JP2003268124A - Cross-linked molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cross-linked molded article having excellent thermal decomposition properties at baking, and favorably applicable to various uses with its excellent basic properties. <P>SOLUTION: This cross-linked molded article has a cross-linked material having an acetal bond and/or a hemiacetal ester bond, and an inorganic filler as indispensable components. It is preferable that when the weight reduction rate is defined as 100% at a temperature at which the weight change comes to a halt in the thermogravimetric analysis, the temperature at which the weight reduction rate is ≥95%, is ≤480°C. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a crosslinked molded article. More specifically, the present invention relates to a crosslinked molded product that can form a molded product or a pattern with an inorganic component because the organic component has a property of easily thermally decomposing.

[0002]

2. Description of the Related Art A molded article made of an inorganic component 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 has been conventionally used. An inorganic filler such as powder, metal oxide powder, fluorescent powder, or glass frit was mixed with a binder resin to prepare a paste-like composition, and a predetermined shape or pattern was formed from this composition and cured. Then, a method is known in which it is formed by firing and then thermally decomposing the organic component.

Further, 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. There is also known a method of forming a pattern made of an inorganic material by pyrolyzing an organic component by firing after formation.

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 pyrolysis, firing must be carried out for a long time under fairly high temperature conditions. Also, pyrolysis tends to be incomplete, so firing will remove organic components. Since the organic component derived from the binder resin is likely to remain in the inorganic molded body or inorganic pattern formed by thermal 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 is excellent in thermal decomposability during firing.
Moreover, it is an object of the present invention to provide a crosslinked molded article that exhibits excellent basic performance and can be suitably applied to various uses.

[0007]

DISCLOSURE OF THE INVENTION The present inventors have proposed a molded article formed of a composition containing a binder resin,
As a result of various studies on molded articles and patterns capable of forming a pattern with an inorganic component, when a crosslinked molded article which essentially requires a crosslinked article, it exhibits excellent basic performance and can be suitably applied to various applications. I focused on what I could do. In such a crosslinked molded article, if the crosslinked body having an acetal bond and / or a hemiacetal ester bond and an inorganic filler are essential, the acetal bond and / or the hemiacetal ester bond are likely to be thermally decomposed, and the heat during firing is It was found that the decomposability was excellent, and it was conceived that the above problems could be solved satisfactorily. Further, when the weight change rate is 100% when the weight change disappears in thermogravimetric analysis, the weight loss rate of the crosslinked product having an acetal bond and / or hemiacetal ester bond and the crosslinked molded product which essentially requires an inorganic filler is 9%.
When the temperature when it becomes 5% or more is below a specific temperature,
Since organic components are less likely to remain under appropriate firing conditions, the present invention has been found to be suitable for various uses in this respect as well, and the present invention has been achieved.

That is, the present invention relates to an acetal bond and / or
Alternatively, it is a crosslinked product having a hemiacetal ester bond and a crosslinked molded product which essentially requires an inorganic filler. The present invention is described in detail below.

The cross-linked molded article of the present invention essentially comprises (1) a cross-linked article having an acetal bond and / or a hemiacetal ester bond and an inorganic filler, but the preferred embodiment is (2) thermogravimetric analysis. The temperature at which the weight loss rate is 95% or more is 480 ° C. or less when the weight loss rate is 100% when the weight change disappears. The crosslinked molded body of the present invention requires a crosslinked body and an inorganic filler, but by making the inorganic filler essential, it becomes possible to form a molded body or a pattern of an inorganic component. The crosslinked body in such a molded body is
It is preferable that it has a structure formed by a curable composition and has a structure crosslinked by molecular chains, and has a gel fraction of 20% by weight or more when immersed in methylene chloride at 50 ° C. for 3 hours. More preferably, the gel fraction is 50% by weight or more. In the present invention, since the crosslinked molded article has excellent thermal decomposability upon firing, the crosslinked article has a structure crosslinked by a molecular chain having an acetal bond and / or a hemiacetal ester bond. It is preferably one.

In the form (2), thermogravimetric analysis (also referred to as "TG (thermogravimetry)") is carried out by increasing the temperature from 25 ° C to 10 ° C / min in an air atmosphere. In the thermogravimetric analysis, the weight reduction rate at which the weight change disappears is 10
The weight reduction rate when 0% is obtained by subtracting the weight (B) when the weight change disappears from the weight (A) of the sample before heat decomposition, the weight reduction (X ) (Value obtained by subtracting the weight of the sample after heat decomposition from the weight of the sample before heat decomposition) is a value expressed in percentage. That is, {X / (A−B)} × 1
00 will be represented. It is small because the thermal decomposition of the organic component does not proceed in the early stage when the temperature is low, but when the temperature rises to a certain temperature, the thermal decomposition proceeds and rapidly increases, and after the thermal decomposition proceeds, it decreases again. In the crosslinked molded article in the form of the above (2), when the point where the weight change in thermogravimetric analysis disappears is 100% at the stage after the pyrolysis has progressed, that is, when the weight change disappears, the weight decrease occurs. When the rate is 100%, the temperature when the weight reduction rate is 95% or more is 480 ° C or less. If this temperature exceeds 480 ° C., it is necessary to give a large amount of heat energy during firing, and it cannot be suitably applied to various uses. Also, this temperature is 25
If the temperature is 0 ° C. or lower, the organic portion may be decomposed before the inorganic component is baked, and a good molded product or pattern may not be obtained. As a preferable temperature range in which the weight reduction rate is 95%, the lower limit is 250 ° C and the upper limit is 480 ° C.
More preferably, the lower limit is 300 ° C and the upper limit is 450 ° C.

The crosslinked molded article of the present invention is preferably formed of an inorganic filler-containing photocurable composition, and the inorganic filler-containing photocurable composition has the following general formula ( 1) and / or a compound (A1) having a group having a (meth) acryloyl group represented by the following general formula (2) and / or a compound having both a group having a (meth) acryloyl group and a carboxyl group ( A
2), a photopolymerization initiator (B), and an inorganic filler are preferably contained. This makes it possible to obtain a fine inorganic pattern by the photolithography method. In addition, in the group having a (meth) acryloyl group represented by the general formula (1) and / or the general formula (2), a (meth) acryloyl group and -O-CH (CH
₂ R ³⁾ -O- or ^{_{-O-CH (CH 2 R 6}} ) -O-CO-
It has an acetal group and / or a hemiacetal ester bond represented by.

[0012]

[Chemical 1]

In the formula, 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.

[0014]

[Chemical 2]

In the formula, R ⁴ represents a hydrogen atom or a methyl group. R ⁵ represents an organic residue. R ⁶ represents a hydrogen atom or an organic residue.

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
An alkyl group having 2 or an aromatic group having 6 to 8 carbon atoms is preferable. 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 intended use of the crosslinked molded article formed from the inorganic filler-containing photocurable composition, the desired physical properties, and the like. For example, a hydroxyl group and / or a carboxyl group in the compound (b) may be used. The compound (a) is preferably 0.02 mol or more per 1 mol. The amount is more preferably 0.1 mol or more, still more preferably 0.2 mol or more. Further, it is preferably 10 mol or less. It is more preferably 5 mol or less, still more preferably 1.5 mol or less.

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 3]

(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.

The crosslinked product having an acetal bond and / or a hemiacetal ester bond in the present invention has a group having a (meth) acryloyl group represented by the above general formula (1) and / or the above general formula (2). It can be formed by a curable composition containing the compound (A1) and / or the compound (A2) having both a group having the (meth) acryloyl group and a carboxyl group, and a polymerization initiator. Such a curable composition is suitable as a material for forming a crosslinked product in the present invention.

The crosslinked product formed from the photocurable composition containing the compound (A2) having both the (meth) acryloyl group-containing group and the carboxyl group and the photopolymerization initiator (B) is a crosslinked material in the present invention. It is one of the preferred forms of the body. 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.

The compound (A2) having both the (meth) acryloyl group-containing group and the carboxyl group can be obtained by, for example, obtaining (1) the compound (A1) having a (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 carboxyl group concentration in the compound (A2) having both a group having a (meth) acryloyl group and a 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 for forming the crosslinked product in the present invention, a usual photocurable crosslinking agent can be used in combination within the range where the easily thermally decomposable property is not impaired.
For example, a C ₁ -C ₁₈ alkyl (meth) acrylate,
C ₁ alcohol ethylene oxide derivative (meth) acrylate -C _8, C ₁ -C ₁₈ of (alkyl) phenol ethylene oxide derivative (meth) acrylates, C
Of ₂ -C ₉ diol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, bisphenol A
There are ethylene oxide derivative di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin ethylene oxide derivative tri (meth) acrylate, etc. They can be used alone or in combination of two or more.

Examples of the photopolymerization initiator (B) include 1-hydroxycyclohexyl phenyl ketone,
2,2-dimethoxy-1,2-diphenylethane-1-
On, 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′-methyldimethyl sulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate , 4-dimethylaminobenzoic acid-
2-isoamyl, 2,2-diethoxyacetophenone,
Benzyl dimethyl ketal, 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. These may be used alone or in combination of two or more.

The photopolymerization initiator (B) is used in an amount of 0. 0 when the photocurable composition is 100% by weight.
It is preferably 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
It is 15% by weight or less.

The crosslinked product having an acetal bond and / or a hemiacetal ester bond in the present invention is
It can also be obtained by reacting a curable composition containing a polyvalent vinyl ether compound and a polyvalent hydroxyl group-containing compound and / or a polyvalent carboxyl group-containing compound. Examples of the polyvalent vinyl ether compound include butanediol divinyl ether, cyclohexanediol divinyl ether, cyclohexanedimethanol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, ethylene glycol divinyl ether, hexanediol divinyl ether. A divinyl ether compound such as vinyl ether can be used. Further, the addition of a hydroxyl group-containing vinyl ether compound to a polyvalent isocyanate compound or a compound having both the above-mentioned (meth) acryloyl group and vinyl ether group and a vinyl ether group obtained by copolymerizing a radical-polymerizable monomer other than the compound It is also possible to use a polymer having a chain.

As the polyvalent hydroxyl group-containing compound or polyvalent carboxyl group-containing compound, use is made of a bifunctional or higher functional compound among the above-mentioned compound having a hydroxyl group, compound having a carboxyl group, and compound having both a hydroxyl group and a carboxyl group. You can In order to react these compounds and obtain a crosslinked product having an acetal bond and / or a hemiacetal ester compound, the acid catalyst as described above can be used. Further, in order to improve work efficiency, it is preferable to initiate the reaction by heat and / or active energy rays, and for that purpose, it is preferable to use a thermal latent acid generator or a photoacid generator.

As the thermal latent acid generator, sulfonic acid esters and phosphoric acid esters are used. Examples of the sulfonic acid esters include sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, nonylnaphthalenesulfonic acid, n-propanol, n-butanol, and n. -Primary alcohols such as hexanol and n-octanol or isopropanol, 2
-Esterification products with secondary alcohols such as butanol, 2-hexanol, 2 octanol, and cyclohexanol, and β-hydroxyalkyl sulfonic acid esters obtained by reacting the sulfonic acids with the oxirane group-containing compound. To be Examples of the phosphoric acid esters include primary alcohols such as n-propanol, n-butanol, n-hexanol, n-octanol and 2-ethylhexanol, or isopropanol, 2-butanol, 2-hexanol, 2-octanol. , Phosphoric acid monoesters and phosphoric acid diesters of secondary alcohols such as cyclohexanol.

As the above-mentioned photo-acid generator, various cationic polymerization initiators such as diazonium salt, iodonium salt,
Onium salts such as bromonium salts, chloronium salts, sulfonium salts, selenonium salts, pyrylium salts, thiapyrylium salts, pyridinium salts; tris (trihalomethyl)-
Halogenated compounds such as S-triazine and its derivatives;
2-Nitrobenzyl ester of sulfonic acid; iminosulfonate; 1-oxo-2-diazonaphthoquinone-4-
Sulfonate derivatives; N-hydroxyimide = sulfonates; tri (methanesulfonyloxy) benzene derivatives; bissulfonyldiazomethanes; sulfonylcarbonylalkanes; sulfonylcarbonyldiazomethanes; disulfone compounds and the like are used.

These photo-acid generators can be used alone or in combination of two or more kinds. Commercially available products include, for example, C manufactured by Union Carbite Corporation.
YRACURE (registered trademark) UVI-6950, UVI
-6970, Asahi Denka Kogyo Optomer SP-15
0, SP-151, SP-152, SP-170, SP
-171, CI-2855 manufactured by Nippon Soda Co., and Dearylce KI85 B manufactured by Degussa Co., etc., and triarylsulfonium salts, unsubstituted or substituted aryldiazonium salts, and diaryliodonium salts. Also,
As the sulfonic acid derivative, PAI-10 manufactured by Midori Kagaku Co., Ltd.
1 or the like can be used.

The inorganic filler-containing curable composition obtained by mixing the above curable composition with an inorganic filler sufficiently exhibits the performance of the above curable composition to form a molded article or a dense pattern of the inorganic filler. Since it can be formed, it is suitable as a material for forming the crosslinked molded article of the present invention. A crosslinked molded body formed from such a curable composition containing an inorganic filler is one of the preferred embodiments of the present invention.

As the above-mentioned inorganic filler, for example, Pb
O-SiO _{2 system, PbO-B 2 O 3 -SiO} 2 system, ZnO-
SiO _{2 system, ZnO-B 2 O 3 -SiO} 2 system, BiO-Si
Glass frit such as O 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, magnesia, 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 crosslinked molded article of the present invention is used for forming a conductive pattern or the like, the purpose can be achieved by adding conductive particles such as iron, nickel, copper, aluminum, silver and gold.

The amount of the above-mentioned inorganic filler used is 3 when the curable composition containing the inorganic filler is 100% by weight.
It is preferably 0% by weight or more and 95% by weight or less. If it is less than 30% by weight, problems such as deterioration in coating property and printability and shrinkage after firing may occur, and if it exceeds 95% by weight, curability may decrease.

Further, for the above-mentioned inorganic filler-containing curable composition, a solvent as exemplified below may be used in order to improve coatability and printability. These may be used alone,
You may use 2 or more types together. 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 amount of the solvent used may be 1000 parts by weight or less, preferably 500 parts by weight or less, based on 100 parts by weight of the inorganic filler-containing curable composition.

In the present invention, if necessary, 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. These may be used alone or in combination of two or more.

In the crosslinked molded article of the present invention, for example, the above-mentioned inorganic filler-containing curable composition is applied to the entire surface or a part of a substrate, or a pattern is formed by printing, photolithography, etc. After being molded into a predetermined shape, for example, a photocurable composition can be formed by curing by irradiation with light such as ultraviolet rays. By firing the crosslinked molded article of the present invention, the organic components are decomposed and volatilized, and the inorganic fillers are fused to each other, so that a strong coating film by an inorganic component such as an inorganic filler, a molded article such as a pattern, etc. Can be obtained.

The crosslinked molded article of the present invention is excellent in thermal decomposability under appropriate firing conditions, and can form an inorganic molded article or an inorganic pattern having a very small amount of organic components remaining. It is preferable to use it as a disintegrated molded body. Further, in the form formed by the above-mentioned inorganic filler-containing photocurable composition, since it has sufficient photocurability and can obtain a high-resolution pattern when using a photolithography method, printing, photo Manufacturing of plasma display panel (PDP) barrier ribs, electrodes, resistors, phosphors, color filters, black matrices, and LCDs by a lithographic method, etc.
It can be suitably applied to the production of electrode patterns constituting organic EL elements, printed circuit boards, multilayer circuit boards, multichip modules, LSIs, etc., the production of conductor patterns on ceramic substrates, and the like.

[0071]

The present invention will be described in more detail with reference to the following 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 inlet 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, 134 g of trimethylolpropane (hydroxyl group = 3 mol) and 2- (vinyloxyethoxy) ethyl acrylate (hereinafter, (It's called "VEEA")
558 g (3 mol) was added, and the mixture was stirred and heated to 60 ° C. to form a uniform mixed solution. Then cool it to 25 ° C,
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 (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 polyglycerin (trade name: polyglycerin # 750, manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.) which had been sufficiently dehydrated = About 3.5 mol), VEEM
700 g (3.5 mol) was added, and the mixture was stirred and heated to 60 ° C to form a uniform mixed solution. 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 (3) was analyzed by IR, the peak at around 3500 cm ^-1 due to the hydroxyl group almost disappeared.

Synthesis Example 4 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. The obtained methacrylic polymer and bis (2-methoxyethyl) ether were reprecipitated with a large amount of n-hexane, filtered and dried to obtain a reaction product (4).
Got

Synthesis Example 5 4-hydroxy-2,2,6,6-tetra as an inhibitor was added to 223 g of a mixed solution of the methacrylic polymer obtained in Synthesis Example 4 and bis (2-methoxyethyl) ether. Methyl piperidino oxyl 0.13g and VEEM 40g
(0.2 mol) was added and stirred, and hydrochloric acid was added at 25 ° C.
063 g (35% aqueous solution, 6 × 10 ⁻⁴ as HCl component)
mol) to bis (2-methoxyethyl) ether 10 g
The solution diluted with was slowly added dropwise while paying attention to heat generation. When the exotherm slowed down, the temperature was raised to 60 ° C and 3
The reaction was carried out over time. The acid value of the curable resin solution thus obtained was measured and found to be 43 mgKOH / g. After reprecipitation with a large amount of n-hexane, filtration,
The reaction product (5) was obtained by drying.

Synthesis Example 6 In a 0.5 liter flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen gas introduction 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 thus obtained was analyzed by IR, it was found to be 3500 due to the hydroxyl group.
It was confirmed that the peak near cm ^-1 was reduced. Subsequently, 38 g (0.25 mol) of tetrahydrophthalic anhydride and 1.51 g of tetraphenylphosphonium bromide were added, and the acid anhydride addition reaction to the hydroxyl group was carried out at 100 ° C. for 4 hours in a mixed gas atmosphere. The acid value of the curable resin solution thus obtained was 37 kmg KOH / g. Further, this was reprecipitated with a large amount of n-hexane, filtered and dried to obtain a reaction product (6).

Synthesis Example 7 Methyl methacrylate 50 was placed in a 1-liter flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen gas introducing tube.
g (0.5 mol), 65.1 g (0.5 mol) of 2-hydroxyethyl methacrylate 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. Then, after adding 0.61 g of n-dodecyl mercaptan, 2,2'-azobis (2,2'-azobis (2
0.58 g of 4-dimethylvaleronitrile) was added to bis (2-
It was dissolved in methoxyethyl) ether, charged into the system over 1 hour, and polymerized at 70 ° C. for 5 hours to obtain a mixed solution of a methacrylic polymer and bis (2-methoxyethyl) ether. Also, stirrer, thermometer, condenser,
In another 0.5 liter flask equipped with a nitrogen gas introducing tube, 84.1 g of hexamethylene diisocyanate (0.
5 mol), 4-hydroxy-2,2,2 as an inhibitor
6,6-Tetramethylpiperidinooxyl 0.014
g, 71 g of bis (2-methoxyethyl) ether as a solvent, and 0.71 g of dibutyltin dilaurate were added.
The temperature was raised to 0 ° C. Subsequently, 58.1 g (0.5 mol) of 2-hydroxyethyl acrylate was charged into the system over 1 hour, and the reaction was performed over 2 hours. Subsequently, 289 g of a mixed solution of the methacrylic polymer and bis (2-methoxyethyl) ether synthesized above, tetrahydrophthalic anhydride 3
8 g (0.25 mol) and 1.51 g of tetraphenylphosphonium bromide were added, and the acid anhydride addition reaction to the hydroxyl group was carried out at 100 ° C. for 4 hours in a mixed gas atmosphere. The acid value of the curable resin solution thus obtained was 43 mgKOH / g. In addition, a large amount of n-
After reprecipitation with hexane, filtration and drying were performed to obtain a reaction product (7).

Examples 1-9 and Comparative Examples 1-2 The compositions shown in Table 1 were kneaded with a three-roll ceramic roll,
A photosensitive paste composition was obtained. 30μm this on a copper plate
After being applied to a thickness of 2 .mu.m, a pattern film was covered on the coating film, and a light amount of ² J / cm.sup.2 was irradiated with a 250 W ultra-high pressure mercury lamp. Then, using the developers shown in Table 1, each coating film was developed at 30 ° C. for 60 seconds. The heat-decomposability, gel fraction, and line moldability of these cured molded products were evaluated by the following methods.

[Pyrolysis] About 20 mg of the molded product obtained by the above method was taken out and the pyrolysis was analyzed by thermogravimetric analysis (TG;
Thermogravimetry, Mac Sci
TG DT-DTA2000). It was heated from 25 ° C. to 600 ° C. at a temperature rising rate of 10 ° C./min in an air atmosphere, and the temperature at which the weight reduction rate became 95% was measured with 100 as the point where the weight did not change.

[Gel Fraction] The molded product obtained by the above method was weighed (a) and (g), put in methylene chloride and heated at 50 ° C.
After holding for 3 hours, it is filtered and the weight of the residue (b) (g)
Was measured. Next, the molded body obtained by the above method was weighed (c) (g) and held in a high temperature furnace at 600 ° C. for 5 hours, and then the weight (d) (g) of the residue was measured. The gel fraction was calculated from these measured values by the following formula. Gel fraction = [1- (a (g) -b (g)) / (c (g)
-D (g))] x 100 (%)

[Line Formability] The formed product obtained by the above method was baked at 600 to 800 ° C. for 10 minutes, and the obtained line pattern was visually evaluated. The one where the contrast between the exposed area and the unexposed area is clearly discerned and there is no disconnection or short-circuit line, ○, the one where the etching of the exposed area is insufficient, △
The sample that could not be etched or was completely dissolved was rated as x.

[0083]

[Table 1]

[0084]

EFFECTS OF THE INVENTION Since the crosslinked molded article of the present invention has the above-mentioned constitution, it is excellent in thermal decomposability during firing and, in addition, exhibits excellent basic performance, and is excellent in thermal decomposition. It can be suitably applied to various uses.

Continued front page    F-term (reference) 4F071 AA33 AA78 AB07 AB28 BA02                       BB02 BC02 BC10 BC17                 4J002 BE061 BG071 DA076 DL006                       FD016

Claims (3)

[Claims] 1. A crosslinked molded article, which essentially comprises an acetal bond and / or a hemiacetal ester bond and an inorganic filler. 2. The temperature at which the weight reduction rate of the crosslinked molded article is 95% or more when the weight change rate is 100% when the weight change disappears in thermogravimetric analysis is 480 ° C.
The crosslinked molded article according to claim 1, wherein: 3. The crosslinked molded body according to claim 1, wherein the crosslinked molded body is used as a thermal decomposition molded body.