JP2009120639A - Polymerizable compound, polymerizable composition and molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a polymerizable compound having a high flexibility and a low thermal decomposition temperature for its cured product, a polymerizable composition comprising the polymerizable compound and a molded article obtained by polymerizing the polymerizable composition. <P>SOLUTION: The polymerizable compound has one or more carbonate bonds, one or more acetal bonds and one or more (meth)acryloyl groups in the molecule. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a polymerizable compound, a polymerizable composition containing the polymerizable compound, and a molded body obtained by polymerizing the polymerizable composition. Specifically, a polymerizable compound and a polymerizable composition containing the polymerizable compound, which are suitable materials for firing pastes used for the formation of PDP partition walls and wiring circuits, and the polymerizable composition are polymerized. The present invention relates to a molded article to be obtained.

  In forming PDP partition walls, electrodes, dielectric layers, wiring circuits, and the like, a firing paste is widely used. In particular, when it is necessary to form a fine pattern, an inorganic pattern is formed by photolithography using a photosensitive baking paste.

  As the binder performance of the photosensitive fired paste, the UV curability is good, the difference in solubility in the developer between the exposed and unexposed parts during development is remarkable, and inorganic particles are bound. The ability is high, the thermal decomposition temperature of the cured product is low, and the binder resin is not softened during firing.

  However, in general, a crosslinked cured product is hardly thermally decomposed.

  A polyfunctional (meth) acrylate having a (meth) acryloyl group linked by an acetal bond has been reported as a compound having good thermal decomposability even when crosslinked (Patent Documents 1-3). For example, a cured product of a compound having trimethylolpropane as a skeleton and having a methacryloyl group via an acetal bond has good thermal decomposability even if it is a crosslinked product.

  However, a material that can be thermally decomposed at a lower temperature is demanded as a material of the firing paste used for forming the partition walls of the PDP.

In addition, as a material for the firing paste used for forming the PDP partition walls, a highly flexible material is required that does not cause cracks or collapse in the patterned material. Although attempts have been made to solve such problems (Patent Documents 4 and 5), it cannot be said to be sufficient.
JP 2003-195497 A JP 2003-201267 A JP 2003-268124 A JP 2001-278906 A JP 2004-123775 A

  An object of the present invention is to provide a polymerizable compound having a high flexibility and a low thermal decomposition temperature of a cured product, a polymerizable composition containing the polymerizable compound, and a molding obtained by polymerizing the polymerizable composition. To provide a body.

  The polymerizable compound of the present invention has one or more carbonate bonds, one or more acetal bonds, and one or more (meth) acryloyl groups in one molecule.

（一般式（１）中、Ｒ^１はＣ１〜Ｃ１２の単官能または多官能アルコール由来の有機残基であり、Ｒ^２は１種または２種以上のＣ１〜Ｃ１２の多官能アルコール由来の有機残基であり、Ｒ^３はＣ１〜４のアルキレン基またはＣ１〜４で重合度が２〜１０のポリアルキレンオキサイド基であり、Ｒ^４は水素原子またはメチル基であり、ｎは１〜１００の整数であり、ｍは１〜１２の整数である。） In a preferred embodiment, the polymerizable compound of the present invention is represented by the general formula (1).

(In General Formula (1), R ¹ is a C1-C12 monofunctional or polyfunctional alcohol-derived organic residue, and R ² is an organic residue derived from one or more C1-C12 polyfunctional alcohols. R ³ is a C1-4 alkylene group or a C1-4 polyalkylene oxide group having a polymerization degree of 2 to 10, R ⁴ is a hydrogen atom or a methyl group, and n is an integer of 1 to 100 And m is an integer from 1 to 12.)

  According to another aspect of the present invention, a polymerizable composition is provided. This polymerizable composition contains the polymerizable compound of the present invention.

  In a preferred embodiment, the polymerizable composition of the present invention includes inorganic particles.

  In preferable embodiment, the said inorganic particle contains at least 1 sort (s) chosen from a metal powder, glass powder, a black pigment, and ceramic fine particles.

  In a preferred embodiment, the polymerizable composition of the present invention includes a thermally decomposable polymer.

  In a preferred embodiment, the thermally decomposable polymer is a (meth) acrylic polymer.

  In a preferred embodiment, the polymerizable composition of the present invention contains a polymerization initiator.

  According to another situation of this invention, a molded object is provided. This molded body is obtained by polymerizing the polymerizable composition of the present invention.

  According to the present invention, a polymerizable compound having a high flexibility and a low thermal decomposition temperature of a cured product, a polymerizable composition containing the polymerizable compound, and a molding obtained by polymerizing the polymerizable composition The body can be provided.

  Such a polymerizable compound and a polymerizable composition containing the polymerizable compound have not only the above effects, but also have good UV curability when used as a binder for a photosensitive baking paste, for example, when developing. The difference in solubility between the exposed portion and the unexposed portion in the developer is significant, and the effect of high ability to bind inorganic particles can be exhibited.

[Polymerizable compound]
The polymerizable compound of the present invention has one or more carbonate bonds, one or more acetal bonds, and one or more (meth) acryloyl groups in one molecule. Thus, a polymerizable compound having at least one carbonate bond, acetal bond, and (meth) acryloyl group in one molecule has high flexibility and a low thermal decomposition temperature of the cured product.

（一般式（１）中、Ｒ^１はＣ１〜Ｃ１２の単官能または多官能アルコール由来の有機残基であり、Ｒ^２は１種または２種以上のＣ１〜Ｃ１２の多官能アルコール由来の有機残基であり、Ｒ^３はＣ１〜４のアルキレン基またはＣ１〜４で重合度が２〜１０のポリアルキレンオキサイド基であり、Ｒ^４は水素原子またはメチル基であり、ｎは１〜１００の整数であり、ｍは１〜１２の整数である。） The polymerizable compound of the present invention is preferably represented by the general formula (1).

(In General Formula (1), R ¹ is a C1-C12 monofunctional or polyfunctional alcohol-derived organic residue, and R ² is an organic residue derived from one or more C1-C12 polyfunctional alcohols. R ³ is a C1-4 alkylene group or a C1-4 polyalkylene oxide group having a polymerization degree of 2 to 10, R ⁴ is a hydrogen atom or a methyl group, and n is an integer of 1 to 100 And m is an integer from 1 to 12.)

R ¹ is an organic residue derived from a C1-C12 monofunctional or polyfunctional alcohol. In this specification, “Cx” (x is an integer) means “carbon number x”.

  Arbitrary appropriate C1-C12 monofunctional alcohol can be employ | adopted as C1-C12 monofunctional alcohol. For example, methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, t-butanol, hexanol, cyclohexanol, phenol, alkylphenol, benzyl alcohol, tetrahydrobenzyl alcohol, terpineol, ethylene glycol monomethyl ether, ethylene Glycol monoethyl ether, polyethylene glycol monomethyl ether, polyethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, polypropylene glycol monomethyl ether, polypropylene glycol monoethyl ether, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) Acrylate, hydroxy Chill (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, hydroxyethyl (meth) acrylamide, N- methylolacrylamide.

  Arbitrary appropriate C1-C12 polyfunctional alcohol can be employ | adopted as C1-C12 polyfunctional alcohol. Examples thereof include diols having 1 to 12 carbon atoms, triols having 1 to 12 carbon atoms, tetraols having 1 to 12 carbon atoms, and alkylene oxide adducts thereof. Examples of the diols having 1 to 12 carbon atoms include diethylene glycol, triethylene glycol, tetraethylene glycol, tripropylene glycol, polypropylene glycol, ethylene glycol, 1,2-propanediol, 1,3-butanediol, and 2-methyl. -1,3-butanediol, neopentyl glycol, hydroxypivalate ester of neopentyl glycol, 2-methylpentanediol, 3-methylpentanediol, 2,2,4-trimethyl-1,6-hexanediol, 3, Examples include 3,5-trimethyl-1,6-hexanediol, 1,6-hexanediol, and alkylene oxide adducts thereto. Examples of triols having 1 to 12 carbon atoms include first aliphatic triols such as trimethylolpropane and trimethylolethane, and alkylene oxide adducts thereof, glycerin and tris (2-hydroxyethyl) isocyanurate. It is done. Examples of the tetraols having 1 to 12 carbon atoms include first aliphatic tetraols such as pentaerythritol, diglycerin, ditrimethylolpropane, and alkylene oxide adducts thereto. Examples of the pentafunctional or higher polyhydric alcohol having 1 to 12 carbon atoms include polyglycerin, polytrimethylolpropane, polypentaerythritol, sorbitol, lactose, and alkylene oxide adducts thereto.

R ² is an organic residue derived from one or more C1-C12 polyfunctional alcohols. Arbitrary appropriate C1-C12 polyfunctional alcohol can be employ | adopted as C1-C12 polyfunctional alcohol. For example, what was illustrated above is mentioned.

R ³ is an alkylene group having _{C1~4 (-CH 2 -, - CH} 2 CH 2 -, - CH 2 CH 2 CH 2 -, - CH 2 CH 2 CH 2 CH 2 - , etc.), or degree of polymerization C1 -4 Are 2-10 polyalkylene oxide groups. Preferably, it is a polyalkylene oxide group having a degree of polymerization of 2 to 10 at C1-4, and more preferably a polyalkylene oxide group having a degree of polymerization of 2 to 3 at C2-3.

R ⁴ is a hydrogen atom or a methyl group.

  n is an integer of 1-100. The lower limit of n is preferably 3, more preferably 5, and even more preferably 7. The upper limit value of n is preferably 50, more preferably 40, and further preferably 30.

  m is an integer of 1-12. The lower limit of m is preferably 2. The upper limit value of m is preferably 10, more preferably 8, and further preferably 4.

  The molecular weight of the polymerizable compound of the present invention is preferably 200, more preferably 300, still more preferably 500 as the lower limit, and preferably 50,000, more preferably 30000 as the upper limit. More preferably, it is 10,000. If the molecular weight of the polymerizable compound of the present invention is smaller than 200, the proportion of (meth) acryloyl groups increases, and the Tg of the cured product may be lowered. When the molecular weight of the polymerizable compound of the present invention is larger than 50000, the viscosity becomes high and workability and alkali developability may be deteriorated.

  The polymerizable compound of the present invention can be produced by any appropriate method. For example, an addition reaction between a carbonate polyol and a compound having a vinyl ether group and a (meth) acryloyl group, or an addition reaction between a carbonate polyol partial (meth) acrylic acid ester and a polyfunctional vinyl ether can be mentioned.

  Examples of the carbonate polyol include DN-980, DN-981 (manufactured by Nippon Polyurethane Co., Ltd.), PNOC-2000, PNOC-1000 (manufactured by Kuraray Co., Ltd.), Plaxel CD220, CD210, CD208, CD205. (Above, Daicel Chemical Industries, Ltd.), PC-THF-CD (BASF).

Examples of the compound having a vinyl ether group and a (meth) acryloyl group include (meth) acrylic acid esters represented by the general formula (2).

_{^{CH 2 = CR 5 -COOR 6 -O}} -CH = CHR 7 (2)

(In the general formula (2), R ⁵ is a hydrogen atom or a methyl group, R ⁶ is a C1-4 alkylene group or a C1-4 polyalkylene oxide group having a polymerization degree of 2 to 10, and R ⁷ is It is a hydrogen atom.)

  Examples of the compound represented by the general formula (2) include 2-vinyloxyethyl (meth) acrylate, 3-vinyloxypropyl (meth) acrylate, 1-methyl-2-vinyloxyethyl (meth) acrylate, (meth ) 2-vinyloxypropyl acrylate, 4-vinyloxybutyl (meth) acrylate, 1-methyl-3-vinyloxypropyl (meth) acrylate, 1-vinyloxymethylpropyl (meth) acrylate, (meth) acrylic acid 2-methyl-3-vinyloxypropyl, 1,1-dimethyl-2-vinyloxyethyl (meth) acrylate, 3-vinyloxybutyl (meth) acrylate, 1-methyl-2-vinyloxypropyl (meth) acrylate, ( (Meth) acrylic acid 2-vinyloxybutyl, (meth) acrylic acid 4-vinyloxycyclohexyl, (meth) 6-vinyloxyhexyl crylate, 4-vinyloxymethylcyclohexylmethyl (meth) acrylate, 3-vinyloxymethylcyclohexylmethyl (meth) acrylate, 2-vinyloxymethylcyclohexylmethyl (meth) acrylate, (meth) P-vinyloxymethylphenylmethyl acrylate, m-vinyloxymethylphenylmethyl (meth) acrylate, o-vinyloxymethylphenylmethyl (meth) acrylate, polyethylene glycol monovinyl ether (meth) acrylate, (meth) acrylic Examples thereof include acid polypropylene glycol monovinyl ether and (meth) acrylic acid polybutylene glycol monovinyl ether.

  Arbitrary appropriate conditions can be employ | adopted about the reaction conditions of addition reaction with carbonate polyol, the compound which has a vinyl ether group and a (meth) acryloyl group. For example, a compound having a vinyl ether group and a (meth) acryloyl group with respect to 1 mol of the functional group in the carbonate polyol has a lower limit of the number of moles of the vinyl ether group, preferably 0.02 mol, more preferably 0.8. The addition reaction is carried out so that the amount is 04 mol, more preferably 0.1 mol, and the upper limit is preferably 50 mol, more preferably 10 mol, still more preferably 2 mol.

  As an addition method at the time of addition reaction between a carbonate polyol and a compound having a vinyl ether group and a (meth) acryloyl group, it may be charged into the reaction system at the beginning of the reaction, and one or both of them may be continuously or intermittently added. May be added to the reaction system.

  The addition reaction between the carbonate polyol and the compound having a vinyl ether group and a (meth) acryloyl group is preferably performed in the presence of a catalyst.

  As the catalyst, an acidic catalyst is preferable. Any appropriate acid can be adopted as the acidic catalyst. 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 Aliphatic carboxylic acids such as benzoic acid, terephthalic acid, etc .; aromatics such as benzenesulfonic acid, p-toluenesulfonic acid, p-toluenesulfonic acid pyridinium salt, p-toluenesulfonic acid quinolinium salt, etc. Sulfonic acid or salts thereof; sulfates such as sodium sulfate, potassium sulfate, magnesium sulfate, calcium sulfate, nickel sulfate, copper sulfate and zirconium sulfate; hydrogen sulfates such as sodium hydrogen sulfate and potassium hydrogen sulfate; sulfuric acid, hydrochloric acid and bromide Mineral acids such as hydroacid, hydroiodic acid, phosphoric acid, polyphosphoric acid; rimvanadomolyb Heteropolyacids such as acid, phosphotungstomolybdic acid, and cytungstomolybdic acid; acidic zeolite; the base resin is a phenolic resin or a styrenic resin, and shows any form of gel type, porous type, or macroporous type, And an acidic ion exchange resin having at least one ion exchange group selected from the group consisting of a sulfonic acid group and an alkylsulfonic acid group. These 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. For example, when hydrochloric acid is used, there is an advantage that the temperature control range is wide because it does not act as a cationic polymerization initiator and works selectively only for the addition reaction.

  Any appropriate amount can be adopted as the amount of the catalyst used. Considering the yield, catalyst stability, productivity, and economy, for example, with respect to 100 parts by weight of a compound having a vinyl ether group and a (meth) acryloyl group, the active ingredient as a catalyst, 0.0005 weight part is preferable, 0.001 weight part is more preferable, and 1 weight part is preferable as an upper limit, and 0.5 weight part is more preferable.

  The addition reaction between the carbonate polyol and the compound having a vinyl ether group and a (meth) acryloyl group is preferably performed in the presence of a polymerization inhibitor.

  Any appropriate polymerization inhibitor can be adopted as the polymerization inhibitor. For example, quinone polymerization inhibitors such as hydroquinone, methoxyhydroquinone, benzoquinone, and p-tert-butylcatechol; 2,6-di-tert-butylphenol, 2,4-di-tert-butylphenol, 2-tert-butyl4, Alkylphenol polymerization inhibitors such as 6-dimethylphenol, 2,6-di-tert-butyl-4-methylphenol, 2,4,6-tri-tert-butylphenol; alkylated diphenylamine, N, N'-diphenyl- amine polymerization inhibitors such as p-phenylenediamine and phenothiazine; N-oxyls such as 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl; copper dimethyldithiocarbamate, copper diethyldithiocarbamate, Dibutyl dithiocarbamate Okarubamin acid copper-based polymerization inhibitor; and the like. These may be used alone or in combination of two or more. Among these, quinone polymerization inhibitors and N-oxyls are preferable, and benzoquinone, phenothiazine, and 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl are more preferable.

  Any appropriate amount can be adopted as the addition amount of the polymerization inhibitor. Considering the polymerization inhibitory effect, yield, productivity, and economy, for example, with respect to 100 parts by weight of carbonate polyol, the lower limit is preferably 0.0001 parts by weight, more preferably 0.0005 parts by weight, 0.001 part by weight is further preferable, and the upper limit is preferably 5 parts by weight, more preferably 1 part by weight, and further preferably 0.1 part by weight.

  In the addition reaction between the carbonate polyol and the compound having a vinyl ether group and a (meth) acryloyl group, a solvent may be used.

  Any appropriate solvent can be adopted as the solvent. Preferably, it is an organic solvent, and only 1 type may be used and it may use 2 or more types together. Examples of the organic solvent include aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as pentane, hexane, cyclohexane, and heptane; ethers such as diethyl ether and diisopropyl ether; acetone, methyl ethyl ketone, and the like. Ketones; polar solvents such as dimethylformamide and dimethyl sulfoxide: halogenated hydrocarbons such as chloroform, methylene chloride, dichloroethane, chlorobenzene; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, propylene glycol dimethyl ether, propylene Glycol ethers such as glycol diethyl ether, diethylene glycol dimethyl ether, and diethylene 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, dipropylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-methoxy Tyl 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, 3-methyl-3-methoxypentyl acetate Acetates such as 3-methyl-4-methoxypentyl acetate and 4-methyl-4-methoxypentyl acetate; diesters such as dimethyl glutarate, dimethyl succinate and dimethyl adipate; It is.

  Any appropriate amount can be adopted as the amount of the solvent used. Considering the yield, productivity, and economic efficiency, for example, 0% by weight is set as the lower limit with respect to 100 parts by weight of the total weight of the carbonate polyol and the compound having a vinyl ether group and a (meth) acryloyl group. Preferably, the upper limit is preferably 200 parts by weight, more preferably 100 parts by weight, and even more preferably 70 parts by weight.

  In the addition reaction of a carbonate polyol, a compound having a vinyl ether group and a (meth) acryloyl group, the reaction temperature is preferably −40 ° C. as the lower limit in consideration of yield, productivity, and economy. 30 ° C. is more preferable, −20 ° C. is more preferable, and the upper limit is 150 ° C., 100 ° C. is more preferable, and 70 ° C. is more preferable.

  In the addition reaction between the carbonate polyol and the compound having a vinyl ether group and a (meth) acryloyl group, any appropriate time can be set as the reaction time.

  In the addition reaction of a carbonate polyol and a compound having a vinyl ether group and a (meth) acryloyl group, the reaction pressure may be any of normal pressure (atmospheric pressure), reduced pressure, and increased pressure.

(Polymerizable composition)
The polymerizable composition of the present invention contains the polymerizable compound. Hereinafter, the polymerizable compound contained in the polymerizable composition may be referred to as a polymerizable compound (A) for convenience of explanation.

  The content of the polymerizable compound (A) in the polymerizable composition of the present invention is preferably 1% by weight, more preferably 2% by weight, and more preferably 3% by weight as a lower limit with respect to 100 parts by weight of the polymerizable composition. % Is more preferable, 4% by weight is particularly preferable, and the upper limit is preferably 90% by weight, more preferably 70% by weight, further preferably 50% by weight, and particularly preferably 40% by weight. When the said content rate is less than 1 weight%, there exists a possibility that sufficient sclerosis | hardenability may not be obtained. When the said content rate is more than 90 weight%, since there are too few inorganic components in a polymeric composition, there exists a possibility that the shrinkage | contraction at the time of baking may become large.

  The polymerizable composition of the present invention preferably contains inorganic particles. Hereinafter, the said inorganic particle which may be contained in a polymeric composition may be called an inorganic particle (B) for convenience of explanation.

  The content ratio of the inorganic particles (B) in the polymerizable composition of the present invention is preferably 10% by weight, more preferably 20% by weight, and more preferably 30% by weight as a lower limit with respect to 100 parts by weight of the polymerizable composition. Is more preferable, 40% by weight is particularly preferable, and the upper limit is preferably 95% by weight, more preferably 90% by weight, still more preferably 80% by weight, and particularly preferably 70% by weight. When the said content rate is less than 10 weight%, since there are too few inorganic components in polymeric composition, there exists a possibility that the shrinkage | contraction at the time of baking may become large, and it may become difficult to form the molded object of an inorganic component. When the said content rate is more than 95 weight%, since there are too many inorganic components in polymeric composition, there exists a possibility that workability | operativity, such as applicability | paintability and printability, may fall.

  Any appropriate inorganic particles can be adopted as the inorganic particles (B) in the polymerizable composition of the present invention. Preferably, it contains at least one selected from metal powder (B-1), glass powder (B-2), black pigment (B-3), and ceramic fine particles (B-4). Whatever inorganic particles are used, it is preferable to use glass powder in order to improve the firing property.

  Arbitrary appropriate metal powder can be employ | adopted as metal powder (B-1). For example, gold, silver, copper, ruthenium, palladium, platinum, aluminum, nickel and the like and alloys thereof can be used. The said metal powder may use only 1 type and may use 2 or more types together. As an average particle diameter of metal powder (B-1), 10 micrometers is preferable as an upper limit from the point of resolution, and 5 micrometers is more preferable. Examples of the shape of the metal powder (B-1) include a spherical shape, a block shape, a flake shape, and a dendrite shape. These shapes may use only 1 type and may use 2 or more types together.

  The metal powder (B-1) is preferably treated with a fatty acid particularly for Ag, Ni, and Al in order to prevent oxidation, improve dispersibility in the polymerizable composition, and stabilize developability. Examples of fatty acids include oleic acid, linoleic acid, linolenic acid, and stearic acid.

Arbitrary appropriate glass powder can be employ | adopted as glass powder (B-2). As the glass powder (B-2), for example, a low melting point glass frit having a softening point of 300 to 600 ° C. is preferable so that firing can be performed at a temperature of 600 ° C. or less. A glass powder mainly composed of lead oxide, bismuth oxide, zinc oxide, lithium oxide, and alkali borosilicate is particularly preferable. As the low melting point glass frit, those having a glass transition temperature of preferably 300 to 550 ° C. and a thermal expansion coefficient α300 of preferably 70 × 10 ⁻⁷ / ° C. to 90 × 10 ⁻⁷ / ° C. can be used. The average particle size of the glass powder (B-2) is preferably 10 μm and more preferably 2.5 μm as an upper limit from the viewpoint of resolution.

  Any appropriate black pigment can be adopted as the black pigment (B-3). For example, a black pigment made of one or more metal oxides such as Fe, Co, Cu, Cr, Mn, and Al can be used. More specifically, for example, Co-Cr-Fe, Co-Mn-Fe, Co-Fe-Mn-Al, Co-Ni-Cr-Fe, Co-Ni-Al-Cr-Fe, Co-Mn- Al-Cr-Fe-Si is mentioned. As a black pigment (B-3), the average particle diameter is preferably 1.0 μm, more preferably 0.6 μm as an upper limit value in terms of blackness.

  In addition, when white is calculated | required for a baked material pattern, you may use white pigments, such as a titanium oxide, an aluminum oxide, a silica, a calcium carbonate.

  Any appropriate ceramic fine particles can be adopted as the ceramic fine particles (B-4). For example, alumina, cordierite, and zircon can be used. Ceramic fine particles (B-4) may be used alone or in combination of two or more. The ceramic fine particles (B-4) have an average particle size of preferably 10 μm, more preferably 2.5 μm as an upper limit from the viewpoint of resolution.

  The ceramic fine particles (B-4) can be added to the glass powder (B-2) to improve the denseness inside the fired product pattern such as the partition walls and increase the mechanical strength of the fired product. That is, the ceramic fine particles (B-4) are preferably blended in an amount of 0.1 to 50 parts by weight with respect to 100 parts by weight of the glass powder (B-2), whereby a fired product such as a dense partition wall having a small shrinkage rate. A pattern can be obtained.

  As the inorganic particles (B) in the polymerizable composition of the present invention, black conductive fine particles (B-5) may be used. For example, since the high temperature firing of 500 to 600 ° C. is involved in the PDP electrode preparation step, the black conductive fine particles (B-5) are preferably those having a color tone at high temperature and conductivity stability. For example, a ruthenium oxide, a ruthenium compound, a copper-chromium black composite oxide, or a copper-iron black composite oxide can be used. In particular, a ruthenium oxide and a ruthenium compound are preferable. This is because the color tone and conductivity stability at high temperatures are extremely excellent.

  As the inorganic particles (B) in the polymerizable composition of the present invention, particles having a particle size of 10 microns or less are preferably used. Therefore, organic acids, inorganic acids, silane coupling agents, titanate coupling agents, aluminum couplings are used within the range that does not impair the properties of the inorganic particles (B) for the purpose of preventing secondary aggregation and improving dispersibility. Inorganic particles that have been surface-treated with a treating agent such as an agent can be used. Moreover, the said processing agent may be contained in the polymeric composition of this invention. In addition, in order to improve the storage stability of the polymerizable composition of the present invention, a compound having an effect such as complexation with metal or oxide powder or salt formation can be added as a stabilizer. Examples of the stabilizer include acids such as inorganic acids, organic acids, and phosphoric acid compounds (inorganic phosphoric acid and organic phosphoric acid). The addition amount of such a stabilizer is preferably 5 parts by weight or less with respect to 100 parts by weight of the inorganic particles (B).

  The polymerizable composition of the present invention preferably contains a thermally decomposable polymer. Hereinafter, the heat decomposable polymer that may be contained in the polymerizable composition may be referred to as a heat decomposable polymer (C) for convenience of explanation.

  The content of the thermally decomposable polymer (C) in the polymerizable composition of the present invention is preferably 10% by weight, more preferably 20% by weight, as a lower limit with respect to 100 parts by weight of the polymerizable composition. 30% by weight is more preferable, 40% by weight is particularly preferable, and the upper limit is preferably 95% by weight, more preferably 90% by weight, still more preferably 80% by weight, and particularly preferably 70% by weight. When the said content rate is less than 10 weight%, since there are too few inorganic components in polymeric composition, there exists a possibility that the shrinkage | contraction at the time of baking may become large, and it may become difficult to form the molded object of an inorganic component. When the said content rate is more than 95 weight%, since there are too many inorganic components in polymeric composition, there exists a possibility that workability | operativity, such as applicability | paintability and printability, may fall.

  Any appropriate thermally decomposable polymer can be adopted as the thermally decomposable polymer (C). For example, (meth) acrylic polymers, polyvinyl alcohol, polyvinyl acetal, styrene-allyl alcohol, phenol resins, polypropylene carbonate resins, olefinic hydroxyl group-containing polymers, hydroxyl groups of these hydroxyl group-containing polymers and amino groups of amino resins Added lactone-modified polymer, homopolymer of monomer having both hydroxyl group or amino group and unsaturated group in the molecule, copolymer of lactone-modified monomer and monomer having other unsaturated group, methylcellulose, ethylcellulose, hydroxyethylcellulose Is mentioned. Among these, (meth) acrylic polymers, ethyl cellulose, and propylene carbonate resins are preferable, and (meth) acrylic polymers are particularly preferable.

  Any appropriate (meth) acrylic polymer can be adopted as the (meth) acrylic polymer. In the present specification, “(meth) acryl” means acryl and / or methacryl. In this specification, “(meth) acrylic polymer” means a homopolymer or copolymer obtained by polymerizing a monomer component containing 50% by weight or more of (meth) acrylic acid and / or a derivative thereof. Means.

  Examples of the (meth) acrylic polymer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) ) Acrylate, t-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and other (meth) acrylates, one or more Or a copolymer of one or more of the (meth) acrylates and other monomer components.

  The thermally decomposable polymer (C) is a component that is removed by firing, but is contained as a binder for the inorganic particles (B) and for the purpose of improving transferability, and exhibits thermoplasticity. preferable. When the thermally decomposable polymer (C) exhibiting thermoplasticity is used, even if the paste itself has a high viscosity, it is softened or melted by heating and can be applied or filled into the groove. In addition, when the thermally decomposable polymer (C) contains a hydroxyl group or a carboxyl group in a range having the stability of the paste, the dispersibility of the inorganic particles (B) is improved, and the paste is imparted with thixotropic properties to make it inorganic. The effect that precipitation of particle | grains (B) can be prevented is also acquired.

  The weight average molecular weight of the thermally decomposable polymer (C) is preferably 3000 as the lower limit, more preferably 10,000, further preferably 100,000, and preferably 300,000 as the upper limit. When the heat decomposable polymer (C) has a weight average molecular weight of less than 3000, pasting may be difficult. When the weight average molecular weight of the thermally decomposable polymer (C) is larger than 300,000, the paste becomes too viscous and the filling property may be deteriorated.

  The thermal decomposition temperature of the thermally decomposable polymer (C) is preferably lower than the glass transition point of the glass powder (B-2). If the thermal decomposition temperature of the thermally decomposable polymer (C) is higher than the glass transition point of the glass powder (B-2), it is not sufficiently removed at the initial stage of firing, and the firing residue (the binder polymer is thermally decomposed in the glass). This is not preferable because it remains as bubbles. Moreover, when the thermal decomposition temperature of the thermally decomposable polymer (C) is higher than the glass transition point of the glass powder (B-2), pasting becomes difficult.

  The thermally decomposable polymer (C) preferably has a carboxyl group in order to impart alkali developability. That is, the thermally decomposable polymer (C) is preferably a carboxyl group-containing polymer. When the thermally decomposable polymer (C) has a carboxyl group, the acid value of the thermally decomposable polymer (C) is preferably 10 as a lower limit, more preferably 30 and even more preferably 40. Yes, particularly preferably 50, and the upper limit is preferably 150, more preferably 130, still more preferably 120, and particularly preferably 110.

  The polymerizable composition of the present invention preferably contains a polymerization initiator. Hereinafter, the polymerization initiator that may be contained in the polymerizable composition may be referred to as a polymerization initiator (D) for convenience of explanation.

  Any appropriate polymerization initiator can be adopted as the polymerization initiator (D). Examples thereof include a thermal polymerization initiator (D-1) and a photopolymerization initiator (D-2). Only one type of polymerization initiator (D) may be used, or two or more types may be used in combination.

  Examples of the thermal polymerization initiator (D-1) include methyl ethyl ketone peroxide, benzoyl peroxide, dicumyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxyoctoate, and t-butyl. And organic peroxides such as peroxybenzoate and lauroyl peroxide; azo compounds such as azobisisobutyronitrile. Moreover, you may mix and use a hardening accelerator at the time of thermal polymerization. Examples of the curing accelerator include cobalt naphthenate, cobalt octylate, and tertiary amine.

  The amount of the thermal polymerization initiator (D-1) used is preferably 0.05 to 5 parts by weight with respect to 100 parts by weight of the polymerizable composition of the present invention.

  Examples of the photopolymerization initiator (D-2) include benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether and alkyl ethers thereof; acetophenone, 2,2-dimethoxy-2- Phenylacetophenone, 1,1-dichloroacetophenone, 4- (1-t-butyldioxy-1-methylethyl) acetophenone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 4- (2-hydroxyethoxy ) Acetophenones such as phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone oligomer; Anthraquinones such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone; 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2- (3-dimethylamino-2-hydroxy) -3,4-dimethyl-9 -Thioxanthones such as thioxanthone-9-one mesochloride; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone, 4- (1-t-butyldioxy-1-methylethyl) benzophenone, 3, 3 ', 4, 4'-tetrakis (t-butyldioxycarbonyl) benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, 3,3 ', 4,4'-tetra ( t-butylperoxylcarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyloxy) ethyl] benzenemethananium bromide , (4-Benzoylbenzyl) to Benzophenones such as limethylammonium chloride; acyl phosphine oxides; xanthones.

  The usage-amount of a photoinitiator (D-2) becomes like this. Preferably it is 0.1-25 weight part with respect to 100 weight part of polymeric compositions of this invention.

  In the present invention, the polymerization initiator (D) is preferably a photopolymerization initiator (D-2), more preferably an acetophenone (acetophenone photopolymerization initiator), more specifically Irgacure 184 (Ciba Japan). Co., Ltd.) and Darocur 1173 (Ciba Japan Co., Ltd.) are particularly preferable.

  The polymerizable composition of the present invention may contain a curable compound. Hereinafter, the said curable compound which may be contained in a polymeric composition may be called a curable compound (E) for convenience of explanation.

  Examples of the curable compound (E) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate. , T-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, ethoxy-diethylene glycol (meth) acrylate, phenoxy Monofunctional (meth) acrylates such as ethyl (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate Nonanediol di (meth) acrylate, polyurethane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane ethylene oxide modified tri ( (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, mono-, di-, tri-, or more polyesters of polybasic acid and hydroxyalkyl (meth) acrylate, many Examples thereof include mono-, di-, tri-, or more polyesters of a basic acid and a polyfunctional (meth) acrylate monomer having an OH group. A curable compound (E) may be used only by 1 type, and may use 2 or more types together. Arbitrary appropriate quantity can be employ | adopted for the usage-amount of a sclerosing | hardenable compound (E).

  The polymerizable composition of the present invention may contain an organic solvent. Hereinafter, the organic solvent that may be contained in the polymerizable composition may be referred to as an organic solvent (F) for convenience of explanation.

  Examples of the organic solvent (F) include 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 ethers such as recall dimethyl ether and diethylene 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-methoxybutyl 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- Acetates such as methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate Ketones such as acetone, methyl ethyl ketone, diethyl ketone, methyl silobutyl ketone, ethyl isobutyl ketone and cyclohexanone; methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, 2-hydroxypropion Ethyl acetate, 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 ethoxy acetate, ethyl oxyacetate, 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, pyruvin Esters such as butyl acid, 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 Aromatics such as methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, glycerin and other alcohols; tetrahydrofuran, etc. And the like. The organic solvent (F) may be used alone or in combination of two or more. Arbitrary appropriate quantity can be employ | adopted for the usage-amount of an organic solvent (F).

  The polymerizable composition of the present invention may contain a dispersant. Hereinafter, the dispersant that may be contained in the polymerizable composition may be referred to as a dispersant (G) for convenience of explanation.

  Examples of the dispersant (G) include compounds having a polar group having an affinity for inorganic particles (B) such as carboxyl groups, hydroxyl groups, and acid esters, and polymer compounds such as acid-containing compounds such as phosphate esters, , A copolymer containing an acid group, a hydroxyl group-containing polycarboxylic acid ester, polysiloxane, a salt of a long-chain polyaminoamide and an acid ester, and the like can be used. Examples of commercially available dispersants include Disperbyk (registered trademark) -101, -103, -110, -111, -160, and -300 (all manufactured by Big Chemie). A dispersing agent (G) may be used only by 1 type, and may use 2 or more types together. Arbitrary appropriate quantity can be employ | adopted for the usage-amount of a dispersing agent (G).

  The polymerizable composition of the present invention may contain other components. Hereinafter, the other components that may be contained in the polymerizable composition may be referred to as other components (Z) for convenience of explanation.

  Examples of other components (Z) include sensitizers, thermal polymerization inhibitors, plasticizers, surfactants, wetting agents, antifoaming agents, leveling agents, and other additives. Other components (Z) may be used alone or in combination of two or more. Arbitrary appropriate quantity can be employ | adopted for the usage-amount of another component (Z).

[Molded body]
The molded product of the present invention is obtained by polymerizing the polymerizable composition.

  The molded body of the present invention is, for example, after the polymerizable composition is applied to the entire surface or a part of the base material, a pattern is formed by printing, photolithography, or the like, or is molded into a predetermined shape. For example, if it is photocurable, it can be formed by curing by irradiating light such as ultraviolet rays. By firing the molded body of the present invention, the organic component is decomposed and volatilized, and the inorganic components are fused to each other, so that a molded body such as a strong coating film or pattern made of the inorganic component can be obtained.

  The molded article of the present invention is used as a thermal decomposition molded article because it is excellent in thermal decomposability under moderate firing conditions and can obtain an inorganic molded article or an inorganic pattern with very little organic component remaining. Is preferred. In addition, when it has photocurability, a high-resolution pattern can be obtained by using a photolithography method, so that the barrier ribs, electrodes, resistors, phosphors of a plasma display panel (PDP) can be obtained by printing, photolithography, or the like. Suitable for the manufacture of color filters, black matrices, etc., the manufacture of electrode patterns constituting LCDs, organic EL elements, printed circuit boards, multilayer circuit boards, multichip modules, LSIs, etc., the production of conductor patterns on ceramic substrates, etc. Can be applied.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these Examples. Unless otherwise specified, parts and% in the examples are based on weight.

[Example 1]: Synthesis of Compound (M-1) To a flask equipped with a stirrer, a thermometer, a condenser, a dropping device, and a mixed gas introduction tube of air and nitrogen, oximer N-112 (manufactured by Perstorp, Poly ( 1000 g of oxycarbonyloxy [2,2-dimethyl-1,3-propanediyl]), 2000 g of ethyl acetate, 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl (hereinafter abbreviated as 4H-TEMPO) ) 0.144 g and heated to 60 ° C. to obtain a homogeneous solution, then cooled to 30 ° C. and charged with 0.52 g of hydrochloric acid (35% hydrogen chloride) and then vinyloxy (2-ethoxy) 440 g of ethyl) methacrylate (hereinafter abbreviated as VEEM) was added dropwise over 2 hours while paying attention to heat generation, and then 0.52 g of hydrochloric acid (35% hydrogen chloride) was added for 30 minutes. Each time, the mixture was added three times, and the temperature was raised to 70 ° C., and the reaction was carried out for 3 hours.After confirming that the VEEM peak almost disappeared by gel permeation chromatography (hereinafter abbreviated as GPC), glycidyl 5.68 g of methacrylate (hereinafter abbreviated as GMA) was added to deactivate hydrochloric acid.
Subsequently, the obtained reaction liquid was heated to 80 ° C. and the solvent was removed by decompression. As a result, the obtained reaction product was liquid at 80 ° C., but was solid at room temperature when cooled. Further, this was dissolved in acetone, dropped into a large amount of methanol and reprecipitated, and then dried in a vacuum dryer. When the obtained compound (M-1) was analyzed by H ¹ -NMR, 5.5 to 6.1 ppm and a peak due to a methacryloyl group in the vicinity of 2 ppm, an acetal bond in the vicinity of 1.2 to 1.3 ppm. A peak attributed to the methyl group was observed in the vicinity of 4.7 to 4.8 ppm (FIG. 1).
Moreover, when analysis by FT-IR was performed, the absorption of the carbonyl considered to originate in a carbonate bond was observed.

[Example 2]: Synthesis of Compound (A-1) In a flask equipped with a stirrer, a thermometer, a condenser, a dropping device, and a mixed gas introduction tube of air and nitrogen, 1000 g of oximer N-112 and 2000 g of ethyl acetate 0.141 g of 4H-TEMPO was charged and heated to 60 ° C. to obtain a uniform solution. Next, after cooling the temperature to 30 ° C. and adding 0.52 g of hydrochloric acid (35% hydrogen chloride), 410 g of vinyloxy (2-ethoxyethyl) acrylate (hereinafter abbreviated as VEEA) was added over 2 hours while paying attention to heat generation. And dripped. Next, after adding 0.52 g of hydrochloric acid (35% hydrogen chloride) three times every 30 minutes, the temperature was raised to 70 ° C. and the reaction was performed for 3 hours. After confirming that the VEEA peak almost disappeared by GPC, 5.68 g of GMA was added to deactivate hydrochloric acid.
Subsequently, the obtained reaction liquid was heated to 80 ° C. and the solvent was removed by decompression. As a result, the obtained reaction product was liquid at 80 ° C., but was solid at room temperature when cooled. Further, this was dissolved in acetone, dropped into a large amount of methanol and reprecipitated, and then dried in a vacuum dryer. When the obtained compound (A-1) was analyzed by H ¹ -NMR, a peak attributed to an acryloyl group was observed in the vicinity of 5.5 to 6.1 ppm, and an acetal-bonded methyl group was present in the vicinity of 1.2 to 1.3 ppm. A peak due to acetal-bound methine was observed in the vicinity of 4.7 to 4.8 ppm (FIG. 2).
Moreover, when analysis by FT-IR was performed, the absorption of the carbonyl considered to originate in a carbonate bond was observed.

[Example 3]: Synthesis of Compound (M-2) To a flask equipped with a stirrer, a thermometer, a condenser, a dropping device, and a mixed gas introduction tube of air and nitrogen, oximer B-112 (manufactured by Perstorp, Poly ( 1000 g of oxycarbonyloxy [2-butyl-2-ethyl-1,3-propanediyl]), 2000 g of ethyl acetate and 0.144 g of 4H-TEMPO were charged and heated to 60 ° C. to obtain a uniform solution. After cooling the temperature to 30 ° C. and adding 0.52 g of hydrochloric acid (35% hydrogen chloride), 440 g of VEEM was added dropwise over 2 hours while paying attention to heat generation. 52 g was added three times every 30 minutes, and the reaction was carried out for 3 hours by raising the temperature to 70 ° C. After confirming that the VEEM peak had almost disappeared by GPC, GMA 5.6 8 g was added to deactivate hydrochloric acid.
Subsequently, when the obtained reaction solution was heated to 80 ° C. and desolvated by reduced pressure, the obtained reaction product was a liquid at room temperature. Further, this was dissolved in acetone, dropped into a large amount of methanol and reprecipitated, and then dried in a vacuum dryer. When the obtained compound (M-2) was analyzed by H ¹ -NMR, peaks due to the methacryloyl group were observed in the vicinity of 5.5 to 6.1 ppm and 2 ppm, and an acetal bond was observed in the vicinity of 1.2 to 1.3 ppm. A peak attributed to the methyl group was observed in the vicinity of 4.7 to 4.8 ppm (FIG. 3).
Moreover, when analysis by FT-IR was performed, the absorption of the carbonyl considered to originate in a carbonate bond was observed.

[Example 4]: Synthesis of Compound (A-2) 1000 g of oximer B-112 and 2000 g of ethyl acetate in a flask equipped with a stirrer, a thermometer, a condenser, a dropping device, and a mixed gas introduction tube of air and nitrogen 0.141 g of 4H-TEMPO was charged and heated to 60 ° C. to obtain a uniform solution. Next, after cooling the temperature to 30 ° C. and adding 0.52 g of hydrochloric acid (35% hydrogen chloride), 410 g of VEEA was added dropwise over 2 hours while paying attention to heat generation. Next, after adding 0.52 g of hydrochloric acid (35% hydrogen chloride) three times every 30 minutes, the temperature was raised to 70 ° C. and the reaction was performed for 3 hours. After confirming that the VEEA peak almost disappeared by GPC, 5.68 g of GMA was added to deactivate hydrochloric acid.
Subsequently, when the obtained reaction solution was heated to 80 ° C. and desolvated by reduced pressure, the obtained reaction product was a liquid at room temperature. Further, this was dissolved in acetone, dropped into a large amount of methanol and reprecipitated, and then dried in a vacuum dryer. When the obtained compound (A-2) was analyzed by H ¹ -NMR, a peak attributed to an acryloyl group was present in the vicinity of 5.5 to 6.1 ppm, and an acetal-bonded methyl group was present in the vicinity of 1.2 to 1.3 ppm. A peak due to acetal-bound methine was observed in the vicinity of 4.7 to 4.8 ppm (FIG. 4).
Moreover, when analysis by FT-IR was performed, the absorption of the carbonyl considered to originate in a carbonate bond was observed.

[Comparative Example 1]: Synthesis of Compound (M-3) In a flask equipped with a stirrer, a thermometer, a condenser, a dripping device, and a mixed gas introduction tube of air and nitrogen, 1000 g of polyethylene glycol having a molecular weight of 1000, 4H-TEMPO 0 .144 g was added, the temperature was adjusted to 30 ° C., 0.52 g of hydrochloric acid (35% hydrogen chloride) was added, and VEEM 440 g was added dropwise over 2 hours while paying attention to heat generation. Next, after adding 0.52 g of hydrochloric acid (35% hydrogen chloride) three times every 30 minutes, the temperature was raised to 70 ° C. and the reaction was performed for 3 hours. After confirming that the VEEM peak almost disappeared by GPC, 5.68 g of GMA was added to deactivate hydrochloric acid.
When the obtained compound (M-3) was analyzed by H ¹ -NMR, the peaks attributed to methacryloyl groups were observed in the vicinity of 5.5 to 6.1 ppm and 2 ppm, and the acetal bond was observed in the vicinity of 1.2 to 1.3 ppm. A peak attributed to the methyl group was observed in the vicinity of 4.7 to 4.8 ppm.

[Comparative Example 2]: Synthesis of Compound (A-3) In a flask equipped with a stirrer, a thermometer, a condenser, a dropping device, and a mixed gas introduction tube of air and nitrogen, 1000 g of polyethylene glycol having a molecular weight of 1000, 4H-TEMPO 0 .141 g was added, the temperature was adjusted to 30 ° C., 0.52 g of hydrochloric acid (35% hydrogen chloride) was added, and 410 g of VEEA was added dropwise over 2 hours while paying attention to heat generation. Next, after adding 0.52 g of hydrochloric acid (35% hydrogen chloride) three times every 30 minutes, the temperature was raised to 70 ° C. and the reaction was performed for 3 hours. After confirming that the VEEA peak almost disappeared by GPC, 5.68 g of GMA was added to deactivate hydrochloric acid.
When the obtained compound (A-3) was analyzed by H ¹ -NMR, a peak attributed to the acryloyl group was observed at around 5.5 to 6.1 ppm, and an acetal-bonded methyl group at around 1.2 to 1.3 ppm. A peak due to acetal-bound methine was observed in the vicinity of 4.7 to 4.8 ppm.

[Comparative Example 3]: Synthesis of Compound (M-4) In a flask equipped with a stirrer, a thermometer, a condenser, an oil / water separator, a dropping device, a mixed gas introduction tube of air and nitrogen, 1000 g of polyethylene glycol having a molecular weight of 1000, 500 g of toluene, 189.2 g of methacrylic acid, 0.238 g of 4H-TEMPO and 2.38 g of p-toluenesulfonic acid were charged, and the dehydration condensation reaction was performed at 110 ° C. over 6 hours. Subsequently, 1000 g of toluene, 200 g of ion-exchange water and 0.50 g of sodium hydroxide were added and stirred sufficiently, and then the aqueous layer was removed with a separatory funnel. Furthermore, the operation of adding 200 g of ion-exchanged water and stirring well to remove the aqueous layer was repeated until the pH of the aqueous layer reached 7. Finally, toluene was removed by heating under reduced pressure to obtain polyethylene glycol dimethacrylate (M-4).

[Comparative Example 4]: Synthesis of Compound (A-4) In a flask equipped with a stirrer, a thermometer, a condenser, an oil / water separator, a dropping device, and a mixed gas introduction tube of air and nitrogen, 1000 g of polyethylene glycol having a molecular weight of 1000, 500 g of toluene, 158.4 g of acrylic acid, 0.232 g of 4H-TEMPO, and 2.32 g of p-toluenesulfonic acid were charged, and the dehydration condensation reaction was performed at 110 ° C. over 6 hours. Subsequently, 1000 g of toluene, 200 g of ion-exchanged water and 0.49 g of sodium hydroxide were added and stirred sufficiently, and then the aqueous layer was removed with a separatory funnel. Furthermore, the operation of adding 200 g of ion-exchanged water and stirring well to remove the aqueous layer was repeated until the pH of the aqueous layer reached 7. Finally, toluene was removed by heating under reduced pressure to obtain polyethylene glycol diacrylate (A-4).

[Synthesis Example 1]: Synthesis of carboxyl group-containing polymer (P-1) In a flask equipped with a stirrer, a thermometer, a condenser, an oil / water separator, a dropping device, and a nitrogen gas inlet tube, propylene glycol monomethyl ether acetate (hereinafter PGMEA). 1263 g were charged, and the temperature was raised to 70 ° C. with nitrogen substitution. Subsequently, a mixture of 997.7 g of methyl methacrylate and 179.7 g of methacrylic acid, 58.9 g of 2,2′-azobis (2,4-dimethylvaleronitrile (V-65, manufactured by Wako Pure Chemical Industries)) and 500 g of PGMEA At the same time, the solution was added dropwise over 1 hour, held at 70 ° C. for 2 hours, and further aged for 3 hours at 90 ° C. and cooled.The molecular weight of the resulting carboxyl group-containing polymer (P-1) Was measured by GPC (polystyrene conversion, THF = 0.6 ml / min, apparatus: HLC-8220 GPC manufactured by Tosoh, column configuration: all TSK Gel-SuperHM-N 2 manufactured by Tosoh + 1 TSK Gel-SuperH2000 1) The average molecular weight was 5100, and the weight average molecular weight was 11800.

[Examples 5 to 8]
100 g of the compounds obtained in Examples 1 to 4 (compound having a carbonate bond, an acetal bond and a (meth) acryloyl group in one molecule), 100 g of ethyl acetate, 2-hydroxy-2-methyl-1-phenyl-propane- 1-one (Darocur 1173, manufactured by Ciba Japan Co., Ltd.) 5 g was uniformly mixed and coated on a glass plate with a thickness of 100 μm. It was left in a hot air dryer heated to 80 ° C. for 30 minutes to remove the solvent. Subsequently, using a 250 W ultra-high pressure mercury lamp in a nitrogen gas atmosphere, irradiation with 33 mW / cm ² was performed for 60 seconds to cure the coating film.
The thermal decomposability of the obtained cured product was measured by thermogravimetric analysis (TG; Thermogravimetry, TG-DTA2000 manufactured by Mac Science). The results are shown in Table 1. The thermal decomposition temperature was defined as the temperature at which both the weight change and the calorific value change disappeared when heated from 25 ° C. to 600 ° C. in the temperature increase test at a temperature increase rate of 10 ° C./min and an air flow rate of 100 mL / min.

[Comparative Examples 5 to 8]
Hardened | cured material was created by the method similar to Example 1-4 with respect to 100g of compounds (compound which has a (meth) acryloyl group) obtained by Comparative Examples 1-4, and the thermal decomposition temperature was measured. The results are shown in Table 1.

Example 9
The compound (M-2), glass frit, and photopolymerization initiator (D1173: Darocur 1173, manufactured by Ciba Japan Co., Ltd., 2-hydroxy-2-methyl-1-phenylpropane-1-one) obtained in Example 3 were used. A paste mixed with the formulation shown in Table 2 was printed on a crow board by a screen printing method, and then UV cured with an irradiation energy of ² J / cm ² . After putting it in an electric furnace at 600 ° C. and baking for 1 hour, the state of the pattern was observed with an optical microscope. The results are shown in Table 2.

[Comparative Example 9]
The pattern was observed with an optical microscope in the same manner as in Example 9 except that the compound (M-3) obtained in Comparative Example 1 was used instead of the compound (M-2). The results are shown in Table 2.

[Comparative Example 10]
It carried out similarly to Example 9 except having used the compound (M-4) obtained by the comparative example 3 instead of the compound (M-2), and observed the state of the pattern with the optical microscope. The results are shown in Table 2.

Example 10
Compound (M-1) obtained in Example 1, glass frit, carboxyl group-containing polymer (P-1) obtained in Synthesis Example 1, solvent (PGMEA: propylene glycol monomethyl ether acetate), photopolymerization initiator ( D1173: Darocur 1173, manufactured by Ciba Japan Co., Ltd., 2-hydroxy-2-methyl-1-phenylpropan-1-one) was mixed at a thickness of 100 μm on a glass plate with the formulation shown in Table 2. This was dried at 80 ° C. for 30 minutes, and then irradiated with UV having an energy of ² J / cm ² through a photomask having a line and space of 40 μm × 40 μm. Subsequently, the film was developed with a 2.5% triethanolamine aqueous solution, washed with water, placed in an electric furnace at 600 ° C. and baked for 1 hour, and the state of the pattern was observed with an optical microscope. The results are shown in Table 3.

[Comparative Example 11]
It carried out similarly to Example 10 except having used the compound (M-3) obtained by the comparative example 1 instead of the compound (M-1), and observed the state of the pattern with the optical microscope. The results are shown in Table 2.

[Comparative Example 12]
It carried out similarly to Example 10 except having used the compound (M-4) obtained by the comparative example 3 instead of the compound (M-1), and observed the state of the pattern with the optical microscope. The results are shown in Table 2.

[Comparative Example 13]
Except having used trimethylol propane trimethacrylate (TMPTMA) instead of the compound (M-1), it carried out similarly to Example 10, and observed the state of the pattern with the optical microscope. The results are shown in Table 2.

Example 11
Compound (A-2) obtained in Example 4, inorganic particles (Ag), photopolymerization initiator (D1173: Darocur 1173, manufactured by Ciba Japan, 2-hydroxy-2-methyl-1-phenylpropane-1 On) a paste mixed with the formulation shown in Table 3 was printed on a glass plate by a screen printing method, and then UV cured with an irradiation energy of ² J / cm ² . After putting it in an electric furnace at 600 ° C. and baking for 1 hour, the state of the pattern was observed with an optical microscope. The results are shown in Table 3.

Example 12
Except that the inorganic particles were replaced with ruthenium oxide, the same procedure as in Example 11 was performed, and the state of the pattern was observed with an optical microscope. The results are shown in Table 3.

Example 13
Except that the inorganic particles were replaced with alumina, the same operation as in Example 11 was performed, and the state of the pattern was observed with an optical microscope. The results are shown in Table 3.

Example 14
Compound (A-1) obtained in Example 2, inorganic particles (Ag), carboxyl group-containing polymer (P-1) obtained in Synthesis Example 1, solvent (PGMEA: propylene glycol monomethyl ether acetate), photopolymerization A paste prepared by mixing an initiator (D1173: Darocur 1173, manufactured by Ciba Japan Co., Ltd., 2-hydroxy-2-methyl-1-phenylpropane-1-one) with the composition shown in Table 3 was applied to a glass plate with a thickness of 20 μm. did. This was dried at 80 ° C. for 30 minutes, and then irradiated with UV having an energy of ² J / cm ² through a photomask having a line and space of 40 μm × 40 μm. Subsequently, the film was developed with a 2.5% triethanolamine aqueous solution, washed with water, placed in an electric furnace at 600 ° C. and baked for 1 hour, and the state of the pattern was observed with an optical microscope. The results are shown in Table 3.

Example 15
Except that the inorganic particles were replaced with ruthenium oxide, the same procedure as in Example 14 was performed, and the state of the pattern was observed with an optical microscope. The results are shown in Table 3.

Example 16
Except that the inorganic particles were replaced with alumina, the same operation as in Example 14 was performed, and the state of the pattern was observed with an optical microscope. The results are shown in Table 3.

  According to Table 1, it can be seen that the polymerizable compound of the present invention has a low thermal decomposition temperature of the cured product. According to Tables 2 and 3, the polymerizable composition containing the polymerizable compound of the present invention has a good pattern state after curing and baking regardless of whether screen printing or photolithography is adopted as a patterning method. It can be seen that there is no coloring.

  The polymerizable compound of the present invention is a material suitable for a fired paste used for forming PDP partition walls, wiring circuits, and the like.

It is ^H 1 -NMR spectrum of Compound (M-1). It is ^H 1 -NMR spectrum of Compound (A-1). It is ^H 1 -NMR spectrum of Compound (M-2). It is ^H 1 -NMR spectrum of Compound (A-2).

Claims (9)

  A polymerizable compound having one or more carbonate bonds, one or more acetal bonds, and one or more (meth) acryloyl groups in one molecule. The polymerizable compound according to claim 1 represented by the general formula (1).

(In General Formula (1), R ¹ is a C1-C12 monofunctional or polyfunctional alcohol-derived organic residue, and R ² is an organic residue derived from one or more C1-C12 polyfunctional alcohols. R ³ is a C1-4 alkylene group or a C1-4 polyalkylene oxide group having a polymerization degree of 2 to 10, R ⁴ is a hydrogen atom or a methyl group, and n is an integer of 1 to 100 And m is an integer from 1 to 12.)   A polymerizable composition comprising the polymerizable compound according to claim 1.   The polymerizable composition according to claim 3, comprising inorganic particles.   The polymerizable composition according to claim 4, wherein the inorganic particles include at least one selected from metal powder, glass powder, black pigment, and ceramic fine particles.   The polymerizable composition according to any one of claims 3 to 5, comprising a thermally decomposable polymer.   The polymerizable composition according to claim 6, wherein the thermally decomposable polymer is a (meth) acrylic polymer.   The polymerizable composition according to any one of claims 3 to 7, comprising a polymerization initiator.   The molded object obtained by polymerizing the polymeric composition in any one of Claim 3-8.

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