JP5056757B2 - Photosensitive resin composition, photosensitive film and pattern forming method - Google Patents

Description

  The present invention relates to a photosensitive resin composition, a photosensitive film, and a pattern forming method. More specifically, it is used for a display panel such as a flat panel display having a display cell composed of a dielectric, an electrode, a resistor, a phosphor, a partition, a color filter, and a black matrix, and an advanced mounting material for electronic components. In the production of a circuit board having a fine circuit pattern, a photosensitive resin composition that is excellent in the thermal decomposability of an organic component and can be suitably used for forming a highly accurate pattern, and a photosensitive property comprising the composition The present invention relates to a photosensitive film having a resin layer and a pattern forming method using the composition or the photosensitive film.

  In recent years, there is an increasing demand for higher density and higher definition for pattern processing in circuit boards and display panels. Among such display panels that have been increasing in demand, particularly flat panel displays (hereinafter referred to as “FPD”) such as plasma display panels (hereinafter also referred to as “PDP”) and field emission displays (hereinafter also referred to as “FED”). ) Is attracting attention.

  FIG. 1 is a schematic diagram showing a cross-sectional shape of an AC type PDP. In FIG. 1, reference numerals 101 and 102 denote opposing glass substrates, and reference numerals 103 and 111 denote partition walls. Cells are partitioned by the glass substrate 101, the glass substrate 102, the rear partition wall 103, and the front partition wall 111. 104 is a transparent electrode fixed to the glass substrate 101, 105 is a bus electrode formed on the transparent electrode 104 for the purpose of reducing the resistance of the transparent electrode 104, and 106 is an address electrode fixed to the glass substrate 102. It is. 107 is a fluorescent material held in the cell, 108 is a dielectric layer formed on the surface of the glass substrate 101 so as to cover the transparent electrode 104 and the bus electrode 105, and 109 is used to cover the address electrode 106. A dielectric layer is formed on the surface of the glass substrate 102, and 110 is a protective film made of, for example, magnesium oxide. In a color FPD, a color filter (red / green / blue) or a black matrix may be provided between the glass substrate and the dielectric layer in order to obtain a high contrast image.

  As a method for forming FPD members such as partition walls, electrodes, resistors, phosphors, color filters, and black matrices, (1) a non-photosensitive resin is screen-printed on a substrate to form a desired pattern; (2) A photosensitive resin layer is formed on a substrate, and the photosensitive resin layer is irradiated with infrared rays or ultraviolet rays through a photomask on which a desired pattern is drawn, and then developed. Thus, a photolithography method is known in which a desired pattern remains on a substrate and is baked (see, for example, Patent Document 1).

  However, the screen printing method has a problem that the demand for pattern accuracy becomes very strict as the panel becomes larger and the definition becomes higher, and cannot be handled by ordinary screen printing. Further, although the photolithography method is excellent in pattern accuracy, when the film thickness is large, the sensitivity of the depth method is insufficient and the pattern accuracy is deteriorated, or the heat of the photosensitive resin composition in the baking process is reduced. There was a problem that poor degradability and significant shrinkage were observed.

  In order to improve the sensitivity of the photosensitive resin composition, it is known to use a resin that reacts with a photocuring agent by light irradiation (for example, see Patent Document 2). As such a resin, a resin having an ethylenically unsaturated bond is known. In order to obtain this resin, for example, a process of reacting a carboxyl group- or hydroxyl group-containing resin with an isocyanate group-containing (meth) acrylate Is required.

However, when this method is used, in addition to the fact that the addition reaction between the carboxyl group- or hydroxyl group-containing resin and the isocyanate group-containing (meth) acrylate cannot be precisely performed, and the storage stability of the resin produced by the addition reaction is deteriorated. There is a demerit that the isocyanate group-containing (meth) acrylate has toxicity.
Japanese Patent Laid-Open No. 11-44949 JP 2005-275071 A

  The present invention is intended to solve the problems associated with the prior art as described above, can form a highly accurate pattern, is excellent in the thermal decomposability of organic components, and shrinks after firing. An object is to provide a small amount of photosensitive resin composition.

  In addition, the present invention provides a photosensitive film having a photosensitive resin layer formed from the photosensitive resin composition, capable of forming a highly accurate pattern and having excellent thermal decomposability of an organic component, Another object of the present invention is to provide a pattern forming method using the composition or photosensitive film of the present invention and a method for producing a flat panel display including the pattern forming method.

  As a result of intensive studies to solve the above problems, the present inventors can form a highly accurate pattern with a photosensitive resin composition containing an alkali-soluble resin having an SH group and a polyfunctional (meth) acrylate. The present inventors have found that the organic component is excellent in thermal decomposability and has little shrinkage after firing, thereby completing the present invention.

  That is, the photosensitive resin composition according to the present invention comprises an alkali-soluble resin (A) having at least one SH group, a polyfunctional (meth) acrylate (B), a photopolymerization initiator (C), and inorganic particles (D ). In the photosensitive resin composition, it is preferable that at least a part of the inorganic particles (D) is a glass powder.

  The alkali-soluble resin (A) comprises an alkali-soluble functional group-containing monomer (A2) and a (meth) acrylic acid derivative (A3) in the presence of a compound (A1) having at least two SH groups in one molecule. A (meth) acrylic resin obtained by polymerization is preferred, and the compound (A1) is preferably an ester of an SH group-containing carboxylic acid and a polyhydric alcohol.

  The polyfunctional (meth) acrylate (B) preferably has a group represented by the following formula (1).

[In formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents a divalent organic group, and R ³ represents a monovalent organic group]
Moreover, it is preferable that the said polyfunctional (meth) acrylate (B) is a compound represented by following formula (2).

ZOCH (CH ₂ OZ) ₂ (2)
[In formula (2), Z is represented by the following formula (3).

[In formula (3), n is a real number of 1 to 10]]
The photosensitive film which concerns on this invention has the photosensitive resin composition layer obtained from the said photosensitive resin composition, It is characterized by the above-mentioned.

  The pattern forming method according to the present invention includes (I) a step of forming a photosensitive resin composition layer obtained from the photosensitive resin composition according to any one of claims 1 to 6 on a substrate, and (II) the photosensitivity. A step of exposing the photosensitive resin composition layer to form a latent image of the pattern, (III) a step of developing the photosensitive resin composition layer after exposure to form a pattern, and (IV) firing the pattern It includes a process step. In the step (I), it is preferable to form a photosensitive resin composition layer on a substrate using the photosensitive film.

  The flat panel display manufacturing method according to the present invention forms at least one display panel member selected from a dielectric, an electrode, a resistor, a phosphor, a partition, a color filter, and a black matrix by the pattern forming method. Including the step of: The display panel is preferably a plasma display panel.

  The photosensitive resin composition and the photosensitive film of the present invention can form a highly accurate pattern, have excellent thermal decomposability of organic components, and have little shrinkage after firing. It can be suitably used for forming a member constituting a display cell and forming a member of a highly mounting material for an electronic component.

FIG. 1 is a schematic diagram showing a cross-sectional shape of an AC FPD (specifically, a PDP). FIG. 2 is a schematic diagram showing evaluation points in the pattern evaluation in Examples 1 to 34 and Comparative Examples 1 to 15. FIG. 3 is an IR spectrum of the SH group-containing methacrylic resin (A1).

Explanation of symbols

101 Glass substrate 102 Glass substrate 103 Back partition 104 Transparent electrode 105 Bus electrode 106 Address electrode 107 Fluorescent substance 108 Dielectric layer 109 Dielectric layer 110 Protective layer 111 Front partition A A Partition pattern B Cut surface details

  Hereinafter, the photosensitive resin composition, photosensitive film, and pattern forming method according to the present invention will be described in detail.

[Photosensitive resin composition]
The photosensitive resin composition of the present invention contains an alkali-soluble resin (A) having at least one SH group, a polyfunctional (meth) acrylate (B), a photopolymerization initiator (C), and inorganic particles (D). To do. In the photosensitive resin composition of the present invention, at least a part of the inorganic particles (D) is preferably glass powder.

<Alkali-soluble resin (A) having SH group>
The alkali-soluble resin (A) having an SH group (hereinafter also referred to as “SH group-containing resin (A)”) used in the composition of the present invention has at least one SH group and is alkali-soluble. Although it does not specifically limit, For example, the (meth) acrylic resin which has SH group is preferable. In the present invention, “alkali-soluble” refers to a property of being dissolved in an alkaline developer to such an extent that the desired development processing can be performed.

  The SH group-containing resin (A) reacts with a polyfunctional (meth) acrylate (B) described later by an ene-thiol reaction by light irradiation, and the resin (A) itself further polymerizes. The sensitivity is higher than that of the resin. Further, since the molecular weight of the resin is increased by this polymerization, the pattern shape after development is improved.

  In the presence of the compound (A1) having at least two SH groups in one molecule, the (meth) acrylic resin having an SH group described above contains an alkali-soluble functional group-containing monomer (A2) and a (meth) acrylic acid derivative (A3). ).

  Examples of the compound (A1) having at least two SH groups in one molecule include esters of SH group-containing carboxylic acids and polyhydric alcohols. Examples of the SH group-containing carboxylic acid include thioglycolic acid or 3-mercaptopropionic acid. Examples of the polyhydric alcohol include ethylene glycol, tetraethylene glycol, butanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitol and the like.

  This compound (A1) acts as a chain transfer agent in the above copolymerization reaction, and it is considered that the resulting resin (A) preferably has SH groups mainly formed at its ends. Moreover, it is preferable to use the said compound (A1) also from a viewpoint of work odor.

  The said compound (A1) may be used individually by 1 type, and may use 2 or more types together. The usage-amount of the said compound (A1) is about 0.5 to 10 weight with respect to 100 weight part of all the monomers used for the said copolymerization.

Examples of the alkali-soluble functional group-containing monomer (A2) include (meth) acrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, mesaconic acid, cinnamic acid, and succinic acid mono (2- (meth) Acryloyloxyethyl), 2-methacryloyloxyethylphthalic acid, 2-acryloyloxyethyl hydrogen phthalate, 2-acryloyloxypropyl hydrogen phthalate, 2-acryloyloxypropyl hexahydrohydrogen phthalate, 2-acryloyloxypropyl tetrahydrophthalate, carboxyl group-containing monomers such as ω-carboxy-polycaprolactone mono (meth) acrylate;
Hydroxyl group-containing monomers such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (α-hydroxymethyl) acrylate;
Examples thereof include monomers having an alkali-soluble functional group and an unsaturated bond, such as phenolic hydroxyl group-containing monomers such as o-hydroxystyrene, m-hydroxystyrene, and p-hydroxystyrene. Among these monomers, (meth) acrylic acid, 2-methacryloyloxyethylphthalic acid, 2-acryloyloxyethyl hydrogen phthalate, 2-acryloyloxypropyl hydrogen phthalate, 2-acryloyloxypropyl hexahydrohydrogen phthalate, 2-acryloyl Oxypropyltetrahydrohydrogenphthalate and 2-hydroxyethyl (meth) acrylate are preferred.

  By copolymerizing the alkali-soluble functional group-containing monomer (A2), alkali solubility can be imparted to the resin (A). The content of the structural unit derived from the alkali-soluble functional group-containing monomer (A2) is usually from 5 to 90% by weight, preferably from 10 to 80% by weight, particularly preferably from 15 to 15% in all the structural units of the resin (A). 70% by weight.

  The (meth) acrylic acid derivative (A3) is not particularly limited as long as it is a (meth) acrylic acid derivative copolymerizable with the alkali-soluble functional group-containing monomer (A2). For example, methyl (meth) acrylate, Ethyl (meth) acrylate, n-butyl (meth) acrylate, lauryl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, totyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate , (Meth) acrylates other than the monomer (A2) such as glycidyl (meth) acrylate and dicyclopentanyl (meth) acrylate.

  In the present invention, for example, styrene, methyl (meth) acrylate, ethyl (meth) acrylate instead of the (meth) acrylic acid derivative (A3) or in addition to the (meth) acrylic acid derivative (A3). Alternatively, a macromonomer having a polymerizable unsaturated group such as a (meth) acryloyl group, an allyl group, or a vinyl group may be used at one chain end of a polymer obtained from benzyl (meth) acrylate or the like.

(Radical polymerization initiator)
In the copolymerization, it is preferable to use a radical polymerization initiator. As the radical polymerization initiator, a radical polymerization initiator used for polymerization of a vinyl monomer can be used. For example, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutylnitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 1,1′-azobis Azo compounds such as (1-cyclohexanecarbonitrile), dimethyl-2,2′-azobisisobutyrate, 4,4′-azobis (4-cyanovaleric acid); t-butyl peroxybivalate, t-butyl Examples thereof include organic peroxides of peroxyesters such as peroxy 2-ethylhexanoate and cumylperoxy 2-ethylhexanoate. These radical polymerization initiators may be used alone or in combination of two or more. The usage-amount of these radical polymerization initiators is about 0.1-10 weight with respect to 100 weight part of all the monomers used for the said copolymerization.

  The weight average molecular weight (hereinafter also referred to as “Mw”) of the SH group-containing resin (A) thus obtained is a polystyrene equivalent value measured by gel permeation chromatography (GPC), preferably 5,000. ~ 100,000, more preferably 10,000 to 50,000. Mw can be controlled by appropriately selecting conditions such as the copolymerization ratio, composition, chain transfer agent, and polymerization temperature of the monomer. When Mw is lower than the above range, film roughness after development is likely to occur, and when Mw exceeds the above range, the solubility of the unexposed portion in the developer may be reduced and resolution may be reduced. .

  The glass transition temperature (Tg) of the (meth) acrylic resin is 0 to 120 ° C, preferably 10 to 100 ° C. When the glass transition temperature is lower than the above range, the coating film tends to be tacky and is difficult to handle. On the other hand, when the glass transition temperature exceeds the above range, the adhesion to the glass substrate as the support may be deteriorated or transfer may not be possible. In addition, the said glass transition temperature can be suitably adjusted by changing the quantity of the said compound (A1), a monomer (A2), and a (meth) acrylic acid derivative (A3).

  The acid value of the SH group-containing resin (A) is preferably in the range of 20 to 200 mgKOH / g, more preferably 30 to 160 mgKOH / g. When the acid value is 20 mgKOH / g or less, the unexposed portion after exposure is not easily removed with an alkaline developer, and it tends to be difficult to form a high-definition pattern. On the other hand, when the acid value is 200 mgKOH / g or more, the portion cured by the exposure light is easily eroded by the alkali developer, and it tends to be difficult to form a high-definition pattern.

<Multifunctional (meth) acrylate (B)>
The polyfunctional (meth) acrylate (B) used in the composition of the present invention may be any bifunctional or higher (meth) acrylate.

Specifically, allylated cyclohexyl di (meth) acrylate, 2,5-hexanedi (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, ethylene glycol Di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, glycerol di (meth) acrylate, methoxylated cyclohexyl di (meth) acrylate, neopentyl glycol di Di (meth) taacrylates such as (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, triglycerol di (meth) acrylate;
Pentaerythritol tri (meth) acrylate, trimethylolpropane (meth) acrylate, trimethylolpropane PO-modified tri (meth) acrylate, trimethylolpropane EO-modified tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol Polyfunctional (meth) acrylates such as monohydroxypenta (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, benzyl mercaptan (meth) acrylate;
Examples include (meth) acrylates in which 1 to 5 of the aromatic ring hydrogen atoms in the compound are substituted with chlorine or bromine atoms.

  The polyfunctional (meth) acrylate (B) is preferably the following formula (1)

[In formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents a divalent organic group, and R ³ represents a monovalent organic group]
A compound having at least 1, more preferably at least 3 groups represented by the formula (2)
ZOCH (CH ₂ OZ) ₂ (2)
[In formula (2), Z is represented by the following formula (3).

[In formula (3), n is a real number of 1 to 10]]
The compound represented by these is mentioned.

  By using a compound in which n is in the above range, a pattern with little dimensional change due to development or baking can be formed.

  By using the above-mentioned compound as the polyfunctional (meth) acrylate (B), a significant shrinkage does not occur after pattern baking, and a high-definition pattern can be formed, and a photosensitive resin composition excellent in thermal decomposability Is obtained.

  The compound represented by the above formula (2) is obtained by addition reaction of tris (polyoxypropylene) glyceryl ether and 2- (vinyloxyethoxy) ethyl methacrylate as represented by the following formula (4). It is done.

[In formula (4), Z is represented by the above formula (3), and R is represented by the following formula (5).

[In formula (5), n is a real number of 1 to 10]]
In addition, n in the formula (3) is a poly-polystyrene obtained by the following formula from the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) of the compound represented by the formula (2). It is the average degree of polymerization of oxypropylene.

Average degree of polymerization (n) of formula (3) = {(Mw—of sites other than polyoxypropylene
Molecular weight (= 201)) / molecular weight of oxypropylene moiety (= 58)} ÷ 3
Moreover, n in Formula (5) is the polyoxypropylene calculated | required by the following formula from the weight average molecular weight (Mw) of polystyrene conversion measured by the gel permeation chromatography (GPC) of tris (polyoxypropylene) glyceryl ether. The average degree of polymerization.

Average degree of polymerization (n) of formula (5) = {(Mw—of sites other than polyoxypropylene
Molecular weight (= 92)) / molecular weight of oxypropylene moiety (= 58)} ÷ 3
As for the weight average molecular weight (Mw) of the said tris (polyoxypropylene) glyceryl ether, 270-1800 are preferable. When the weight average molecular weight of tris (polyoxypropylene) glyceryl ether is in the above range, a pattern with little dimensional change due to development or baking can be formed.

  As the catalyst used in the addition reaction, an acid is suitable. Examples of the acid include 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, Aliphatic polycarboxylic acids such as tartaric acid and citric acid; aromatic carboxylic acids such as benzoic acid and terephthalic acid; benzenesulfonic acid, p-toluenesulfonic acid, p-toluenesulfonic acid pyridinium salt, p-toluenesulfonic acid quinolinium salt Aromatic sulfonic acids or salts thereof such as; sulfates such as sodium sulfate, potassium sulfate, magnesium sulfate, calcium sulfate, nickel sulfate, copper sulfate, zirconium sulfate; hydrogen sulfates such as sodium hydrogen sulfate and potassium hydrogen sulfate; Mineral acids such as hydrochloric acid, phosphoric acid, polyphosphoric acid; phosphovanadmolybdic acid, lanta Heteropolyacids such as gustmolybdic acid and silicic acid moisturic acid; acidic zeolite; base resin is phenolic resin or styrenic resin, and shows any form of gel type, porous type or macroporous type, and sulfonic acid And acidic ion exchange resins having at least one ion exchange group selected from the group consisting of a group and an alkylsulfonic acid group.

  The said catalyst may be used individually by 1 type, and may use 2 or more types together. Among these, oxalic acid, maleic acid, potassium hydrogen sulfate, hydrochloric acid, sulfuric acid, and phosphoric 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 for vinyl ether. Therefore, it is necessary to strictly control the temperature, but in the case of hydrochloric acid, in particular, it does not act as a cationic polymerization initiator and works selectively only for the addition reaction. It is advantageous and is a particularly preferred catalyst.

  The amount of the catalyst used is appropriately set according to the amount of tris (polyoxypropylene) glyceryl ether and 2- (vinyloxyethoxy) ethyl methacrylate used for the addition reaction and the type of tris (polyoxypropylene) glyceryl ether. However, from the viewpoints of yield, catalyst stability, productivity, and economy, for example, with respect to 100 parts by weight of 2- (vinyloxyethoxy) ethyl methacrylate, preferably 0.0005 parts by weight or more, More preferably, it is 0.001 part by weight or more. Moreover, Preferably it is 3 weight part or less, More preferably, it is 1 weight part or less.

  The said polyfunctional (meth) acrylate (B) may be used individually by 1 type, or may be used in combination of 2 or more type. Content of the said polyfunctional (meth) acrylate (B) in the composition of this invention is 20-200 weight part normally with respect to 100 weight part of said SH group containing resin (A), Preferably it is 30-100 weight part. Range. When there is too little content of polyfunctional (meth) acrylate (B), an exposed part will become easy to be eroded by a developing solution, and a pattern cannot be formed. If the content is too large, the development process takes a long time, which is not preferable for production. Furthermore, shrinkage increases during firing, causing peeling.

<Photopolymerization initiator (C)>
As the photopolymerization initiator (C) used in the composition of the present invention, a radical is generated in an exposure step described later, and a polymerization reaction of the SH group-containing resin (A) and the polyfunctional (meth) acrylate (B). The compound is not particularly limited as long as it is a compound that initiates.

  Specifically, benzophenone, methyl o-benzoylbenzoate, 4,4-bis (dimethylamine) benzophenone, 4,4-bis (diethylamino) benzophenone, 4,4-dichlorobenzophenone, 4-benzoyl-4-methyldiphenyl Ketone, dibenzyl ketone, fluorenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenyl-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyldichloroacetophenone, Thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propylthioxanthone, 2,4-diethylthioxanthone, benzyldimethylketanol Benzylmethoxyethyl acetal, benzoin, benzoin methyl ether, benzoin butyl ether, anthraquinone, 2-t-butylanthraquinone, 2-amylanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibenzosuberone, methyleneanthrone, 4-azidobenzal Acetophenone, 2,6-bis (p-azidobenzylidene) cyclohexanone, 2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone, 2-phenyl-1,2-butadion-2- (o-methoxycarbonyl) Oxime, 1-phenyl-propanedione-2- (o-ethoxycarbonyl) oxime, 1,3-diphenyl-propanetrione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-eth Xyl-propanetrione-2- (o-benzoyl) oxime, Michler's ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propan-1-one, 2-benzyl-2-dimethylamino -1- (4-morpholinophenyl) butanone-1,2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2′-dimethoxy-1,2-diphenylethane-1-one, Bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenyl Phosphine oxide, naphthalene sulfonyl chloride, quinoline sulfonyl chloride, N-F Nylthioacridone, 4,4-azobisisobutyronitrile, diphenyl disulfide, benzthiazole disulfide, triphenylformine, camphorquinone, carbon tetrabrominated, tribromophenyl sulfone, benzoin peroxide, eosin and methylene blue And a combination of a photoreducing dye such as ascorbic acid and a reducing agent such as triethanolamine.

  The said photoinitiator (C) may be used individually by 1 type, or may be used in combination of 2 or more type. The photopolymerizable initiator (C) is usually 0.1 to 50 parts by weight, preferably 100 parts by weight of the total amount of the SH group-containing resin (A) and the polyfunctional (meth) acrylate (B), preferably It is used in the range of 0.5 to 40 parts by weight. If the amount is less than 0.1 part by weight, the effect of improving the photosensitivity may not be exhibited. If the amount exceeds 50 parts by weight, the residual ratio of the exposed part may be too small.

<Inorganic particles (D)>
The inorganic particles (D) used in the composition of the present invention vary depending on the type of forming material. In particular, as the inorganic particles used in the dielectric and the partition wall forming material constituting the FPD, it is preferable that at least a part of the inorganic particles (D) is glass powder.

  Examples of the glass powder used in the composition of the present invention include a low melting point glass powder having a heat softening point of 300 to 650 ° C., preferably 350 to 600 ° C. If the thermal softening point of the glass powder is lower than the above range, the glass powder will melt at the stage where the organic substance such as resin is not completely decomposed and removed in the baking process of the photosensitive resin layer formed from the composition. . Therefore, a part of the organic substance remains in the formed member, and as a result, members such as the dielectric layer and the partition are colored, and the light transmittance may be reduced. On the other hand, when the thermal softening point of the glass powder exceeds the above range, it is necessary to fire at a high temperature, so that the glass substrate is likely to be distorted.

Examples of the glass powder include (1) Bi ₂ O ₃ —ZnO—B ₂ O ₃ system, (2) Bi ₂ O ₃ —SiO ₂ —B ₂ O ₃ system, and (3) Bi ₂ O ₃ —SiO. ₂ -B ₂ O ₃ -Li ₂ O _{system, (4) Bi 2 O 3} -SiO 2 -B 2 O 3 -Na 2 O _{based, (5) Bi 2 O 3} -SiO 2 -B 2 O 3 -K ₂ O _{system, (6) Bi 2 O 3} -SiO 2 -Li 2 O _{system, (7) Bi 2 O 3} -SiO 2 -Na 2 O _{-based, (8) Bi 2 O 3} -SiO 2 -K 2 O (9) Bi ₂ O ₃ —SiO ₂ —B ₂ O ₃ —ZnO system, (10) SiO ₂ —B ₂ O ₃ —Li ₂ O system, (11) SiO ₂ —B ₂ O ₃ —Na ₂ O type, (12) SiO ₂ —B ₂ O ₃ —K ₂ O type, (13) SiO ₂ —B ₂ O ₃ —ZrO ₂ —MgO type, (14) SiO ₂ —B ₂ O ₃ —ZrO ₂ — CaO-based, (15) SiO ₂ —B ₂ O ₃ — ZrO _{2-MAO type, (16) SiO 2 -B 2} O 3 -ZrO 2 -SrO _{system, (17) SiO 2 -B 2} O 3 -ZrO 2 -Li 2 O system, (18) SiO ₂ -B ₂ O ₃ —ZrO ₂ —Na ₂ O system, (19) SiO ₂ —B ₂ O ₃ —ZrO ₂ —K ₂ O system, (20) Al ₂ O ₃ —B ₂ O ₃ —SiO ₂ —BaO—CaO— _{Li 2 O-MgO-Na 2} O-SrO-TiO 2 -ZnO _{system, (21) Al 2 O 3} -B 2 O 3 -SiO 2 -BaO-CaO-Li 2 O-MgO-Na 2 O-TiO 2 -ZnO system, and glass powder, such as _{(22) Al 2 O 3 -B} 2 O 3 -SiO 2 -BaO-CaO-Li 2 O-MgO-Na 2 O-Fe 2 O 3 -TiO 2 -ZnO system be able to.

  The shape of the glass powder is not particularly limited. The above glass powders may be used alone or in combination of two or more glass powders having different glass powder compositions, different softening points, different shapes, and different average particle diameters.

  The glass powder preferably contains silicon oxide in the range of 5 to 50% by weight, and more preferably in the range of 10 to 30% by weight, in order to obtain higher definition patterning. Silicon oxide has a function of improving the denseness, strength and stability of the glass and is effective in reducing the refractive index of the glass. In addition, the thermal expansion coefficient can be controlled to prevent peeling due to mismatch with the glass substrate. When the content of silicon oxide is 5% by weight or more, the coefficient of thermal expansion can be suppressed to be small, the occurrence of cracks occurring when baked on a glass substrate can be reduced, and the refractive index can be suppressed to a low level. Moreover, when the content of silicon oxide is 50% by weight or less, the glass transition point and the load softening point can be kept low, and the baking temperature on the glass substrate can be lowered.

  The glass powder preferably contains boron oxide in the range of 10 to 50% by weight, and more preferably in the range of 20 to 45% by weight. When the content of boron oxide is 10% by weight or more, the glass transition point and the load softening point can be kept low, and baking onto the glass substrate can be facilitated. Further, when the content of boron oxide is 50% by weight or less, the chemical stability of the glass can be maintained. Boron oxide is also effective for lowering the refractive index.

  The glass powder preferably contains at least one of barium oxide and strontium oxide so that the total amount is in the range of 1 to 30% by weight, and is contained in the range of 2 to 20% by weight. More preferably. These components are effective in adjusting the thermal expansion coefficient, and have the effect of preventing deformation of the substrate during firing, the effect of imparting electrical insulation, the effect of improving the stability and denseness of the partition walls to be formed, etc. Have. When the content is 1% by weight or more, devitrification due to crystallization of the glass can be prevented, and when the content is 30% by weight or less, the thermal expansion coefficient and the refractive index can be kept small. At the same time, chemical stability can be maintained.

  The glass powder preferably contains aluminum oxide in the range of 1 to 40% by weight. Aluminum oxide has the effect of stabilizing the glass by expanding the vitrification range, and is effective in extending the pot life of the composition. When the content of aluminum oxide is within the above range, the glass transition point and the load softening point can be kept low, and the adhesion to the substrate can be improved.

  The glass powder preferably contains at least one of calcium oxide and magnesium oxide so that the total amount is 1 to 20% by weight. These components have the effect of making the glass easier to melt and controlling the thermal expansion coefficient. When the content is 1% by weight or more, devitrification due to crystallization of the glass can be prevented, and when the content is 15% by weight or less, the chemical stability of the glass can be maintained. .

  The glass powder preferably contains an alkali metal oxide of lithium oxide, sodium oxide and potassium oxide in the range of 1 to 20% by weight. Alkali metal oxides have the effect of facilitating control of the thermal softening point and thermal expansion coefficient of glass and lowering the refractive index as glass powder. Since alkali metal oxides may promote ion migration and diffusion, the total amount of 20% by weight or less can maintain the chemical stability of the glass and keep the thermal expansion coefficient small. .

  The glass powder may contain zinc oxide, titanium oxide, zirconium oxide and the like in addition to the above components.

The average particle diameter of the glass powder is selected in consideration of the shape of the pattern to be produced, but is preferably 0.01 to 10 μm, more preferably 0.1 to 5 μm for pattern formation. Moreover, it is preferable on pattern formation that the specific surface area of glass powder is 0.1-300 m < ² > / g.

  The glass powder may be contained in a composition for forming components other than the dielectric of FPD and barrier ribs (for example, electrodes, resistors, phosphors, color filters, black matrix). In this case, the content of the glass powder varies depending on the use, but is usually 1 to 90 parts by weight, preferably 1 to 80 parts by weight with respect to 100 parts by weight of the total amount of inorganic particles (D) including the glass powder. .

  As inorganic particles (D) used for electrode forming materials such as FPD, LCD, organic EL, printed circuit board, multilayer circuit board, module, inductor and LSI, Al, Ag, Ag—Pd alloy, Au, Ni, Cr, Cu, etc. can be mentioned. Among these, it is preferable to use Ag which is relatively inexpensive and does not cause a decrease in conductivity due to oxidation even when baked in the air. The shape of the inorganic particles (D) used for the electrode forming material is not particularly limited, such as granular, spherical, flake, etc. Even if the same shape of the inorganic particles (D) is used, two or more different shapes are used. You may mix and use an inorganic particle (D). The average particle diameter is preferably 0.01 to 10 μm, more preferably 0.05 to 5 μm, and inorganic particles (D) having different average particle diameters can be mixed and used.

  When the inorganic particles used for these electrode forming materials (hereinafter also referred to as “conductive powder”) and glass powder are used in combination, the content of the glass powder depends on the type of conductive powder. Usually, it is 1-30 weight part normally with respect to 100 weight part of inorganic particles (D) whole quantity.

As a specific example, when Ag, Cu, Ni, Sn, Zn is used as the conductive powder, 1 to 10 parts by weight, preferably 2 parts by weight of the glass powder with respect to 100 parts by weight of the total amount of inorganic particles (D). Use ~ 7 parts by weight.
When using Ag-Pt, 1-10 weight part of glass powder is used with respect to 100 weight part of inorganic particles (D) whole quantity, Preferably 1-5 weight part is used.
When Au or Pt is used, 1 to 5 parts by weight, preferably 1 to 4 parts by weight of glass powder is used with respect to 100 parts by weight of the total amount of inorganic particles (D).
When Al is used, the glass powder is used in an amount of 5 to 30 parts by weight, preferably 9 to 20 parts by weight, based on 100 parts by weight of the total amount of inorganic particles (D).

Inorganic particles (D) used for transparent electrode forming materials such as FPD, LCD and organic EL elements include indium oxide, tin oxide, tin-containing indium oxide (ITO), antimony-containing tin oxide (ATO), and fluorine-added oxidation. Oxidation containing indium (FIO), fluorine-added tin oxide (FTO), fluorine-added zinc oxide (FZO), and one or more metals selected from Al, Co, Fe, In, Sn and Ti Examples thereof include zinc fine particles. Examples of the inorganic particles (D) used for the resistor forming material of PDP include particles made of RuO ₂ or the like.

Inorganic particles (D) used for phosphor forming materials for FPD and PDP are:
For red, Y ₂ O ₃ : Eu ³⁺ , Y ₂ SiO ₅ : Eu ³⁺ , Y ₃ Al ₅ O ₁₂ : Eu ³⁺ , YVO ₄ : Eu ³⁺ , (Y, Gd) BO ₃ : Eu ³⁺ , Zn ₃ (PO ₄ ) ₂ : Mn, etc.
Examples of green include Zn ₂ SiO ₄ : Mn, BaAl ₁₂ O ₁₉ : Mn, BaMgAl ₁₄ O ₂₃ : Mn, LaPO ₄ : (Ce, Tb), Y ₃ (Al, Ga) ₅ O ₁₂ : Tb, and the like. And
For blue, Y ₂ SiO ₅ : Ce, BaMgAl ₁₀ O ₁₇ : Eu ²⁺ , BaMgAl ₁₄ O ₂₃ : Eu ²⁺ , (Ca, Sr, Ba) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu ²⁺ , (Zn, Cd) S: Ag and the like.

Inorganic particles (D) used in color filter forming materials such as FPD, PDP, LCD, and organic EL elements are Fe ₂ O ₃ for red, Cr ₂ O ₃ for green, and blue Examples thereof include CoO.Al ₂ O ₃ .

  Examples of inorganic particles (D) used for black stripe (matrix) forming materials such as FPD, PDP, LCD, and organic EL elements include metals such as Co, Cr, Cu, Fe, Mn, Ni, Ti, and Zn. And oxides thereof, composite oxides, carbides, nitrides, sulfides, silicides, borides, carbon black, graphite, and the like. These may be used alone or in combination of two or more. May be. Among these, metal particles, metal oxide particles and composite oxide particles selected from the group of Co, Cr, Cu, Fe, Mn, Ni and Ti are preferable. Moreover, as an average particle diameter, Preferably it is 0.01-10 micrometers, More preferably, it is 0.05-5 micrometers, Most preferably, it is 0.1-2 micrometers.

  When these inorganic particles and glass powder are used in combination, the content of the glass powder is usually 60 to 90 parts by weight, preferably 70 to 90 parts per 100 parts by weight of the total amount of inorganic particles (D). More preferably, it is 73-86 weight part.

  Content of the inorganic particle (D) in the composition of this invention is the range of 100-2000 weight part with respect to 100 weight part of said SH group containing resin (A), Preferably it is the range of 130-1000 weight part. When the content of the inorganic particles (D) is within the above range, a pattern having a good shape can be formed.

<Ultraviolet absorber>
It is also effective to add an ultraviolet absorber to the photosensitive resin composition of the present invention. By adding a compound having a high ultraviolet absorption effect, a high aspect ratio, high definition, and high resolution can be obtained. As the ultraviolet absorber, an organic dye or an inorganic pigment can be used, and among them, an organic dye or an inorganic pigment having a high UV absorption coefficient in a wavelength range of 350 to 450 nm is preferably used. Specifically, azo dyes, amino ketone dyes, xanthene dyes, quinoline dyes, quinone dyes, amino ketone dyes, anthraquinone dyes, benzophenone dyes, diphenyl cyanoacrylate dyes, triazine dyes, p-aminobenzoic acid dyes Inorganic pigments such as organic dyes such as zinc oxide, titanium oxide, and cerium oxide can be used. In these, since organic dye does not remain in the insulating film after baking, it is preferable because the deterioration of the insulating film characteristics can be reduced. However, from the viewpoint of the reliability of the flat display panel, such as zinc oxide, titanium oxide, and cerium oxide. More preferred are inorganic pigments.

  The said inorganic pigment can be added in the quantity used as the range which is 0.01-10 weight part with respect to 100 weight part of polyfunctional (meth) acrylate (B), Preferably it is 0.03-5 weight part. If the amount of the inorganic pigment added is too small, the effect of adding the ultraviolet light absorber is reduced. If the amount added is too large, the insulating film characteristics after firing may be deteriorated and the film strength may not be maintained.

<Sensitizer>
A sensitizer may be added to the photosensitive resin composition of the present invention in order to improve sensitivity. Examples of the sensitizer include 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propylthioxanthone, 2,4-diethylthioxanthone, 2,3-bis ( 4-diethylaminobenzal) cyclopentanone, 2,6-bis (4-dimethylaminibenzal) cyclohexanone, 2,6-bis (4-dimethylaminobenzal) -4-methylcyclohexanone, Michler's ketone, 4,4- Bis (diethylamino) -benzophenone, 4,4-bis (dimethylamino) chalcone, 4,4-bis (diethylamino) chalcone, p-dimethylaminocinnamylidene indanone, p-dimethylaminobenzylidene indanone, 2- (p -Dimethylaminopheny Vinylene) -isonaphthothiazole, 1,3-bis (4-dimethylaminobenzal) acetone, 1,3-carbonyl-bis (4-diethylaminobenzal) acetone, 3,3-carbonyl-bis (7-diethylaminocoumarin) ), N-phenyl-N-ethylethanolamine, N-phenylethanolamine, N-tolyldiethanolamine, N-phenylethanolamine, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 3-phenyl-5-benzoylthiotetrazole, Examples thereof include 1-phenyl-5-ethoxycarbonylthiotetrazole.

  The above sensitizers may be used alone or in combination of two or more. Some sensitizers can also be used as photopolymerization initiators. The sensitizer is usually added in an amount of 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight with respect to 100 parts by weight of the polyfunctional (meth) acrylate (B). be able to. If the amount of the sensitizer is too small, the effect of improving the photosensitivity may not be exhibited, and if the amount of the sensitizer is too large, the residual ratio of the exposed portion may be too small.

<Polymerization inhibitor>
A polymerization inhibitor may be added to the photosensitive resin composition of the present invention in order to improve the thermal stability during storage. Examples of the polymerization inhibitor include hydroquinone, monoesterified hydroquinone, N-nitrosodiphenylamine, phenothiazine, pt-butylcatechol, N-phenylnaphthylamine, 2,6-di-tert-butyl-p-methylphenol, Examples include chloranil and pyrogallol. The polymerization inhibitor can be added to the composition in an amount usually ranging from 0.001 to 5% by weight.

<Antioxidant>
An antioxidant may be added to the photosensitive resin composition of the present invention in order to prevent oxidation of the SH group-containing resin (A) during storage, particularly the SH group-containing (meth) acrylic resin. Examples of the antioxidant include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, stearyl-β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2 , 6-di-t-4-ethylphenol, 2,2-methylene-bis- (4-methyl-6-t-butylphenol), 2,2-methylene-bis- (4-ethyl-6-t-butylphenol) ), 4,4-butylidenebis- (3-methyl-6-tert-butylphenol), 4,4-thiobis- (3-methyl-6-tert-butylphenol), 4,4-bis- (3-methyl-6) -T-butylphenol), 1,1,3-tris- (2-methyl-6-t-butylphenol), 1,1,3-tris- (2-methyl-4-hydroxy-t-butylphenyl) butyl Emissions, bis [3,3-bis - (4-hydroxy -3-t-butylphenyl) butyric acid] glycol ester, dilauryl thiodipropionate, triphenyl phosphite. The antioxidant can be added to the composition in an amount usually in the range of 0.001 to 5% by weight.

<Organic solvent>
An organic solvent may be added to the photosensitive resin composition of the present invention in order to adjust the viscosity of the solution. Examples of the organic solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, ethyl-3-ethoxypropionate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, methyl Cellosolve, ethyl cellosolve, butyl cellosolve, methoxypropyl acetate, diethyl ketone, methyl butyl ketone, dipropyl ketone, methyl ethyl ketone, dioxane, acetone, cyclohexanone, cyclopentanone, n-pentanol, diacetone alcohol, 4-methyl-2-pen Tanol, cyclohexanol, isobutyl alcohol, isopropyl alcohol, tetrahydride Furan, dimethyl sulfoxide, γ-butyrolactone, bromobenzene, chlorobenzene, dibromobenzene, dichlorobenzene, bromobenzoic acid, chlorobenzoic acid, acetic acid-n-butyl, amyl acetate, ethyl lactate, ethyl lactate-n-butyl, terpineol, Examples include dihydroterpineol, dihydroterpinel acetate, limonene, carveol, carvinyl acetate, citronellol, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dimethyl sulfoxide and the like. The said organic solvent may be used individually by 1 type, or 2 or more types may be mixed and used for it.

<Adhesion aid>
An adhesion assistant may be added to the photosensitive resin composition of the present invention in order to improve the adhesion to the support. As the adhesion assistant, a silane compound is preferably used. Specific examples of the silane compound include n-propyldimethylmethoxysilane, n-butyldimethylmethoxysilane, n-decyldimethylmethoxysilane, n-hexadecyldimethylmethoxysilane, n-icosanedimethylmethoxysilane, and n-propyldiethylmethoxy. Silane, n-butyldiethylmethoxysilane, n-decyldiethylmethoxysilane, n-hexadecyldiethylmethoxysilane, n-icosanediethylmethoxysilane, n-butyldipropylmethoxysilane, n-decyldipropylmethoxysilane, n- Hexadecyldipropylmethoxysilane, n-icosanedipropylmethoxysilane, n-propyldimethylethoxysilane, n-butyldimethylethoxysilane, n-decyldimethylethoxysilane, n-hexadecyldimethyl Ruethoxysilane, n-icosanedimethylethoxysilane, n-propyldiethylethoxysilane, n-butyldiethylethoxysilane, n-decyldiethylethoxysilane, n-hexadecyldiethylethoxysilane, n-icosanediethylethoxysilane, n -Butyldipropylethoxysilane, n-decyldipropylethoxysilane, n-hexadecyldipropylethoxysilane, n-icosanedipropylethoxysilane, n-propyldimethylpropoxysilane, n-butyldimethylpropoxysilane, n-decyldimethyl Propoxysilane, n-hexadecyldimethylpropoxysilane, n-icosanedimethylpropoxysilane, n-propyldiethylpropoxysilane, n-butyldiethylpropoxysilane, n-decyldie Lupropoxysilane, n-hexadecyldiethylpropoxysilane, n-icosanediethylpropoxysilane, n-butyldipropylpropoxysilane, n-decyldipropylpropoxysilane, n-hexadecyldipropylpropoxysilane, n-icosanedipropyl Propoxysilane, n-propylmethyldimethoxysilane, n-butylmethyldimethoxysilane, n-decylmethyldimethoxysilane, n-hexadecylmethyldimethoxysilane, n-icosanemethyldimethoxysilane, n-propylethyldimethoxysilane, n-butyl Ethyldimethoxysilane, n-decylethyldimethoxysilane, n-hexadecylethyldimethoxysilane, n-icosaneethyldimethoxysilane, n-butylpropyldimethoxysilane, n-decyl Propyldimethoxysilane, n-hexadecylpropyldimethoxysilane, n-icosanepropyldimethoxysilane, n-propylmethyldiethoxysilane, n-butylmethyldiethoxysilane, n-decylmethyldiethoxysilane, n-hexadecylmethyldi Ethoxysilane, n-icosanemethyldiethoxysilane, n-propylethyldiethoxysilane, n-butylethyldiethoxysilane, n-decylethyldiethoxysilane, n-hexadecylethyldiethoxysilane, n-icosaneethyl Diethoxysilane, n-butylpropyldiethoxysilane, n-decylpropyldiethoxysilane, n-hexadecylpropyldiethoxysilane, n-icosanepropyldiethoxysilane, n-propylmethyldipropoxysilane, n-butyl Tildipropoxysilane, n-decylmethyldipropoxysilane, n-hexadecylmethyldipropoxysilane, n-icosanemethyldipropoxysilane, n-propylethyldipropoxysilane, n-butylethyldipropoxysilane, n-decyl Ethyldipropoxysilane, n-hexadecylethyldipropoxysilane, n-icosaneethyldipropoxysilane, n-butylpropyldipropoxysilane, n-decylpropyldipropoxysilane, n-hexadecylpropyldipropoxysilane, n- Icosanpropyl dipropoxysilane, n-propyltrimethoxysilane, n-butyltrimethoxysilane, n-decyltrimethoxysilane, n-hexadecyltrimethoxysilane, n-icosanetrimethoxysilane, n-propylto Ethoxysilane, n-butyltriethoxysilane, n-decyltriethoxysilane, n-hexadecyltriethoxysilane, n-icosanetriethoxysilane, n-propyltripropoxysilane, n-butyltripropoxysilane, n-decyltri Propoxysilane, n-hexadecyltripropoxysilane, n-icosanetripropoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-amino Ethyl) 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl)- Examples include 1-propanamine, N, N′-bis- [3- (trimethoxysilyl) propyl] ethylenediamine, and the like. These may be used alone or in combination of two or more.

  As content of the adhesion assistant in the said photosensitive resin composition, Preferably it is 0.05-15 weight part with respect to 100 weight part of said SH group containing resin (A), More preferably, it is 0.1-10 weight Part.

<Solubility promoter>
The composition of the present invention preferably contains a dissolution accelerator for the purpose of exhibiting sufficient solubility in a developer described later. As the dissolution accelerator, a surfactant is preferably used. Examples of such surfactants include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants.

  Examples of the fluorosurfactant include “BM-1000” and “BM-1100” manufactured by BM CHIMIE, “Megafac F142D”, “Same F172” and “Same F172” manufactured by Dainippon Ink & Chemicals, Inc. "F173", "F183", "Florard FC-135", "FC-170C", "FC-430", "FC-431" manufactured by Sumitomo 3M Ltd., "Asahi Glass Co., Ltd." “Surflon S-112”, “S-113”, “S-131”, “S-141”, “S-145”, “S-382”, “SC-101”, “Same” Commercial products such as “SC-102”, “SC-103”, “SC-104”, “SC-105”, and “SC-106” can be mentioned.

  Examples of the silicone surfactant include “SH-28PA”, “SH-190”, “SH-193”, “SZ-6032”, “SF-8428” manufactured by Toray Dow Corning Silicone Co., Ltd. ”,“ DC-57 ”,“ DC-190 ”,“ KP341 ”manufactured by Shin-Etsu Chemical Co., Ltd.,“ F-top EF301 ”,“ same EF303 ”,“ same EF352 ”manufactured by Shin-Akita Kasei Co., Ltd., etc. Can be mentioned.

  Examples of the nonionic surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene distyrenated phenyl ether, polyoxyethylene octyl Examples include polyoxyethylene aryl ethers such as phenyl ether and polyoxyethylene nonylphenyl ether; polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate.

  Examples of commercially available nonionic surfactants include “Emulgen A-60”, “A-90”, “A-550”, “B-66”, and “PP-99” manufactured by Kao Corporation. “(Meth) acrylic acid copolymer polyflow No. 57” and “No. 90” manufactured by Kyoeisha Chemical Co., Ltd. can be mentioned.

  Among the above surfactants, nonionic surfactants are preferable, polyoxyethylene aryl ethers are more preferable, and particularly the following formula (6), since it is easy to remove the photosensitive resin layer in the unexposed area during development. ) Is preferred.

In the above formula (6), R ¹ is an alkyl group having 1 to 5 carbon atoms, preferably a methyl group, p is an integer from 1 to 5, s is an integer from 1 to 5, preferably 2, t is an integer of 1 to 100, preferably an integer of 10 to 20.

  The content of the dissolution accelerator in the composition of the present invention is preferably 0.001 to 20 parts by weight, more preferably 0.01 to 15 parts by weight, with respect to 100 parts by weight of the SH group-containing resin (A). Particularly preferred is 0.1 to 10 parts by weight. When the content of the dissolution accelerator is in the above range, a composition having excellent solubility in a developer can be obtained.

<Preparation of photosensitive resin composition>
The photosensitive resin composition of the present invention comprises the above SH group-containing resin (A), polyfunctional (meth) acrylate (B), photopolymerization initiator (C) and inorganic particles (D), and various other types as required. After the components are prepared so as to have a predetermined composition ratio, they are mixed and dispersed homogeneously with a three roll or kneader.

  The viscosity of the composition can be adjusted as appropriate depending on the amount of inorganic particles (D), thickener, organic solvent, plasticizer, precipitation inhibitor, etc., but the range is 100 to 500,000 cps (centimeters · cm). Poise).

[Photosensitive film]
The photosensitive film of the present invention usually has a support film and a photosensitive resin layer formed thereon, and a protective film may be provided on the surface of the photosensitive resin layer.

<Support film>
The support film constituting the photosensitive film is preferably a resin film having heat resistance and solvent resistance and flexibility. When the support film has flexibility, the paste-like composition can be applied by a roll coater, and the photosensitive film can be stored and supplied in a state of being wound into a roll. In addition, as thickness of a support film, it should just be a range suitable for use, for example, is 20-100 micrometers.

  Examples of the resin forming the support film include fluorine-containing resins such as polyethylene terephthalate, polyester, polyethylene, polypropylene, polystyrene, polyimide, polyvinyl alcohol, polyvinyl chloride, and polyfluoroethylene, nylon, and cellulose.

  The surface of the support film on which the photosensitive resin layer is formed is preferably subjected to a release treatment. Thereby, when forming the member for display panels and the member for electronic components, peeling operation of a support film can be performed easily.

  Furthermore, as the protective film layer that may be provided on the surface of the photosensitive resin layer, a resin film having the same flexibility as the support film can be used, and the surface (surface in contact with the photosensitive resin layer) ) May be subjected to a mold release treatment.

<Method for producing photosensitive film>
The said photosensitive film is obtained by apply | coating the said photosensitive resin composition on the said support film, forming a coating film, drying this coating film, and forming the photosensitive resin layer. After drying, it is rolled or laminated with a protective film. The photosensitive film is also preferably formed by a method in which a photosensitive resin composition is applied to each of the support film and the protective film to form a photosensitive resin layer, and the resin layer surfaces are stacked and pressure-bonded. can do.

  The method for applying the composition onto the support film is not particularly limited as long as it is a method capable of efficiently forming a coating film having a large film thickness (for example, 10 μm or more) and excellent uniformity. Examples include a coating method using a knife coater, a coating method using a roll coater, a coating method using a doctor blade, a coating method using a curtain coater, a coating method using a die coater, and a coating method using a wire coater.

  What is necessary is just to adjust suitably the drying conditions of a coating film so that the residual ratio of the solvent after drying may be less than 2 weight%, for example, is about 0.5 to 60 minutes at the drying temperature of 50-150 degreeC.

  The thickness of the photosensitive resin layer formed as described above is 30 to 300 μm, preferably 50 to 200 μm.

[Pattern formation method]
The pattern forming method of the present invention comprises a step of forming a photosensitive resin layer comprising the above photosensitive resin composition on a substrate (resin layer forming step), and exposing the photosensitive resin layer to form a latent image of the pattern. And a step of developing the photosensitive resin layer to form a pattern (developing step), and a step of baking the pattern (baking step).

  In the present invention, in the resin layer forming step, the photosensitive resin composition may be applied on a substrate to form a coating film, and the coating film may be dried to form a photosensitive resin layer. You may form a photosensitive resin layer on a board | substrate by transferring the photosensitive resin layer which comprises this photosensitive film on a board | substrate using a photosensitive film.

<Resin layer forming step>
In this step, a photosensitive resin layer made of the photosensitive resin composition is formed on the substrate. Examples of the method for forming the photosensitive resin layer include a method in which the photosensitive resin composition is applied on a substrate to form a coating film, and the coating film is dried to form the photosensitive resin layer. And a method of forming a photosensitive resin layer constituting the photosensitive film by transferring it onto a substrate.

  The method for applying the composition onto the substrate is not particularly limited as long as the method can efficiently form a coating film having a large film thickness (for example, 10 μm or more) and excellent uniformity. Examples include a coating method using a knife coater, a coating method using a roll coater, a coating method using a doctor blade, a coating method using a curtain coater, a coating method using a die coater, and a coating method using a wire coater.

  What is necessary is just to adjust suitably the drying conditions of a coating film so that the residual ratio of the solvent after drying may be less than 2 weight%, for example, is about 0.5 to 60 minutes at the drying temperature of 50-150 degreeC.

  The thickness of the photosensitive resin layer formed as described above is 30 to 300 μm, preferably 50 to 200 μm. In addition, you may form the laminated body which has a resin layer of n layer (n shows an integer greater than or equal to 2) by repeating application | coating a composition n times.

  On the other hand, by laminating the photosensitive film on the substrate and transferring the photosensitive resin layer onto the substrate, a resin layer having excellent film thickness uniformity can be easily formed on the substrate. The film thickness of the pattern can be made uniform. When transferring the photosensitive resin layer, a laminate having n layers (n represents an integer of 2 or more) of resin layers may be formed by repeating the transfer n times using the photosensitive film. Or you may form the said laminated body by batch-transferring on the board | substrate using the photosensitive film in which the laminated body which consists of a resin layer of n layers was formed on the support film.

  An example of a transfer process using a photosensitive film is as follows. After peeling off the protective film layer of the photosensitive film used as necessary, the photosensitive film is overlaid so that the surface of the photosensitive resin layer is in contact with the surface of the substrate, and this photosensitive film is heated by a heating roller or the like. After pressure bonding, the support film is peeled off from the resin layer. As a result, the photosensitive resin layer is transferred and adhered to the surface of the substrate.

As the transfer conditions, for example, the surface temperature of the heating roller is 40 to 140 ° C., the roll pressure by the heating roller is 0.1 to 10 kg / cm ² , and the moving speed of the heating roller is 0.1 to 10 m / min. Moreover, the board | substrate may be preheated and the preheating temperature is 40-140 degreeC, for example.

  Examples of the substrate material used in the present invention include a plate-like member made of an insulating material such as glass, silicone, polycarbonate, polyester, aromatic amide, polyamideimide, and polyimide. If necessary, the surface of the plate-like member may be subjected to chemical treatment with a silane coupling agent or the like; plasma treatment; thin film formation treatment by an ion plating method, a sputtering method, a gas phase reaction method, a vacuum deposition method, or the like. Processing may be performed. In the present invention, a glass substrate having heat resistance is preferably used as the substrate. Examples of such a glass substrate include “PD200” manufactured by Asahi Glass Co., Ltd.

<Exposure process>
After forming the photosensitive resin layer on the substrate by the resin layer forming step, exposure is performed using an exposure apparatus. As the exposure is performed by ordinary photolithography, a mask exposure method using a photomask can be employed. As the mask to be used, either a negative type or a positive type is selected depending on the type of the organic component of the photosensitive resin layer. The exposure pattern of the exposure mask varies depending on the purpose, but is, for example, a stripe or lattice having a width of 10 to 500 μm.

  Alternatively, a direct drawing method using a red or blue visible laser beam, an Ar ion laser, or the like without using a photomask may be used.

  The surface of the photosensitive resin layer is selectively irradiated (exposed) with radiation such as ultraviolet rays through an exposure mask to form a pattern latent image on the resin layer. In addition, it is preferable to expose in the state which does not peel the support film coat | covered on the resin layer.

  As the exposure apparatus, a parallel light exposure machine, a scattered light exposure machine, a stepper exposure machine, a proximity exposure machine, or the like can be used. Moreover, when performing exposure of a large area, after applying a photosensitive resin composition on a substrate such as a glass substrate, exposure is performed while being conveyed, thereby exposing a large area with an exposure machine having a small exposure area. be able to.

  Examples of the active light source used in the exposure include visible light, near ultraviolet light, ultraviolet light, electron beam, X-ray, and laser light. Among these, ultraviolet light is preferable, and as the light source, for example, Low pressure mercury lamp, high pressure mercury lamp, super high pressure mercury lamp, halogen lamp, etc. can be used. Among these, an ultra high pressure mercury lamp is preferable.

Exposure conditions vary depending on the coating thickness, but exposure is performed for 0.05 to 1 minute using an ultrahigh pressure mercury lamp with an output of 1 to 100 mW / cm ² . In this case, by using a wavelength filter to narrow the wavelength region of the exposure light, light scattering can be suppressed and pattern formation can be improved. Specifically, pattern formation can be improved by using a filter that cuts off i-line (365 nm) light or a filter that cuts off i-line and h-line (405 nm) light.

<Development process>
After the exposure, the resin layer is developed using the difference in solubility between the photosensitive portion and the non-photosensitive portion in the developer to form a resin layer pattern. Development methods (eg, dipping method, rocking method, shower method, spray method, paddle method, brush method, etc.) and development processing conditions (eg, developer type / composition / concentration, development time, development temperature, etc.) And may be appropriately selected and set according to the type of the resin layer.

  As the developer used in the development step, an organic solvent capable of dissolving the organic component in the resin layer can be used. Further, water may be added to the organic solvent as long as its dissolving power is not lost. When a compound having an acidic group such as a carboxyl group is present in the resin layer, development can be performed with an alkaline aqueous solution.

  Since the inorganic particles (D) contained in the resin layer are uniformly dispersed by the SH group-containing resin (A), the inorganic particles (D) can be obtained by dissolving the resin (A) with a developer and washing. Are also removed at the same time.

  Examples of the alkaline aqueous solution include lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium hydrogen phosphate, diammonium hydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, ammonium dihydrogen phosphate, phosphorus Potassium dihydrogen phosphate, sodium dihydrogen phosphate, lithium silicate, sodium silicate, potassium silicate, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium carbonate, sodium carbonate, potassium carbonate, lithium borate, boric acid Sodium, potassium borate, aqueous ammonia, tetramethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, Bruno isopropylamine, diisopropylamine, ethanolamine, diethanolamine, triethanolamine.

  The concentration of the alkaline aqueous solution is usually 0.01 to 10% by weight, more preferably 0.1 to 5% by weight. If the alkali concentration is too low, the soluble portion is not removed, and if the alkali concentration is too high, the pattern portion may be peeled off and the non-soluble portion may be corroded. The development temperature during development is preferably 20 to 50 ° C. in terms of process control.

  The alkaline aqueous solution may contain additives such as nonionic surfactants and organic solvents. In addition, after the development process with an alkali developer is performed, a washing process is usually performed.

<Baking process>
In order to burn off the organic substance in the resin layer remaining portion (resin layer pattern) after the development, the resin layer pattern is baked in a baking furnace.

  The firing atmosphere varies depending on the composition and the type of substrate, but firing is performed in an atmosphere of air, ozone, nitrogen, hydrogen, or the like. As the firing furnace, a batch-type firing furnace or a belt-type continuous firing furnace can be used.

  As the baking treatment conditions, it is necessary that the organic substance in the resin layer residual portion is burned out. Therefore, the baking temperature is usually 300 to 1000 ° C. and the baking time is 10 to 90 minutes. For example, in the case of forming a pattern on a glass substrate, baking is performed by holding at a temperature of 350 to 600 ° C. for 10 to 60 minutes.

  By the pattern forming method of the present invention including these steps, it is possible to form a display panel member such as a dielectric, an electrode, a resistor, a phosphor, a partition, a color filter, a black matrix, or a circuit pattern of an electronic component. it can. In addition, you may introduce | transduce a 50-300 degreeC heating process in each process of the said transfer, exposure, image development, and baking for the purpose of drying or preliminary reaction.

  The flat display panel manufacturing method of the present invention includes a step of forming at least one display panel member selected from a dielectric, an electrode, a resistor, a phosphor, a partition, a color filter, and a black matrix as described above. It is suitable for the manufacturing method of a plasma display panel.

[Example]
EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited at all by these Examples. In the examples and comparative examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively, unless otherwise specified.

  First, a method for measuring and evaluating physical properties will be described.

[Method for Measuring Weight Average Molecular Weight (Mw) and Weight Average Molecular Weight (Mw) / Number Average Molecular Weight (Mn) (hereinafter referred to as Mw / Mn)]
Mw and Mw / Mn are values in terms of polystyrene measured by gel permeation chromatography (GPC) (“HLC-8220GPC” manufactured by Tosoh Corporation). The GPC measurement was performed using “TSK guard column Super HZM-M” manufactured by Tosoh Corporation as a GPC column under the conditions of a tetrahydrofuran (THF) solvent and a measurement temperature of 40 ° C.

[Method for evaluating pattern after development (Examples 1 to 12, Comparative Examples 1 to 7)]
A panel test piece (150 mm × 150 mm × 2.8 mm) after development was cut, and the pattern cut surface at the position shown in FIG. 2 was observed with a scanning electron microscope (“S4200” manufactured by Hitachi, Ltd.). Height was measured and each was evaluated according to the following criteria. The desired standard is a pattern width of 50 μm, a height of 180 μm, and an interval of 200 μm.
A: Desired standard within ± 3 μm.
B: Within ± 5 μm exceeding the desired standard ± 3 μm.
C: Those exceeding the desired standard ± 5 μm and within ± 10 μm.
D: Desired standard exceeds ± 10 μm.

[Method for evaluating pattern after firing (Examples 1 to 12, Comparative Examples 1 to 7)]
A panel test piece (150 mm × 150 mm × 2.8 mm) after firing was cut, and the pattern cut surface at the position shown in FIG. 2 was observed with a scanning electron microscope (“S4200” manufactured by Hitachi, Ltd.). Height was measured and each was evaluated according to the following criteria. The desired standard is a pattern width of 50 μm, a height of 180 μm, and an interval of 200 μm.
A: The desired standard.
B: Desired standard within ± 3 μm.
C: A desired standard exceeding ± 3 μm and within ± 5 μm.
D: Desired standard exceeds ± 5 μm.

[Evaluation Method of Electrical Resistance Measurement (Examples 13 to 34, Comparative Examples 8 to 15)]
The volume resistance [μΩ · cm] was obtained by preparing a 10 μm-thick coating film on a test piece (150 mm × 150 mm × 2.8 mm) of the panel after firing, and “Resistivity Processor Model Σ-5” manufactured by NPS. Was used to evaluate.

[Measurement method of infrared absorption spectrum]
The absorption spectrum [cm ⁻¹ ] was measured using an “FT-IR / Fourier transform infrared spectrophotometer FT-720” manufactured by HORIBA after the alkali-soluble resin was purified and dried.

[Evaluation Method of Curing Depth (Examples 13 to 34, Comparative Examples 8 to 15)]
An inorganic powder-containing resin layer having a thickness of 10 μm is formed on a glass substrate, and an i-line (ultraviolet light having a wavelength of 365 nm) is irradiated from the glass substrate side toward the inorganic powder-containing resin layer with an ultrahigh pressure mercury lamp. The body-containing resin layer was cured. Here, the irradiation amount was 800 mJ / cm ² . After the exposure, a developing process was performed for 30 seconds by a shower method using a 0.5 mass% sodium carbonate aqueous solution at a liquid temperature of 25 ° C. as a developing solution, followed by washing with ultrapure water. Thereby, the ultraviolet-ray was irradiated and the inorganic powder containing resin which was not hardened | cured was removed. The remaining film thickness of the obtained 5 cm × 5 cm-shaped inorganic powder-containing resin layer was measured using a fine column height measuring device P-10 (manufactured by KLA-TENCOR). In order to express the goodness of the curing depth by A, B and C, it was defined in the following range of remaining film values. The results are shown in the table.
A: Remaining film thickness exceeds 6 μm B: Remaining film thickness is 5-6 μm
C: Remaining film thickness is less than 5 μm [Pattern Evaluation Method (Examples 13 to 34, Comparative Examples 8 to 15)]
A panel test piece (150 mm × 150 mm × 2.8 mm) after pattern development and after firing was cut, and the pattern cut surface was observed with a scanning electron microscope (“S4200”, manufactured by Hitachi, Ltd.). Were measured and evaluated according to the following criteria. The desired standard is a pattern width of 50 μm, a height of 10 μm, and an interval of 100 μm.
A: Within ± 5% of desired standard.
B: Those exceeding the desired standard ± 5% and within ± 10%.
C: Over the desired standard ± 10%.

[Evaluation of pattern adhesion after firing (Examples 13 to 34, Comparative Examples 8 to 15)]
A pattern was prepared and fired on a panel test piece (150 mm × 150 mm × 2.8 mm), and the adhesion between the fired pattern and the support was evaluated. The desired standard is a pattern width of 50 μm, a height of 10 μm, and an interval of 100 μm. Cello tape (manufactured by Nichiban Co., Ltd., registered trademark) was thermocompression bonded with a heating roller. The pressure bonding conditions were such that the surface temperature of the heating roller was 23 ° C., the roll pressure was 4 kg / cm ² , and the moving speed of the heating roller was 0.5 m / min. As a result, the cellophane tape was transferred to the surface of the support and brought into close contact. Evaluation was made by peeling the cellophane from the support.

  A: No pattern peeling.

B: Pattern peeling occurs partially on the substrate.
C: Pattern peeling occurred entirely on the substrate.

[Synthesis Example A1]
55 g of benzyl methacrylate, 45 g of 2-methacryloyloxyethylphthalic acid, 1 g of azobisisobutyronitrile (AIBN), 5 g of pentaerythritol tetrakis (3-mercaptopropionic acid) (manufactured by Sakai Chemical Industry Co., Ltd.) in an autoclave with a stirrer The mixture was stirred and stirred in 150 parts of propylene glycol monomethyl ether under nitrogen atmosphere until uniform. Next, polymerization was carried out at 80 ° C. for 4 hours, and the polymerization reaction was further continued at 100 ° C. for 1 hour, followed by cooling to room temperature and methacrylic resin (A1) having SH groups (hereinafter referred to as “SH group-containing methacrylic resin (A1)). Is also written). The polymerization rate of this SH group-containing methacrylic resin (A1) was 98%, and the SH group-containing methacrylic resin (A1) had a weight average molecular weight of 20000 (Mw / Mn was 1.8). The IR spectrum of the obtained resin is shown in FIG.

[Synthesis Example A2]
The SH group was changed in the same manner as in Synthesis Example A1 except that 5 g of tetraethylene glycol bis (3-mercaptopropionic acid) (manufactured by Sakai Chemical Industry Co., Ltd.) was used instead of pentaerythritol tetrakis (3-mercaptopropionic acid). Methacrylic resin (A2) (hereinafter also referred to as “SH group-containing methacrylic resin (A2)”) was obtained. The polymerization rate of the SH group-containing methacrylic resin (A2) was 98%, and the SH group-containing methacrylic resin (A2) had a weight average molecular weight of 15000 (Mw / Mn was 1.7).

[Synthesis Example A3]
A methacrylic resin as in Synthesis Example A1 except that 5 g of dipentaerythritol hexakis (3-mercaptopropionic acid) (manufactured by Sakai Chemical Industry Co., Ltd.) was used instead of pentaerythritol tetrakis (3-mercaptopropionic acid). (A3) (hereinafter also referred to as “methacrylic resin (A3)”) was obtained. The polymerization rate of this methacrylic resin (A3) was 98%, and the weight average molecular weight of the methacrylic resin (A3) was 25000 (Mw / Mn was 1.9).

[Synthesis Example A4]
A methacrylic resin (A4) was obtained in the same manner as in Synthesis Example A1, except that 5 g of 2,4-diphenyl-4-methyl-1-pentene was used instead of pentaerythritol tetrakis (3-mercaptopropionic acid). The polymerization rate of this methacrylic resin (A4) was 98%, and the weight average molecular weight of the methacrylic resin (A4) was 25000 (Mw / Mn was 2.2).
[Synthesis Example A5]
The SH group was changed in the same manner as in Synthesis Example A1 except that 5 g of trimethylolpropane tris (3-mercaptopropionic acid) (manufactured by Sakai Chemical Industry Co., Ltd.) was used instead of pentaerythritol tetrakis (3-mercaptopropionic acid). A methacrylic resin (A5) (hereinafter also referred to as “SH group-containing methacrylic resin (A5)”) was obtained. The polymerization rate of this SH group-containing methacrylic resin (A5) was 98%, and the weight average molecular weight of the SH group-containing methacrylic resin (A5) was 15000 (Mw / Mn 1.7).

[Synthesis Example A6]
80 g of benzyl methacrylate, 20 g of methacrylic acid, 1 g of azobisisobutyronitrile (AIBN), 5 g of pentaerythritol tetrakis (3-mercaptopropionic acid) (manufactured by Sakai Chemical Industry Co., Ltd.) were charged into an autoclave equipped with a stirrer, and in a nitrogen atmosphere The mixture was stirred in 150 parts of propylene glycol monomethyl ether until uniform. Next, polymerization was carried out at 80 ° C. for 4 hours, and the polymerization reaction was further continued at 100 ° C. for 1 hour, followed by cooling to room temperature and methacrylic resin (A6) having SH groups (hereinafter referred to as “SH group-containing methacrylic resin (A6)). Is also written). The polymerization rate of the SH group-containing methacrylic resin (A6) was 99%, and the SH group-containing methacrylic resin (A6) had a weight average molecular weight of 30000 (Mw / Mn 1.9).
[Synthesis Example A7]
A methacrylic resin (A7) is obtained in the same manner as in Synthesis Example A1, except that 5 g of methyl-3-mercaptopropionate (manufactured by Sakai Chemical Co., Ltd.) is used instead of pentaerythritol tetrakis (3-mercaptopropionic acid). It was. The polymerization rate of this methacrylic resin (A7) was 98%, and the weight average molecular weight of the methacrylic resin (A7) was 25000 (Mw / Mn 2.3).

[Synthesis Example A8]
80 g of 2-phenoxy-ethyl methacrylate, 20 g of methacrylic acid, 1 g of azobisisobutyronitrile (AIBN), 1 g of trimethylolpropane tris (3-mercaptopropionate) (manufactured by Sakai Chemical Industry Co., Ltd.) in an autoclave with a stirrer The mixture was stirred and stirred in 150 parts of propylene glycol monomethyl ether under nitrogen atmosphere until uniform. Next, polymerization was carried out at 80 ° C. for 4 hours, and the polymerization reaction was further continued at 100 ° C. for 1 hour, followed by cooling to room temperature and a methacrylic resin having SH groups (A8) (hereinafter referred to as “SH group-containing methacrylic resin (A8)”). Is also written). The polymerization rate of this SH group-containing methacrylic resin (A8) was 98%, and the SH group-containing methacrylic resin (A8) had a weight average molecular weight of 33,000.

[Synthesis Example A9]
Except that 70 g of 2-phenoxyethyl methacrylate, 15 g of methacrylic acid, 15 g of cyclohexyl methacrylate, and 0.5 g of pentaerythritol tetrakis (3-mercaptopropionate) (manufactured by Sakai Chemical Industry Co., Ltd.) were charged into an autoclave with a stirrer, In the same manner as in Synthesis Example A8, an SH group-containing methacrylic resin (A9) (hereinafter also referred to as “SH group-containing methacrylic resin (A9)”) was obtained. The polymerization rate of this SH group-containing methacrylic resin (A9) was 98%, and the weight average molecular weight of the SH group-containing methacrylic resin (A9) was 46,000.

[Synthesis Example A10]
In the same manner as in Synthesis Example A8 except that 0.5 g of 2,4-diphenyl-4-methyl-1-pentene was used instead of trimethylolpropane tris (3-mercaptopropionate) in Synthesis Example A8. Resin (A10) (hereinafter also referred to as “methacrylic resin (A10)”) was obtained. The polymerization rate of this methacrylic resin (A10) was 98%, and the weight average molecular weight of the methacrylic resin (A10) was 30,000.

[Synthesis Example A11]
A methacrylic resin as in Synthesis Example A9, except that 0.5 g of 2,4-diphenyl-4-methyl-1-pentene was used instead of pentaerythritol tetrakis (3-mercaptopropionate) in Synthesis Example A9. (A11) (hereinafter also referred to as “methacrylic resin (A11)”) was obtained. The polymerization rate of this methacrylic resin (A11) was 98%, and the weight average molecular weight of the methacrylic resin (A11) was 50,000.

[Synthesis Example B1]
Tris (polyoxypropylene) glyceryl ether (Mw300) (manufactured by Wako Pure Chemical Industries, Ltd., n = in the above formula (5)) was added to a 1 liter flask equipped with a stirrer, thermometer, condenser and nitrogen gas introduction tube. 1.2) Add 300 g (hydroxyl group = 3 mol) and 1.56 g of hydrochloric acid (35% aqueous solution, 0.015 mol as HCl component) and stir to generate 600 g (3 mol) of 2- (vinyloxyethoxy) ethyl methacrylate as an exotherm. It was slowly dripped carefully. When the exotherm became mild, the temperature was raised to 60 ° C. and the reaction was carried out for 4 hours. When the reaction product thus obtained was analyzed by IR, the peak in the vicinity of 3500 cm ⁻¹ due to the hydroxyl group almost disappeared, and the desired polyfunctional methacrylate (B1) was obtained.

[Synthesis Example B2]
Tris (polyoxypropylene) glyceryl ether (Mw400) (manufactured by Mitsui Polyurethane Co., Ltd., n = 1. In the above formula (5)) was added to a 2 liter flask equipped with a stirrer, thermometer, condenser and nitrogen gas inlet tube. 8) A polyfunctional methacrylate (B2) was obtained in the same manner as in Synthesis Example B1, except that 400 g (hydroxyl group = 3 mol) and 1.56 g of hydrochloric acid (35% aqueous solution, 0.015 mol as HCl component) were added. When this polyfunctional (meth) acrylate (B2) was analyzed by IR, the peak in the vicinity of 3500 cm ⁻¹ due to the hydroxyl group almost disappeared.

[Synthesis Example B3]
700 g of tris (polyoxypropylene) glyceryl ether of Mw 700 (manufactured by Wako Pure Chemical Industries, Ltd., n = 3.5 in the above formula (5)) instead of Mw 400 of tris (polyoxypropylene) glyceryl ether (hydroxyl group = 3 mol) ) Was used in the same manner as in Synthesis Example B2, except that a polyfunctional methacrylate (B3) was obtained. When this polyfunctional (meth) acrylate (B3) was analyzed by IR, the peak in the vicinity of 3500 cm ⁻¹ due to the hydroxyl group almost disappeared.

[Synthesis Example B4]
Instead of Mw400 tris (polyoxypropylene) glyceryl ether, 1000w (hydroxyl group = 3 mol) of Mw1000 tris (polyoxypropylene) glyceryl ether (Mitsui Polyurethane Co., Ltd., n = 5.2 in the above formula (5)) A polyfunctional methacrylate (B4) was obtained in the same manner as in Synthesis Example B2 except that it was used. When this polyfunctional methacrylate (B4) was analyzed by IR, the peak in the vicinity of 3500 cm ⁻¹ due to the hydroxyl group almost disappeared.

[Synthesis Example B5]
Tris (polyoxypropylene) glyceryl ether (Mw1500) (manufactured by Wako Pure Chemical Industries, Ltd., n = in the above formula (5)) was added to a 3 liter flask equipped with a stirrer, thermometer, condenser and nitrogen gas introduction tube. 8.1) A polyfunctional methacrylate (B5) was obtained in the same manner as in Synthesis Example B1, except that 1500 g (hydroxyl group = 3 mol) and 1.56 g of hydrochloric acid (35% aqueous solution, 0.015 mol as HCl component) were added. . When this polyfunctional (meth) acrylate (B5) was analyzed by IR, the peak in the vicinity of 3500 cm ⁻¹ due to the hydroxyl group almost disappeared.

[Examples 1 to 12]
100 g of organic components (methacrylic resin (60% by weight), polyfunctional methacrylate (35% by weight), photopolymerization initiator (4% by weight) and sensitizer (1% by weight)) shown in Table 1 were mixed with propylene glycol monomethyl ether. After being dissolved in 30 g of (PGME), 300 g of glass powder shown in Table 1 as an inorganic particle, 5 g of surfactant A-60 (manufactured by Kao Corporation) and UV absorber TTO-V-4 (Ishihara Sangyo ( 0.05 g) was added and kneaded with a kneader to prepare an inorganic particle-containing photosensitive resin composition (hereinafter also referred to as “photosensitive paste”).

As a support film, two pieces of polyethylene terephthalate (PET) film (width 200 mm, length 30 m, thickness 50 μm) which have been subjected to release treatment in advance are prepared, and the photosensitive paste is placed on each of these support films by a roll coater. A coating film was formed by coating, and the formed coating film was dried at 90 ° C. for 10 minutes to remove the solvent, thereby forming a photosensitive resin layer having a thickness of 90 μm. Next, the photosensitive resin layers formed on the two PET films were bonded together and thermocompression bonded with a heating roller. The pressure bonding conditions were such that the surface temperature of the heating roller was 90 ° C., the roll pressure was 4 kg / cm ² , and the moving speed of the heating roller was 0.5 m / min. Thus, the photosensitive film which has an inorganic particle containing photosensitive resin layer (thickness 180 micrometers) was produced.

Next, one support film is peeled off, the photosensitive resin layer is overlaid on the surface of a glass test piece (150 mm × 150 mm × 2.8 mm), and the remaining support film is peeled off. Thermocompression bonding was performed with a heating roller. The pressure bonding conditions were such that the surface temperature of the heating roller was 90 ° C., the roll pressure was 4 kg / cm ² , and the moving speed of the heating roller was 0.5 m / min. As a result, the inorganic particle-containing photosensitive resin layer was transferred and adhered to the surface of the glass substrate. The thickness of the transferred inorganic particle-containing photosensitive resin layer was measured and found to be in the range of 180 μm ± 3 μm in any of Examples 1-12.

Next, using a negative chrome mask (pattern width 50 μm, pattern interval 150 μm), the photosensitive resin layer containing inorganic particles was exposed to ultraviolet rays with an ultrahigh pressure mercury lamp having an output of 25 mJ / cm ² from the upper surface. The exposure amount was 200 mJ / cm ² .

  Next, the inorganic particle-containing photosensitive resin layer after exposure was developed by applying a 0.5% aqueous solution of sodium carbonate maintained at 23 ° C. for 180 seconds in a shower. Then, it washed with water using shower spray, the space part which is not photocured was removed, and the lattice-shaped inorganic particle containing photosensitive resin pattern was formed on the glass substrate for panels. The developed pattern was evaluated by the above evaluation method. The results are shown in Table 1.

  Next, the obtained photosensitive resin pattern was baked at 580 ° C. for 30 minutes to form a partition wall pattern. This fired pattern was evaluated by the above evaluation method. The results are shown in Table 1.

  As shown in Table 1, the patterns of Examples 1, 2, and 6 to 10 were particularly excellent in pattern evaluation after development. Moreover, in the pattern evaluation after baking, all Examples 1-12 were favorable, and the chip | tip of the pattern after baking, peeling, etc. were not seen.

[Comparative Examples 1 to 7]
Except for using 100 g of organic components (methacrylic resin (60% by weight), polyfunctional methacrylate (35% by weight), photopolymerization initiator (4% by weight) and sensitizer (1% by weight)) shown in Table 2. A pattern was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 2.

  In Comparative Examples 1 to 6, a desired pattern was observed in the pattern evaluation after development, but pattern chipping or peeling was observed in the pattern evaluation after baking.

  In Comparative Example 7, defective patterns such as insufficient aspect ratio and development residue were observed in pattern evaluation after development. In addition, a pattern with insufficient aspect ratio was observed in the pattern evaluation after firing.

[Examples 13 to 27]
After mixing the organic components shown in Table 3 (methacrylic resin, polyfunctional acrylate, photopolymerization initiator, sensitizer, dissolution accelerator and solvent), the glass powder shown in Table 3 as an inorganic powder in this composition The conductive powder was added and kneaded with a kneader to prepare an inorganic particle-containing photosensitive resin composition (hereinafter also referred to as “photosensitive paste”).

In addition, as the conductive powder described in Table 3,
Ag (specific surface area: 1.5 m ² / g, average particle diameter (D50): 1.5 μm), Cu (average particle diameter (D50): 0.6 μm), Ni (average particle diameter (D50): 0.4 μm) ), Sn (average particle size (D50): 0.5 μm) and Zn (average particle size (D50): 2.0 μm), Ag—Pt (average particle size (D50): 2.5 μm), Pt (average particle size) One of diameter (D50): 2.2 μm, Au (average particle diameter (D50): 0.6 μm), and Al (average particle diameter (D50): 2.0 μm) was used.

As the glass frit, Bi ₂ O ₃ —SiO ₂ —B ₂ O ₃ —Al ₂ O ₃ —ZnO glass frit (indefinite shape, average particle diameter (D50): 3.0 μm, softening point: 520 ° C.) is used. Using.

As a support film, two pieces of polyethylene terephthalate (PET) film (width 200 mm, length 30 m, thickness 50 μm) prepared in advance are prepared, and the photosensitive paste is applied onto the support film by a roll coater. A coating film was formed, and the formed coating film was dried at 100 ° C. for 5 minutes to remove the solvent, thereby forming a photosensitive resin layer having a thickness of 10 μm. Next, a PET film that had been subjected to a release treatment in advance was bonded and thermocompression bonded with a heating roller. The pressure bonding conditions were a heating roller surface temperature of 90 ° C., a roll pressure of 4 kg / cm ² , and a heating roller moving speed of 0.5 m / min. Thus, the photosensitive film which has an inorganic powder containing photosensitive resin layer (10 micrometers in thickness) was produced.

Next, one support film is peeled off, the photosensitive resin layer is overlaid on the surface of a glass test piece (150 mm × 150 mm × 2.8 mm), and the remaining support film is peeled off. Thermocompression bonding was performed with a heating roller. The pressure bonding conditions were such that the surface temperature of the heating roller was 90 ° C., the roll pressure was 4 kg / cm ² , and the moving speed of the heating roller was 0.5 m / min. As a result, the inorganic powder-containing photosensitive resin layer was transferred and adhered to the surface of the glass substrate. When the thickness of the transferred inorganic powder-containing photosensitive resin layer was measured, all of Examples 13 to 27 were in the range of 10 μm ± 1 μm.

Next, using a negative chrome mask (pattern width 50 μm, pattern interval 100 μm), the photosensitive resin layer containing inorganic particles was exposed to ultraviolet rays with an ultrahigh pressure mercury lamp having an output of 25 mJ / cm ² from the upper surface. The exposure amount was 1000 mJ / cm ² .

  Next, the inorganic powder-containing photosensitive resin layer after exposure was developed by applying a 0.5% aqueous solution of sodium carbonate kept at 23 ° C. for 60 seconds in a shower. Then, it washed with water using shower spray, the space part which is not photocured was removed, and the lattice-shaped inorganic particle containing photosensitive resin pattern was formed on the glass substrate for panels. The developed pattern was evaluated by the above evaluation method. The results are shown in Table 3.

  Next, the obtained photosensitive resin pattern was baked at 580 ° C. for 30 minutes to form a partition wall pattern. This fired pattern was evaluated by the above evaluation method. The results are shown in Table 3.

  As shown in Table 3, Examples 13 to 18 were particularly excellent in pattern evaluation after development. Examples 19-26 were good. Moreover, Examples 13-18 were especially excellent in the pattern evaluation after baking. Examples 19 to 26 were good, and no chipping or peeling of the pattern after firing was observed. In the evaluation of the volume resistance, all of Examples 13 to 27 were in the range of 2 to 100 μΩ · cm and were at a level that could be used as electrodes.

[Examples 28 to 34]
After mixing the organic components shown in Table 3 (methacrylic resin, polyfunctional acrylate, photopolymerization initiator, sensitizer, dissolution accelerator, and solvent), the glass powder shown in Table 3 as an inorganic powder and The conductive powder was added and kneaded with a kneader to prepare an inorganic particle-containing photosensitive resin composition (hereinafter also referred to as “photosensitive paste”). The photosensitive paste was printed on a glass substrate (150 mm square, 2.8 mm thick) to a size of 100 mm square using a 325 mesh screen, dried at 100 ° C. for 10 minutes. In any of Examples 28 to 34, the range was 10 μm ± 1 μm.

Next, using a negative chrome mask (pattern width 50 μm, pattern interval 100 μm), the photosensitive resin layer containing inorganic particles was exposed to ultraviolet rays with an ultrahigh pressure mercury lamp having an output of 25 mJ / cm ² from the upper surface. The exposure amount was 1000 mJ / cm ² .

  Next, the inorganic powder-containing photosensitive resin layer after exposure was developed by applying a 0.5% aqueous solution of sodium carbonate kept at 23 ° C. for 60 seconds in a shower. Then, it washed with water using shower spray, the space part which is not photocured was removed, and the lattice-shaped inorganic particle containing photosensitive resin pattern was formed on the glass substrate for panels. The developed pattern was evaluated by the above evaluation method. The results are shown in Table 3.

  Next, the obtained photosensitive resin pattern was baked at 580 ° C. for 30 minutes to form a partition wall pattern. This fired pattern was evaluated by the above evaluation method. The results are shown in Table 3.

As shown in Table 3, Examples 28 and 29 were particularly excellent in pattern evaluation after development in Examples 28 to 34. Examples 30-34 were good. Moreover, in the pattern evaluation after baking, Examples 28 and 29 were particularly excellent. Examples 30 to 34 were good, and no chipping or peeling of the pattern after firing was observed. In the evaluation of the volume resistance, Examples 28 to 34 were in the range of 3 to 100 μΩ · cm, and could be used as electrodes. .
[Comparative Examples 8 to 11]
Comparative Examples 8 to 11 were carried out in the same manner as in Example 13 except that the compositions shown in Table 3 were used, and the same evaluation as in Example 13 was performed. In the pattern evaluation after development, Comparative Examples 8 to 11 resulted in defects. Moreover, in the pattern evaluation after baking, Comparative Examples 8-11 were unsatisfactory, and the chip | tip of the pattern after baking, peeling, etc. were seen. In the evaluation of volume resistance, all of Comparative Examples 8 to 11 were in the range of 6 to 50 μΩ · cm, and were at a level that could be used as electrodes.
[Comparative Examples 12-15]
Comparative Examples 12 to 15 were carried out in the same manner as in Example 28 except that the compositions shown in Table 3 were used, and the same evaluation as in Example 28 was performed. In the pattern evaluation after development, Comparative Examples 12 to 15 resulted in defects. Moreover, in the pattern evaluation after baking, Comparative Examples 12-15 were unsatisfactory, and the chip | tip of the pattern after baking, peeling, etc. were seen. In the evaluation of volume resistance, all of Comparative Examples 12 to 15 were in the range of 3 to 50 μΩ · cm, and were at a level that could be used as electrodes.

  In Table 3, TMP represents trimethylolpropane triacrylate, MTPMP represents 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propan-1-one, and DETX represents 2,4-diethylthioxanthone is shown, and PGME is propylene glycol monomethyl ether. A-60 represents Emulgen A-60 (trade name, manufactured by Kao Corporation, polyoxyethylene distyrenated phenyl ether), and TNOL represents terpineol.

  Moreover, a number shows a mass part.

[Example 35]
(1) Preparation of Inorganic Powder-Containing Photosensitive Resin Composition As inorganic powder, MnCo ₂ O ₄ —CoMn ₂ O ₄ —CuMn ₂ O ₄ —Cu ₃ Mn ₃ O ₈ pigment (specific surface area: 18.9 m ²⁾ / G, average particle diameter (D50): 0.3 μm, hereinafter also referred to as “Pigment 1”) 15 parts and Bi ₂ O ₃ —ZnO—B ₂ O ₃ —BaO—SiO ₂ glass powder (indefinite shape, average Particle size (D50): 0.6 μm, softening point: 456 ° C., linear expansion coefficient: 8.6 × 10 ⁻⁶ / K, hereinafter also referred to as “glass 1”) 95 parts, and alkali-soluble resin (A) 24 parts of SH group-containing methacrylic resin (A8) and 16 parts of trimethylolpropane EO-modified (n≈2) triacrylate (trade name: M360, manufactured by Toagosei Co., Ltd.) as polyfunctional (meth) acrylate (B) And 2-benzyl as a photopolymerization initiator (C) 2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one (hereinafter also referred to as “photoinitiator c-1”) and 2,2-dimethoxy-1,2-diphenylethane 1 part of -1-one (hereinafter also referred to as “photopolymerization initiator c-2”), 0.22 part of 3-methacryloxypropylmethoxysilane as an adhesion assistant, and 20 parts of propylene glycol monomethyl ether as a solvent. It knead | mixed with the bead mill. Next, the kneaded product was filtered with a stainless mesh (400 mesh, 25 μm diameter) to prepare an inorganic powder-containing resin composition (I) for forming a black matrix.

(2) Preparation of transfer film The inorganic powder-containing resin composition (I) prepared in the above step (1) was coated on a support film made of a PET film having a film thickness of 38 μm, which had been subjected to a mold release process in advance, using a blade coater. Then, the coating film was dried at 100 ° C. for 1 minute 30 seconds to remove the solvent, thereby producing a transfer film of the present invention in which an inorganic powder-containing resin layer having a thickness of 6 μm was formed on the support film.

(3) Transfer process of transfer film Using the transfer film prepared in the above step (2), the transfer film is superposed so that the surface of the inorganic powder-containing resin layer is brought into contact with the surface of the glass substrate, and a heating roller is used. Thermocompression bonding was performed. Here, as the pressure bonding conditions, the surface temperature of the heating roller was 90 ° C., the roll pressure was 0.25 MPa, and the moving speed of the heating roller was 0.5 m / min. As a result, the inorganic powder-containing resin layer was transferred and adhered to the surface of the glass substrate.

(4) Inorganic powder-containing resin layer exposure step and development step For the inorganic powder-containing resin layer formed on the glass substrate in the step (3), after the support film is peeled off, an exposure mask (5 cm × 5 cm, A pattern latent image was formed on the inorganic powder-containing resin layer by irradiating i-line (ultraviolet light having a wavelength of 365 nm) with an ultra-high pressure mercury lamp through a pattern width of 50 μm and a pattern interval of 150 μm. The irradiation dose was 800 mJ / cm ² . After the exposure, development treatment was performed for 20 seconds by a shower method using a 0.5 mass% sodium carbonate aqueous solution at a liquid temperature of 25 ° C. as a developing solution, followed by washing with ultrapure water. Thereby, the inorganic powder containing resin of the part which was not irradiated with an ultraviolet-ray was removed, and the inorganic powder containing resin pattern was formed.

(5) Firing step The glass substrate having the inorganic powder-containing resin pattern formed in the step (4) was baked for 30 minutes in a temperature atmosphere of 520 ° C. As a result, a black matrix having a thickness of 2.0 μm was formed on the surface of the glass substrate.

  The composition and black matrix obtained in the above steps were evaluated by the following methods.

[Evaluation of curing depth]
Irradiation of the inorganic powder-containing resin layer formed on the glass substrate in the above step (3) with i-line (ultraviolet light having a wavelength of 365 nm) from the glass substrate side toward the inorganic powder-containing resin layer with an ultra-high pressure mercury lamp. Then, the inorganic powder-containing resin layer was cured. The irradiation dose was 800 mJ / cm ² . After the exposure, the support film is peeled off and then developed for 30 seconds by a shower method using a 0.5 mass% sodium carbonate aqueous solution at a liquid temperature of 25 ° C. as a developer, followed by washing with ultrapure water. Went. This removed the inorganic powder containing resin of the part which was not irradiated with the ultraviolet-ray.

  The residual film thickness of the inorganic powder-containing resin layer obtained in the above step was measured using a fine column height measuring device P-10 (manufactured by KLA-TENCOR). From the measured values, the goodness of the curing depth was evaluated by the following AA, BB and CC. The results are shown in Table 4.

AA: Remaining film thickness exceeds 6 μm BB: Remaining film thickness is 4-6 μm
CC: Remaining film thickness is less than 4 μm [Pattern evaluation after firing (Examples 35 to 38, Comparative Examples 16 to 19)]
The substrate obtained in the above step (5) was observed with a scanning electron microscope, and the patterning property was evaluated by visually observing whether warpage occurred. The occurrence of warpage is represented by AA, BB and CC. The results are shown in Table 4.

  AA: No pattern warpage or peeling from the substrate.

  BB: Pattern warpage occurs but the BM layer does not peel off from the substrate.

CC: The pattern warps and peels off from the substrate.
[Transmission evaluation of black matrix]
A spectrophotometer (UV-2450PC manufactured by Shimadzu Corp., multi-purpose large sample chamber unit MPC-2200 manufactured by Shimadzu Corp.) was used using the black matrix of 5 cm x 5 cm obtained in the above step (5). The transmittance at a wavelength of 550 nm was measured using an accessory (same below). The results are shown in Table 4.
[Reflectance evaluation of black matrix]
The reflectance at a wavelength of 550 nm was measured using a spectrophotometer using the 5 cm × 5 cm-shaped black matrix obtained in the above step (5). The results are shown in Table 4.

[Examples 36 to 40, Comparative Examples 16 to 18]
Except having used the composition of Table 4, it carried out similarly to Example 35, preparation of the inorganic powder containing resin composition, preparation of a transfer film, and formation and evaluation of the black matrix. The results are shown in Table 4.

[Example 41]
(1) Production of Laminated Structure Steps (1) to (4) of Example 35 were performed in the same manner as Example 35, and an inorganic powder-containing resin pattern (linear expansion coefficient 8.6 × 10 ^{− 6} / K), and the upper layer of the inorganic powder-containing resin pattern,
Al ₂ O ₃ —B ₂ O ₃ —Bi ₂ O ₃ —Na ₂ O—SiO ₂ —ZnO-based glass powder (indefinite shape, average grain size (D50): 1.0 μm, softening point: 470 ° C., linear expansion coefficient : 9.2 × 10 ⁻⁶ / K) 100 parts,
15 parts of cyclohexyl methacrylate / 2-phenoxy-ethyl acrylate / 2-hydroxypropyl methacrylate / methacrylic acid copolymer (= 40/30/10/20 (mass ratio)),
5 parts of trimethylolpropane PO-modified triacrylate (trade name: M320, manufactured by Toagosei Co., Ltd.), 5 parts of tripropylene glycol diacrylate (trade name: M220, manufactured by Toagosei Co., Ltd.),
2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 1 part, 2,2-dimethoxy-1,2-diphenylethan-1-one, 0.4 part,
A 25 μm thick layer was formed from an inorganic powder-containing composition comprising 0.1 part of 3-methacryloxypropylmethoxysilane and propylene glycol monomethyl ether acetate.

This layer was irradiated with i-line (ultraviolet light having a wavelength of 365 nm) with an ultrahigh pressure mercury lamp through an exposure mask (5 cm × 5 cm, pattern width 50 μm, pattern interval 200 μm), and a pattern was formed on the inorganic powder-containing resin layer. The latent image of was formed. The irradiation dose was 800 mJ / cm ² . After the exposure, development treatment was performed for 20 seconds by a shower method using a 0.5 mass% sodium carbonate aqueous solution at a liquid temperature of 25 ° C. as a developing solution, followed by washing with ultrapure water. Thereby, the inorganic powder containing resin of the part which was not irradiated with an ultraviolet-ray was removed, and the lamination pattern was obtained.

  The laminated pattern was baked for 30 minutes in a temperature atmosphere of 520 ° C. Thereby, the laminated structure was formed on the surface of the glass substrate. Patterning evaluation after firing was performed by the same method and standard as in Example 35. The results are shown in Table 5.

[Example 42, Comparative Example 19]
(1) Production of laminated structure The same procedure as in Example 41 was performed, except that the composition shown in Table 5 was used. Table 5 shows the patterning evaluation results after firing.

Claims (10)

An alkali-soluble resin (A) having at least one SH group, a polyfunctional (meth) acrylate (B), a photopolymerization initiator (C), and inorganic particles (D) ;
In the presence of the compound (A1) in which the alkali-soluble resin (A) has at least two SH groups in one molecule, the alkali-soluble functional group-containing monomer (A2) and the (meth) acrylic acid derivative (A3) A photosensitive resin composition, which is a (meth) acrylic resin obtained by polymerization .   The photosensitive resin composition according to claim 1, wherein at least a part of the inorganic particles (D) is a glass powder. The compound (A1) The photosensitive resin composition according to claim 1 or 2, characterized in that the SH group-containing carboxylic acid esters of polyhydric alcohols. The said polyfunctional (meth) acrylate (B) has group represented by following formula (1), The photosensitive resin composition in any one of Claims 1-3 characterized by the above-mentioned.

[In formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents a divalent organic group, and R ³ represents a monovalent organic group] The polyfunctional (meth) acrylate (B) is a photosensitive resin composition according to any one of claims 1 to 4, characterized in that a compound represented by the following formula (2).
ZOCH (CH ₂ OZ) ₂ (2)
[In formula (2), Z is represented by the following formula (3).

[In formula (3), n is a real number of 1 to 10]] It has the photosensitive resin composition layer obtained from the photosensitive resin composition in any one of Claims 1-5 , The photosensitive film characterized by the above-mentioned. (I) The process of forming the photosensitive resin composition layer obtained from the photosensitive resin composition in any one of Claims 1-5 on a board | substrate,
(II) a step of exposing the photosensitive resin composition layer to form a latent image of a pattern;
(III) A pattern forming method comprising a step of developing a photosensitive resin composition layer after exposure to form a pattern, and (IV) a step of baking the pattern. In the said process (I), the photosensitive resin composition layer is formed on a board | substrate using the photosensitive film of Claim 6 , The pattern formation method of Claim 7 characterized by the above-mentioned. The pattern forming method according to claim 7 or 8, dielectric, electrode, resistor, phosphor, the barrier ribs, further comprising the step of forming at least one display panel member selected from the color filter and black matrix box A method for manufacturing a flat panel display. The method for manufacturing a flat panel display according to claim 9 , wherein the display panel is a plasma display panel.

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