixed solution of the obtained methacrylic polymer and bis (2-methoxyethyl) ether.
2,2,6,6-tetramethylpiperidinooxyl 0.
13 g, 1.01 g of tetraphenylphosphonium bromide as an esterification catalyst and glycidyl methacrylate 2
8.4 g (0.2 mol) was added and stirred, and the reaction was carried out at 110 ° C. for 4 hours. The acid value of the curable resin solution (9) thus obtained was measured and found to be 45 mgKOH.
/ G.

Examples 1 to 8 and Comparative Examples 1 to 2 Using each of the obtained reactants and curable resin solutions, photosensitive resin compositions were prepared according to the composition (parts by weight) shown in Table 1,
The thermal decomposition property, solvent developability, and alkali developability were evaluated by the following methods. The results are shown in Table 2.

[0077]

[Table 1]

In Table 1, "TMPTMA" is trimethylolpropane trimethacrylate, and "PMPTMA" is
"MA" is polymethylmethacrylate (number average molecular weight =
35,000, weight average molecular weight = 50,000).

[0079]

[Table 2]

Evaluation method [Thermal decomposability] Component 1 other than the solvent in each photosensitive resin composition
Irgacure 907 which is a photopolymerization initiator for 00 parts
5 parts (manufactured by Ciba Specialty Chemicals) was added and applied on a glass plate to a thickness of 20 to 30 μm, and then dried in a hot air circulation type drying oven at 80 ° C. for 1 hour. Cover it with a transparent film and irradiate it with a light amount of 2000 mJ / cm ² with a 250 W ultra-high pressure mercury lamp.
A cured coating film was obtained. The thermal decomposability of this cured coating is
hermal gravity analysis, M
ac Science, TG-DTA2000). It was heated from 25 ° C. to 500 ° C. at a temperature rising rate of 20 ° C./min in an air atmosphere, and the temperature at which the weight loss rate was 98% was measured.

[Solvent Developability] Each photosensitive resin composition was applied on a copper plate to a thickness of 20 to 30 μm, and then dried in a hot air circulation type drying oven at 80 ° C. for 1 hour to obtain a coating film.
Then, using propylene glycol monomethyl ether acetate, development is carried out at 30 ° C. for 60 seconds, and the remaining coating film is visually evaluated. One that has been completely developed is ◯, one that slightly retains deposits is Δ, Those with a lot of deposits were marked with x.

[Alkali Developability] Each photosensitive resin composition was applied on a copper plate to a thickness of 20 to 30 μm, and then dried in a hot air circulation drying oven at 80 ° C. for 1 hour to obtain a coating film. Then, using 1% Na ₂ CO ₃ aqueous solution, 30
The film was developed at 60 ° C. for 60 seconds, and the remaining coating film was visually evaluated. A sample that was completely developed was evaluated as ◯, a sample with a small amount of adhered substance was evaluated as Δ, and a film with a large amount of adhered substance was evaluated as x.

Examples 9 to 16 A composition prepared according to the composition (parts by weight) shown in Table 3 was kneaded with a three-roll ceramic roll to obtain a photosensitive paste composition. This was applied on a copper plate to a thickness of 20 to 30 μm, and then dried at 80 ° C. for 1 hour in a hot air circulation type drying oven to obtain a coating film. Cover the obtained coating film with a pattern film and use a 250W ultra-high pressure mercury lamp to obtain 2000mJ.
Irradiation with a light amount of / cm ² . Next, each coating film was developed at 30 ° C. for 60 seconds using the developing solution shown in Table 3, and then baked at a baking temperature (600 to 800 ° C.) shown in Table 3 for 10 minutes to obtain a coating film. The line pattern was visually evaluated. In the evaluation, the contrast between the exposed part and the unexposed part is clearly distinguished, and there is no disconnection, short-circuit line, etc., ○, insufficient etching in the exposed part is Δ, etching is not possible, or the whole is dissolved. The thing was marked as x. The results are summarized in Table 3.

[0084]

[Table 3]

In Table 3, "glass frit" is Z
nO · _PbO · _B a 2 O 3 · SiO ₂ based glass frit, "Irgacure 907" is a Ciba Specialty Chemicals Inc. photopolymerization initiator. Also,
"1" in the column of "developer" is a propylene glycol monomethyl ether acetate as a developing solution 1, "2" is a 1% Na ₂ CO ₃ aqueous solution is a developing solution 2.

[0086]

The photocurable composition and the inorganic powder-containing photocurable composition of the present invention have the above-mentioned constitution, have sufficient photocurability, and have a photolithographic method. Has a high-resolution pattern and is excellent in thermal decomposability during firing.

Continued front page    F term (reference) 2H025 AA02 AA17 AB14 AB17 AC01                       AD01 BC14 BC42 BC83 CA00                       CC08 CC09 CC20 FA17                 4J011 PA04 PA07 PA13 PA14 PA15                       PB22 PB27 PC02                 4J027 AC02 AC03 AC04 AC06 AC07                       CA14 CA18 CA19 CA32 CA33                       CA36 CB10 CC04 CC05 CD10                 4J100 AL75P BA02P BA08P BC04P                       BC43P CA01 CA04 JA37                       JA38

Claims (5)

[Claims] 1. A photocurable composition containing a compound (A1) having a group having a (meth) acryloyl group and a photopolymerization initiator (B), wherein the group having a (meth) acryloyl group is: The following general formula (1): (In the formula, R ¹ represents a hydrogen atom or a methyl group. R ² represents
Represents an organic residue. R ³ represents a hydrogen atom or an organic residue. ) And / or the following general formula (2); (In the formula, R ⁴ represents a hydrogen atom or a methyl group. R ⁵ represents
Represents an organic residue. R ⁶ represents a hydrogen atom or an organic residue. ) It represents with these, The photocurable composition characterized by the above-mentioned. 2. A photocurable composition comprising a compound (A2) having both a group having a (meth) acryloyl group and a carboxyl group and a photopolymerization initiator (B), wherein the (meth) acryloyl group is The group having is represented by the following general formula (1): (In the formula, R ¹ represents a hydrogen atom or a methyl group. R ² represents
Represents an organic residue. R ³ represents a hydrogen atom or an organic residue. ) And / or the following general formula (2); (In the formula, R ⁴ represents a hydrogen atom or a methyl group. R ⁵ represents
Represents an organic residue. R ⁶ represents a hydrogen atom or an organic residue. ) It represents with these, The photocurable composition characterized by the above-mentioned. 3. The group having a (meth) acryloyl group is a compound (b) having a vinyl ether group in the compound (a) having both a (meth) acryloyl group and a vinyl ether group, and a hydroxyl group and / or a carboxyl group. The photocurable composition according to claim 1, wherein the photocurable composition is a group formed by an addition reaction with a hydroxyl group and / or a carboxyl group therein. 4. The compound (a) having both a (meth) acryloyl group and a vinyl ether group is represented by the following general formula (3); (In the formula, R ⁷ represents a hydrogen atom or a methyl group. R ⁸ represents
Represents an organic residue. R ⁹ represents a hydrogen atom or an organic residue. 4. A photocurable composition according to claim 1, which is a (meth) acrylic acid ester represented by the formula (4). 5. An inorganic powder-containing photocurable composition, which is obtained by mixing the photocurable composition according to claim 1, 2, 3 or 4 with an inorganic powder (C).