WO2008023712A1 - Photosensitive resin composition, photosensitive film, and method for formation of pattern - Google Patents

Photosensitive resin composition, photosensitive film, and method for formation of pattern Download PDF

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Publication number
WO2008023712A1
WO2008023712A1 PCT/JP2007/066213 JP2007066213W WO2008023712A1 WO 2008023712 A1 WO2008023712 A1 WO 2008023712A1 JP 2007066213 W JP2007066213 W JP 2007066213W WO 2008023712 A1 WO2008023712 A1 WO 2008023712A1
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WIPO (PCT)
Prior art keywords
photosensitive resin
pattern
resin composition
meth
group
Prior art date
Application number
PCT/JP2007/066213
Other languages
French (fr)
Japanese (ja)
Inventor
Kazunari Kudou
Takeshi Yoshida
Hideaki Masuko
Kouji Itano
Original Assignee
Jsr Corporation
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Filing date
Publication date
Application filed by Jsr Corporation filed Critical Jsr Corporation
Priority to JP2008530926A priority Critical patent/JP5056757B2/en
Priority to KR1020097005618A priority patent/KR101363126B1/en
Publication of WO2008023712A1 publication Critical patent/WO2008023712A1/en

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J9/00—Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
    • H01J9/02—Manufacture of electrodes or electrode systems
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J11/00—Gas-filled discharge tubes with alternating current induction of the discharge, e.g. alternating current plasma display panels [AC-PDP]; Gas-filled discharge tubes without any main electrode inside the vessel; Gas-filled discharge tubes with at least one main electrode outside the vessel
    • H01J11/10—AC-PDPs with at least one main electrode being out of contact with the plasma
    • H01J11/12—AC-PDPs with at least one main electrode being out of contact with the plasma with main electrodes provided on both sides of the discharge space
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J9/00—Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
    • H01J9/24—Manufacture or joining of vessels, leading-in conductors or bases
    • H01J9/241—Manufacture or joining of vessels, leading-in conductors or bases the vessel being for a flat panel display
    • H01J9/242—Spacers between faceplate and backplate

Definitions

  • the present invention relates to a photosensitive resin composition, a photosensitive film, and a pattern forming method.
  • a photosensitive resin composition excellent in the thermal decomposability of organic components and suitable for forming a highly accurate pattern comprising the composition.
  • the present invention relates to a photosensitive film having a photosensitive resin layer and a pattern forming method using the composition or the photosensitive film.
  • FIG. 1 is a schematic diagram showing a cross-sectional shape of an AC type PDP.
  • 101 and 102 are opposing glass substrates
  • 103 and 111 are partition walls
  • cells are defined by the glass substrate 101, the glass substrate 102, the rear partition wall 103, and the front partition wall 111.
  • Electrode. 107 is a fluorescent substance held in the cell
  • 10 8 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
  • 109 covers the address electrode 106
  • a dielectric layer is formed on the surface of the glass substrate 102
  • 110 is a protective film made of, for example, magnesium oxide.
  • color FPD a glass substrate is used to obtain a high-contrast image. The ability to install color filters (red, green, blue) or a black matrix between the electrical layers is necessary.
  • FPD members such as barrier ribs, electrodes, resistors, phosphors, color filters, and black matrices
  • a non-photosensitive resin is formed on a substrate so as to form a desired pattern.
  • a photolithography method is known in which a desired pattern is left on a substrate by developing the substrate, and this is baked (see, for example, Patent Document 1).
  • the screen printing method has a problem that the demand for pattern accuracy becomes very strict as the panel size increases and the definition becomes high, and cannot be handled by normal screen printing.
  • 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 photosensitive resin composition in the baking process is deteriorated. There were problems of poor thermal degradability and significant shrinkage.
  • Patent Document 1 Japanese Patent Laid-Open No. 11 44949
  • Patent Document 2 Japanese Patent Laid-Open No. 2005-250771
  • the present invention is intended to solve the problems associated with the prior art as described above, and can form a highly accurate pattern, is excellent in the thermal decomposability of organic components, and is fired.
  • An object of the present invention is to provide a photosensitive resin composition with less shrinkage later.
  • the present invention is a photosensitivity having a photosensitive resin layer which is formed from the above-described photosensitive resin composition and can form a highly accurate pattern and has excellent thermal decomposability of organic components. It is another object of the present invention to provide a film, and 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.
  • the present inventors have found that a photosensitive resin composition containing an SH-containing alkyl-soluble resin and a polyfunctional (meth) acrylate is highly accurate!
  • the present inventors have found that a pattern can be formed, the organic component is excellent in thermal decomposability, and there is little shrinkage after firing, and the present invention has been completed.
  • 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).
  • A alkali-soluble resin
  • B polyfunctional (meth) acrylate
  • C photopolymerization initiator
  • D inorganic particles
  • the alkali-soluble resin (A) is a compound having at least two SH groups in one molecule.
  • (meth) acrylic resin obtained by polymerizing an alkali-soluble functional group-containing monomer (A2) and a (meth) acrylic acid derivative (A3) in the presence of (A1).
  • (A2) 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).
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents a divalent organic group
  • R 3 represents a monovalent organic group.
  • polyfunctional (meth) acrylate (B) is preferably a compound represented by the following formula (2).
  • n is a real number from ! 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 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. ) 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) The method includes a step of firing the pattern. 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 includes at least one display panel selected from a dielectric, an electrode, a resistor, a phosphor, a partition, a color filter, and a black matrix by the pattern forming method.
  • the display panel is preferably a plasma display panel.
  • the photosensitive resin composition and the photosensitive film of the present invention are capable of forming a highly accurate pattern, are excellent in the thermal decomposability of organic components, and have little shrinkage after firing. V. Therefore, it can be suitably used for forming a member constituting each display cell of a flat panel display and forming a member for an advanced mounting material for electronic components.
  • FIG. 1 is a schematic diagram showing a cross-sectional shape of an AC type FPD (specifically, a PDP).
  • FIG. 2 is a schematic diagram showing evaluation points in pattern evaluation in Examples;! -34 and Comparative Examples 1-;
  • FIG. 3 is an IR spectrum of SH group-containing methacrylic resin (A1).
  • the photosensitive resin composition of 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). Is included.
  • A alkali-soluble resin
  • B polyfunctional (meth) acrylate
  • C photopolymerization initiator
  • D inorganic particles
  • at least a part of the inorganic particles (D) is glassy. It is preferred to be a powder.
  • the alkali-soluble resin (A) having an SH group used in the composition of the present invention (hereinafter also referred to as “SH group-containing resin (A)”) has at least one SH group and is alkali-soluble.
  • SH group-containing resin (A) has at least one SH group and is alkali-soluble.
  • a (meth) acrylic resin having an SH group is preferable.
  • alkali-soluble means a property of being dissolved in an alkaline developer to such an extent that the intended development processing is possible.
  • the SH group-containing resin (A) does not have an SH group because the resin (A) itself further polymerizes by reacting with a polyfunctional (meth) acrylate (B), which will be described later, by en-thiol reaction by light irradiation.
  • the sensitivity is higher than that of resin, and the molecular weight of the resin is increased by this polymerization, so that the pattern shape after image formation is good.
  • the (meth) acrylic resin having an SH group described above contains an alkali-soluble functional group-containing monomer (A2) and (meth) in the presence of a compound (A1) having at least two SH groups in one molecule. It is possible to manufacture by copolymerizing with allylic acid derivative (A3).
  • Examples of the compound (A1) having at least two SH groups in one molecule include esters of SH group-containing rubonic acid and polyhydric alcohols.
  • Examples of the SH group-containing carboxylic acid include thioglycolic acid and 3-mercaptopropionic acid.
  • Examples of the polyhydric alcohol include ethylene glycol, tetraethylenedaricol, butanediol, trimethylololepropane, 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.
  • the above compound (A1) from the viewpoint of odor and work!
  • the compound (A1) may be used alone or in combination of two or more.
  • the amount of the compound (A1) used is about 0.5 to 10 weights per 100 parts by weight of the total monomers used for the copolymerization.
  • the alkali-soluble functional group-containing monomer (A2) includes (meth) acrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, mesaconic acid, cinnamate, and succinic acid.
  • (2- (meth) atariloy oral kichetyl) 2-methacryloyl oral kichetyl phthalic acid, 2-alkylene phthalate, 2-atearliestunoreoxypropinorehexahydrohydrogen phthalate, 2 taliloyloxypropyltetrahydrophthalate , ⁇ - carboxyl-containing monomers such as carboxy-polycaprolatatone mono (meth) atarylate;
  • Hydroxyl-containing monomers such as (meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid 2-hydroxypropyl, (meth) acrylic acid 3-hydroxypropyl, -hydroxymethyl) acrylate;
  • Phenolic hydroxyl group-containing monomers such as hydroxystyrene, m-hydroxystyrene, and p-hydroxystyrene
  • a monomer having an alkali-soluble functional group and an unsaturated bond a monomer having an alkali-soluble functional group and an unsaturated bond.
  • monomers (meth) acrylic acid, 2-methacryloyl oral xichetyl phthalic acid, 2-atari oral oxyxetyl hydrogen phthalate, 2-atallyloyloxypropyl hydrogen phthalate, 2-ataliroyoleoxypropinole Hexahydrohydrogen phthalate, 2-acryloyloxypropyl tetrahydrohydrogen phthalate, and (meth) acrylic acid 2-hydroxychetyl are preferred.
  • alkali-solubility 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 in all the structural units of the resin (A). Is 15 to 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).
  • methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, lauryl (meth) acrylate, benzyl (meth) acrylate, phenoxychetyl (meth) acrylate, totyl (meth) (Meth) atalylates other than the above monomer (A2) such as attalylate, cyclohexyl (meth) acrylate, isopolonyl (meth) acrylate, glycidyl (meth) acrylate, dicyclopentanyl (meth) acrylate And the like.
  • (meth) acrylic acid derivative (A3) instead of the (meth) acrylic acid derivative (A3), or In addition to (a) acrylic acid derivative (A3), for example, at one chain end of a polymer obtained from styrene, methyl (meth) acrylate, ethyl (meth) acrylate, benzyl (meth) acrylate, etc. ) Macromonomer with polymerizable unsaturated group such as attalyloyl group, aryl group, bur group, etc.
  • a radical polymerization initiator used for the polymerization of the bull monomer can be used.
  • a radical polymerization initiator used for the polymerization of the bull monomer.
  • These radical polymerization initiators may be used alone or in combination
  • the weight average molecular weight (hereinafter referred to as "Mw") of the SH group-containing resin (A) thus obtained is a polystyrene conversion value measured by gel permeation chromatography (GPC).
  • Mw polystyrene conversion value measured by gel permeation chromatography
  • the preferred ⁇ is 5,000-100,000, and the more preferred ⁇ is 10,000-50,000.
  • 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.When Mw exceeds the above range, the solubility in the unexposed portion of the developer may be reduced and resolution may be reduced. is there.
  • the glass transition temperature (Tg) of the (meth) acrylic resin is 0 to 120 ° C, preferably 10 to 100 ° C. If the glass transition temperature is lower than the above range, the coating tends to be tacky or difficult to handle. If the glass transition temperature exceeds the above range, the adhesion to the glass substrate as a support may be deteriorated or transfer may not be possible.
  • the glass transition temperature of the compound (A1), monomer (A2), and (meth) acrylic acid derivative (A3) It can be adjusted as appropriate by changing the amount.
  • 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.
  • the acid value is 20 mgKOH / g or less, it tends to be difficult to form a high-definition pattern in which the unexposed part after exposure is difficult to remove quickly with an alkaline developer.
  • the acid value is 200 mgKOH / g or more, the portion hardened by the exposure light is easily eroded by the alkali developer, and it is in the # 1 direction that makes it difficult to form a high-definition pattern.
  • the polyfunctional (meth) acrylate (B) used in the composition of the present invention may be any bifunctional or higher (meth) acrylate.
  • the polyfunctional (meth) acrylate (B) is preferably represented by the following formula (1):
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents a divalent organic group
  • R 3 represents a monovalent organic group.
  • n is a real number from;! To 10]
  • n is a real number from ! to 10]
  • n in the formula (3) is a polyperoxide obtained by the following formula from the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation: graphy (GPC) of the compound represented by the formula (2). It is the average degree of polymerization of oxypropylene.
  • Average polymerization degree of formula (3) (n) ⁇ (Mw—in a portion other than polyoxypropylene, and n in formula (5) is a gel permeation chromatography of tris (polyoxypropylene) glyceryl ether. This is the average degree of polymerization of polyoxypropylene determined by the following formula from the weight average molecular weight (Mw) in terms of polystyrene measured by chromatography (GPC).
  • Average polymerization degree of formula (5) (n) ⁇ (Mw—weight average molecular weight (Mw) of the above tris (polyoxypropylene) glyceryl ether other than polyoxypropylene is from 2 70 to 1800 force S
  • the force S can be formed to form a pattern with little dimensional change by development or baking.
  • an acid is suitable.
  • the acid include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butanoic acid, trichloro oral acetic acid, dichloroacetic acid, pyruvic acid and glycolic acid; oxalic acid, maleic acid, oxa oral acetic acid, malon acid, Aliphatic polycarboxylic acids such as fumaric acid, tartaric acid and citrate; aromatic carboxylic acids such as benzoic acid and terephthalic acid; benzenesulfonic acid, p-toluenesulfonic acid, p-toluenesulfonic acid pyridinium salt, p-toluene Aromatic sulfonic acids such as quinolinium sulfonate or salts thereof; sulfates such as sodium sulfate, potassium sulfate, magnesium sulfate
  • the above catalysts may be used alone or in combination of two or more.
  • oxalic acid, maleic acid, potassium hydrogen sulfate, hydrochloric acid, sulfuric acid, and phosphoric acid are preferable.
  • hydrochloric acid in addition to acting as an addition reaction catalyst, it may act as a cationic polymerization initiator for butyl ether. Therefore, hydrochloric acid does not act as a cationic polymerization initiator, but it works selectively only for addition reactions, and it is very advantageous in terms of production with a wide temperature control range. It is a particularly preferred catalyst.
  • the amount of the catalyst used depends on the type of tris (polyoxypropylene) glyceryl ether and tris (polyoxypropylene) glyceryl ether used in the addition reaction and the amount of 2- (vinyloxyethoxy) methacrylic acid used.
  • it is preferably 0.100 parts by weight with respect to 100 parts by weight of methacrylic acid 2- (vinyl chloride) ethyl ester. 0005 parts by weight or more, more preferably 0.001 part by weight or more. Further, it is preferably 3 parts by weight or less, more preferably 1 part by weight or less.
  • the polyfunctional (meth) acrylate (B) may be used singly or in combination of two or more! /.
  • the content of the polyfunctional (meth) acrylate (B) in the composition of the present invention is usually 20 to 200 parts by weight, preferably 100 to parts by weight of the SH group-containing resin (A). Or 30 to 100 parts by weight. If the content of the polyfunctional (meth) acrylate (B) is too small, the exposed portion is easily eroded by the developer, 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. In addition, shrinkage increases during firing, causing peeling.
  • the photopolymerization initiator (C) used in the composition of the present invention radicals are generated in the exposure process described later, and the SH group-containing resin (A) and the polyfunctional (meth) acrylate (B) are used. As long as it is a compound that initiates the polymerization reaction with
  • the photopolymerization initiator (C) may be used alone or in combination of two or more.
  • the photopolymerizable initiator (C) is usually 0.;! 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) alkyl relay HB). Is used in the range of 0.5 to 40 parts by weight. 0.1 is less than 1 part by weight, the effect of improving light sensitivity is not exerted, and when it exceeds 50 parts by weight, this a force s residual rate of exposed portions may be too small.
  • the inorganic particles (D) used in the composition of the present invention vary depending on the type of forming material.
  • the inorganic particles used for the dielectric and the partition wall forming material constituting the FPD at least a part of the inorganic particles (D) is preferably glass powder.
  • Examples of the glass powder used in the composition of the present invention include a low-melting glass powder having a heat softening point of 300 to 650 ° C, preferably 350 to 600 ° C.
  • the thermal softening point of the glass powder is lower than the above range! /.
  • the organic substance such as resin is not completely decomposed and removed.
  • the glass powder melts. Therefore, a part of the organic substance remains in the formed member, and as a result, the members such as the dielectric layer and the partition are colored, and the light transmittance may be reduced.
  • the glass substrate needs to be fired at a high temperature.
  • Examples of the glass powder include (l) BiO-ZnO-BO system and (2) BiO-SiO. -BO system, (3) Bi O-SiO -BO-Li O system, (4) Bi O-SiO-BO -Na O system
  • 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 sizes.
  • the glass powder preferably contains silicon oxide in the range of 5 to 50% by weight in order to obtain a higher-definition patterning. More preferable. Silicon oxide has a function of improving the denseness, strength and stability of the glass, and is also effective in lowering 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 silicon oxide content is 5% by weight or more, the coefficient of thermal expansion can be kept small, the generation of cracks occurring when baked on a glass substrate can be reduced, and the refractive index can be kept low. . Further, 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 wt%.
  • the boron oxide content 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 boron oxide content is 50% by weight or less, the chemical stability of the glass can be maintained. In addition, boron oxide Elemental 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 in the range of 2 to 20% by weight. It is more preferable to contain it.
  • These components are effective in adjusting the thermal expansion coefficient, prevent the substrate from being deformed during firing, provide electrical insulation, improve the stability and denseness of the partition walls 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 are kept small. And maintain chemical stability.
  • the glass powder preferably contains aluminum oxide in the range of 1 to 40% by weight.
  • Aluminum oxide has the effect of expanding the vitrification range and stabilizing the glass, and is also effective in extending the pot life of the composition. When the aluminum oxide content is within the above range, the glass transition point and the load softening point are kept low and the adhesion to the substrate is improved with the force S.
  • 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 an effect of making glass easily 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 a 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. Alkali metal oxides may promote ion migration and diffusion, so the total amount should be 20% by weight or less to maintain the chemical stability of the glass and keep the thermal expansion coefficient small. be able to.
  • the glass powder may contain zinc oxide, titanium oxide, zirconium oxide and the like in addition to the above components.
  • the average particle size of the glass powder is selected in consideration of the shape of the pattern to be produced.
  • S is preferably from 0.01 to 10 m, more preferably from 0.1 to 5111.
  • the specific surface area of the glass powder 0.5;! That force pattern shape Naruue preferably ⁇ 300m 2 / g.
  • the glass powder may be contained in a composition for forming components other than the FPD dielectric and barrier ribs (eg, electrode 'resistor ⁇ phosphor' color filter ⁇ black matrix). Good.
  • the content of the glass powder in this case varies depending on the application, but it is usually from! To 90 parts by weight, preferably from! Part.
  • Inorganic particles (D) used in electrode forming materials such as FPD, LCD, organic EL, printed circuit board, multilayer circuit board, module, inductor and LSI include Al, Ag, Ag-Pd alloy, Au , Ni, Cr, Cu, etc. Among these, it is preferable to use Ag which is relatively inexpensive because it 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, or flaky. Even if inorganic particles (D) having the same shape are used, two or more different shapes are used. Inorganic particles (D) may be mixed and used. Further, the average particle size is preferably ⁇ or 0.01—lO ⁇ m, more preferably (0.05 to 5 to 111 mm, mixed with inorganic particles (D) having different average particle sizes. You can also
  • inorganic particles used in these electrode forming materials hereinafter also referred to as “conductive powder”
  • glass powder When inorganic particles used in these electrode forming materials (hereinafter also referred to as “conductive powder”) and glass powder are used in combination, depending on the type of conductive powder, The content is usually 1 to 30 parts by weight with respect to 100 parts by weight of the total amount of inorganic particles (D).
  • the glass powder is used in an amount of 1 to 5 parts by weight, preferably 1 to 4 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), fluorine-doped indium oxide (FIO), fluorine-doped tin oxide (FTO), fluorine-doped zinc oxide (FZO), and one or two selected from Al, Co, Fe, In, Sn and Ti Examples thereof include zinc oxide fine particles containing at least one kind of metal.
  • the inorganic particles (D) used for the resistor-forming material of PDP mention is made of particles made of RuO or the like with the force S.
  • the inorganic particles (D) used in the phosphor forming materials of FPD and PDP are
  • Inorganic particles (D) used in color filter forming materials such as FPD, PDP, LCD, and organic EL devices are Fe O for red, Cr O for green, and blue for green.
  • Examples of inorganic particles (D) used in black stripe (matrix) forming materials such as FPD, PDP, LCD, and organic EL elements include Co, Cr, Cu, Fe, Mn, Ni, Ti, Zn And their oxides, composite oxides, carbides, nitrides, sulfides, silicides, borides, carbon black, graphite, etc., even if used alone or in combination of two or more. You may mix and use.
  • metal particles, metal oxide particles and composite oxide particles selected from the group of Co, Cr, Cu, Fe, Mn, Ni and Ti are preferred! / ,.
  • the average particle diameter is preferably 0.01 to 10 ⁇ m, more preferably 0.05 to 5 ⁇ m, and particularly preferably 0.1 to 2 ⁇ m.
  • the content of the glass powder is usually 60 to 90 parts by weight, preferably 70 to 100 parts by weight of the total amount of inorganic particles (D). ⁇ 90, more preferably 73 to 86 weight.
  • the content of the inorganic particles (D) in the composition of the present invention is in the range of 100 to 2000 parts by weight, preferably 130 to 1000 parts by weight, with respect to 100 parts by weight of the SH group-containing resin (A). is there .
  • a force S can be formed to form a pattern having a good shape.
  • an ultraviolet absorber it is also effective to add an ultraviolet absorber to the photosensitive resin composition of the present invention. By adding a compound with a high ultraviolet absorption effect, a high aspect ratio, high definition, and high resolution can be obtained.
  • the ultraviolet absorber organic dyes or inorganic pigments can be used, and among them organic dyes or inorganic pigments having a high UV absorption coefficient in the wavelength range of 350 to 450 nm are preferably used.
  • organic dyes such as dyes and inorganic pigments such as zinc oxide, titanium oxide, and cerium oxide.
  • organic dyes are preferred because they do not remain in the insulating film after firing, and can reduce deterioration of insulating film characteristics.
  • zinc oxide, titanium oxide, and cerium oxide are preferable.
  • Inorganic pigments such as are more preferred.
  • the inorganic pigment is added in an amount ranging from 0.01 to 10 parts by weight, preferably from 0.03 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 inorganic pigment added is too small, the effect of adding the UV light absorber will be reduced. If the amount added is too large, the insulating film properties after firing may be deteriorated or the film strength may not be maintained. .
  • a sensitizer may be added to the photosensitive resin composition of the present invention in order to improve sensitivity.
  • sensitizers include 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 4 isopropylthioxanthone, 1 chloro-4-propylthioxanthone, 2, 4 jetylthioxanthone, 2, 3 bis (4 Getinoreaminobenzanol) cyclopentanone, 2, 6 bis (4-dimethylaminibenzanol) cycloto Xanone, 2, 6 bis (4-dimethylaminobenzal) -4-methylcyclohexanone, Michler's ketone, 4, 4 bis (jetylamino) monobenzophenone, 4, 4 bis (dimethylamino) chalcone, 4, 4 bis (jetylamino) chalcone, p dimethylaminocinnamylidindanone, p dimethylaminobenzylid
  • the above sensitizers may be used alone or in combination of two or more. Some sensitizers can also be used as photopolymerization initiators.
  • the amount of the sensitizer is usually 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). Can be added. If the amount of the sensitizer is too small, the effect of improving the photosensitivity may not be exhibited. If the amount of the sensitizer is too large, the residual ratio of the exposed area may be too small.
  • a polymerization inhibitor may be added to the photosensitive resin composition of the present invention in order to improve thermal stability during storage.
  • the polymerization inhibitor include hydroquinone, monoesterified hydroquinone, N-nitrosodiphenylamine, phenothiazine, p-t-butylcatenole, N-phenylnaphthylamine, 2,6-di-tert-butyl-p-methylphenol. , Chloranil, pyrogallol and the like.
  • the polymerization inhibitor can be added to the composition in an amount usually ranging from 0.00;! To 5% by weight.
  • 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.
  • Antioxidants include, for example, 2,6-di-tert-butyl-p-cresol, butylated hydroxy.
  • the antioxidant is added to the composition
  • an organic solvent may be added to the photosensitive resin composition of the present invention.
  • the organic solvent include ethylene glycol monomethyl ether, ethylene glycol monomethino enoate, ethylene glycol monobutino enoate, propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, propylene glycol Noremonomethinoreethenole, Propyleneglycolenoremonoechinoreetenore, MethinorecelloSoreolev, Echinorecerosonoreb, Butinorecerosonoreb, Methoxypropinoreacetate, Jetylketone, Methylbutylketone, Dipropyl Ketone, Methyl ethyl ketone, Dioxane, Acetone, Cyclohexanone, Cyclopentanone, n-Pentanolol, Diacetone alcohole, 4-
  • An adhesion assistant may be added to the photosensitive resin composition of the present invention in order to improve the adhesion to the support.
  • a silane compound is preferably used as the adhesion assistant.
  • Specific examples of silane compounds include n-propyldimethylmethoxysilane, n-
  • the content of the adhesion assistant in the photosensitive resin composition is the SH group-containing resin.
  • the amount is preferably from 0.05 to 15 parts by weight, more preferably from 0.;! To 10 parts by weight with respect to 100 parts by weight.
  • the composition of the present invention preferably contains a dissolution accelerator for the purpose of exhibiting sufficient solubility in a developer described later.
  • a surfactant is preferably used as the dissolution accelerator.
  • surfactants include fluorine-based surfactants, silicone-based surfactants, and noion-based surfactants.
  • fluorosurfactant examples include BM CHIMIE “: BM-1000", “: BM-1100”, Dainippon Ink & Chemicals “Megafac F142D”, “ F172, F173, F183, FLORAD FC-135, FC 170C, FC-430, FC-431, Asahi Glass Co., Ltd. ) “Surflon S-112”, “S-113”, “S-131”, “S-141”, “S-145”, “S-382”, “SC-101” , “SC-102”, “SC-103”, “SC-104”, “SC-105”, “SC106”, and the like.
  • silicone surfactants examples include "SH-28PA”, “SH-190”, “SH-193", “SZ-6032”, “SF” manufactured by Toray 'Dowcoung' Silicone Co., Ltd. — 8428, DC-57, DC-190, Shin-Etsu Chemical KP341, Shin-Akita Kasei F-top EF301, EF303, EF352 ”And other commercial products
  • nonionic surfactant examples include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene distyrenylated phenyl ether Polyoxyethylene aryl ethers such as polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether; polyoxyethylene dialkyl ethers such as polyoxyethylene dilaurate and polyoxyethylene distearate Examples include stealth.
  • polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether
  • polyoxyethylene distyrenylated phenyl ether Polyoxyethylene aryl ethers such as polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether
  • polyoxyethylene dialkyl ethers such as polyoxyethylene d
  • nonionic surfactants examples include “Emulgen A-60”, “A-90”, “A-550”, “B-66”, “B-66” manufactured by Kao Corporation. PP-99 ”,“ (Meth) acrylic acid copolymer polyflow No. 57 ”and“ No. 90 ”manufactured by Kyoeisha Chemical Co., Ltd. can be mentioned.
  • polyoxyethylene aryl ethers that are preferred for nonionic surfactants are the ability to easily remove the unexposed photosensitive resin layer during development. More preferred is a compound represented by the following formula (6).
  • R 1 is an alkyl group having 1 to 5 carbon atoms, preferably a methyl group
  • p is an integer of 1 to 5
  • s is an integer of !! to 5
  • t is an integer from 1 to 100, preferably an integer from 10 to 20.
  • the content of the dissolution accelerator in the composition of the present invention is preferably from 0.00;! To 20 parts by weight, more preferably 0.01 to 100 parts by weight of the SH group-containing resin (A). ⁇ ; 15 parts by weight, particularly preferably 0.;! ⁇ 10 parts by weight.
  • the content of the dissolution accelerator is in the above range, a composition having excellent solubility in a developer can be obtained.
  • the photosensitive resin composition of the present invention comprises the above-mentioned SH group-containing resin (A), polyfunctional (meth) atrelate (B), photopolymerization initiator (C) and inorganic particles (D), as required. It is prepared by blending various components to a predetermined composition ratio and then uniformly mixing and dispersing them with a three roll or kneader.
  • the viscosity of the above composition is a force that can be appropriately adjusted depending on the addition amount of inorganic particles (D), thickeners, organic solvents, plasticizers, precipitation inhibitors, and the like. cps (centimeter boise).
  • 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.
  • the support film constituting the photosensitive film is preferably a resin film having heat resistance and solvent resistance and flexibility. Since 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 in a roll shape.
  • the thickness of the supporting film is, for example, 20 ⁇ ; lOO ⁇ m as long as it is in a range suitable for use.
  • Examples of the resin forming the support film include polyethylene terephthalate, polyester, polyethylene, polypropylene, polystyrene, polyimide, polybutyl alcohol, polychlorinated butyl, polyfluoroethylene, and other fluorine-containing resins, nylon, and cellulose. Can be mentioned.
  • 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.
  • the protective film layer that may be provided on the surface of the photosensitive resin layer
  • a resin film having flexibility similar to that of the support film can be used, and the surface (photosensitive resin) can be used.
  • the surface that is in contact with the layer) has been subjected to a mold release process!
  • the photosensitive film can be obtained by applying the photosensitive resin composition on the support film to form a coating film, and drying the coating film to form a photosensitive resin layer. After drying, it is rolled or laminated with a protective film.
  • the photosensitive film can also be suitably applied 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 be formed.
  • any method can be used as long as it can efficiently form a coating film having a large film thickness (for example, 10 m or more) and excellent uniformity. It is not limited.
  • Examples thereof 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.
  • the drying condition of the coating film may be adjusted as appropriate so that the residual ratio force of the solvent after drying is within 3 ⁇ 4% by weight, for example, 50 to; at a drying temperature of 150 ° C for 0.5 to 60 minutes. Is about
  • the thickness of the photosensitive resin layer formed as described above is 30 to 300 Hm, preferably 50 to 200 111.
  • 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. It includes a step of forming (exposure step), a step of developing the photosensitive resin layer to form a pattern (development step), and a step of baking the pattern (baking step).
  • the photosensitive resin composition in the resin layer forming step, may be applied on a substrate to form a coating film, and the coating film may be dried to form a photosensitive resin layer.
  • the photosensitive resin layer may be formed on the substrate by transferring the photosensitive resin layer constituting the photosensitive film onto the substrate using the photosensitive film.
  • a photosensitive resin layer made of the photosensitive resin composition is formed on the substrate.
  • the method for forming the photosensitive resin layer include a method in which the photosensitive resin composition is applied onto 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 of applying the above composition on a substrate is not particularly limited as long as it is a method capable of efficiently forming a coating film having a large film thickness (eg, 10 m or more) and excellent uniformity.
  • 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.
  • the drying condition of the coating film may be adjusted as appropriate so that the residual ratio force of the solvent after drying is within 3 ⁇ 4% by weight, for example, 50 to; at a drying temperature of 150 ° C for 0.5 to 60 minutes. Is about
  • the thickness of the photosensitive resin layer formed as described above is 30 to 300 Hm, preferably 50 to 200 ⁇ m.
  • a laminate having n layers (n is an integer of 2 or more) may be formed by repeating application of the composition n times.
  • a resin layer having excellent film thickness uniformity can be easily formed on the substrate.
  • the thickness of the pattern to be formed can be made uniform.
  • a laminate having n layers (n represents an integer of 2 or more) of resin layers may be formed by repeating transfer n times using the photosensitive film.
  • the laminate may be formed by collectively transferring a laminate comprising n resin layers onto a substrate using a photosensitive film formed on a 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 contacts 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.
  • 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
  • the moving speed of the heating roller is 0. ⁇ 10m / min.
  • the preheating temperature at which the substrate may be preheated is, for example, 40 to 140 ° C.
  • 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 is treated with chemicals such as silane coupling agent; plasma treatment; ion plating method, sputtering method, Pre-treatment such as thin film formation by vapor phase reaction or vacuum deposition may be applied! /.
  • 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 is performed using an exposure apparatus.
  • the exposure can be performed by a mask exposure method using a photomask, as is done in ordinary photolithography.
  • the mask used should be either negative or positive depending on the type of organic component in the photosensitive resin layer.
  • the exposure pattern of the exposure mask varies depending on the purpose, for example, a stripe or grid of 10 to 500 111 widths.
  • 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 latent image of the pattern on the resin layer. Do not peel off the support film that is coated on the resin layer!
  • 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.
  • the photosensitive resin composition is applied on a substrate such as a glass substrate and then exposed while being conveyed. Can be exposed.
  • Examples of the active light source used for exposure include visible light, near ultraviolet light, ultraviolet light, electron beam, X-ray, and laser light.
  • ultraviolet light is preferred as the light source.
  • a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, or a halogen lamp can be used.
  • an ultra high pressure mercury lamp is preferable.
  • the exposure conditions different forces by the coating thickness; performing 0.05 to 1 min exposure using an ultra high pressure water silver lamp with an output of ⁇ 100mW / cm 2!.
  • a wavelength filter by narrowing the wavelength region of the exposure light using a wavelength filter, it is possible to suppress light scattering and improve pattern formation.
  • a filter that cuts off i-line (365 nm) light, or i Using a filter that cuts off the light of h-line and h-line (405 nm), improve the pattern formability with force S.
  • the resin layer is developed using the difference in solubility in the developer between the photosensitive part and the non-photosensitive part to form a resin layer pattern.
  • Development method eg, dipping method, rocking method, shutter method, spray method, paddle method, brush method, etc.
  • development processing conditions eg, developer type 'composition' concentration, development time, development temperature, etc.
  • an organic solvent capable of dissolving the organic components 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.
  • a compound having an acidic group such as a carboxyl group is present in the resin layer, development can be performed with an aqueous alkaline solution.
  • the inorganic particles (D) contained in the resin layer are uniformly dispersed in the SH group-containing resin (A), the inorganic particles (D) are dissolved in a developer and washed to obtain inorganic particles. (D) is also removed at the same time.
  • alkaline aqueous solution examples include lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium hydrogen phosphate, dihydrogen ammonium phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, dihydrogen phosphate.
  • the concentration of the alkaline aqueous solution is usually 0.01 to 10% by weight, more preferably 0.! To 5% by weight. If the alkali concentration is too low, the soluble portion will not be removed, and if the alkali concentration is too high, the pattern portion may be peeled off and the non-soluble portion may be corroded. It ’s not.
  • 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 a noion surfactant and an organic solvent.
  • a washing process is usually performed after the development process with an alkali developer.
  • the resin layer pattern is baked in a baking furnace.
  • Firing is performed in an atmosphere of air, ozone, nitrogen, hydrogen, or the like, which varies depending on the composition and the type of substrate.
  • a batch-type firing furnace or a belt-type continuous firing furnace can be used as the firing furnace.
  • the baking treatment condition requires that the organic substance in the resin layer residual portion is burned off.
  • the firing temperature is 300 to 1000 ° C, and the firing time is 10 to 90 minutes.
  • firing is performed at a temperature of 350 to 600 ° C for 10 to 60 minutes.
  • a display panel member such as a dielectric, an electrode, a resistor, a phosphor, a partition, a color filter, a black matrix, a circuit pattern of an electronic component, etc.
  • a heating step of 50 to 300 ° C. may be introduced for the purpose of drying or preliminary reaction during the transfer, exposure, development and firing steps.
  • the method for producing a flat display panel of the present invention comprises at least one kind of 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. Suitable for the method of manufacturing a plasma display panel.
  • Mw and Mw / Mn are values in terms of polystyrene measured by gel permeation chromatography (GPC) (“HLC-8220GPC” manufactured by Tosoh Corporation).
  • GPC gel permeation chromatography
  • M—M was used under the conditions of a tetrahydrofuran (THF) solvent and a measurement temperature of 40 ° C.
  • Desired standard exceeds ⁇ 5 m.
  • volume resistance [ ⁇ 'cm] is the panel specimen after firing (150mm X 150mm X 2.8mm
  • the absorption spectrum [cm- 1 ] was measured using a “FT IR / Fourier transform infrared spectrophotometer FT-720” manufactured by HORIBA after the alkali-soluble resin was purified and dried.
  • An inorganic powder-containing resin layer with a thickness of 10 ⁇ is formed on a glass substrate, and an i-line (ultraviolet light with a wavelength of 365 nm) is irradiated from the glass substrate side toward the inorganic powder-containing resin layer with an ultra-high pressure mercury lamp.
  • the powder-containing resin layer was cured.
  • the dose was 800 mj / cm 2 .
  • development treatment 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 rays were irradiated to remove the uncured inorganic powder-containing resin.
  • 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 specified in the following range of remaining film values. The results are shown in the table.
  • Residual film thickness exceeds 6 m
  • Remaining film thickness is less than 5 ⁇ 111
  • the panel test piece 150mm x 150mm x 2.8mm
  • the desired standard is a pattern width of 50 mm, height of 10 mm111, and spacing of 100 mm.
  • a pattern was prepared and fired on a panel test piece (150 mm XI 50 mm X 2 ⁇ 8 mm), and the adhesion between the fired pattern and the support was evaluated.
  • the desired standard is a pattern width of 50 111, a height of 10 m, and an interval of 100 m.
  • Cellotape (Nichiban's registration) (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 and adhered to the surface of the support. Evaluation was made by peeling the cellophane from the support.
  • Benzylmetatalylate 55g 2-methacryloyloxetylphthalic acid 45g, azobisisobutyronitrile (AIBN) lg, 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 in a 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.
  • AIBN azobisisobutyronitrile
  • SH group-containing methacrylate resin ( A1) methacrylic resin having SH groups (hereinafter referred to as “SH group-containing methacrylate resin ( A1) ”) was obtained.
  • the polymerization rate of the SH group-containing methacrylic resin (A1) was 98%, and the weight average molecular weight of the SH group-containing methacrylic resin (A1) was 20000 (Mw / Mn was 1 ⁇ 8).
  • Fig. 3 shows the IR spectrum of the obtained resin.
  • the SH group was the same as in Synthesis Example A1.
  • a 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).
  • A3 (hereinafter referred to as ⁇ methacrylic resin (A3) '' Also described).
  • 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).
  • a methacrylic resin (A4) was obtained in the same manner as in Synthesis Example A1 except that 5 g of 2,4 diphenyl diru 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 methallyl resin (A4) was 25000 (Mw / Mn was 2.2).
  • the SH group was synthesized in the same manner as in Synthesis Example A1.
  • 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).
  • a methacrylic resin (A7) was obtained in the same manner as in Synthesis Example A1, except that 5 g of methyl-3-mercaptopropionate (manufactured by Sakai Chemical Co., Ltd.) was 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]
  • AIBN Azobisisobutyronitrile
  • Trimethylolpropane tris (3-mercaptopropionate) manufactured by Sakai Chemical Industry Co., Ltd.
  • stirrer The mixture was charged into an autoclave and stirred in 150 parts of polypropylene alcohol monomethyl ether until uniform in a nitrogen atmosphere. Next, polymerization was carried out at 80 ° C. for 4 hours, and further polymerization reaction was continued at 100 ° C. for 1 hour. After cooling to room temperature, a methacrylic resin having SH groups (A8) A8) is also written).
  • the polymerization rate of this SH group-containing methacrylic resin (A8) was 98%, and the
  • a methacrylic resin (A10) was prepared 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). (Hereinafter also referred to as “methacrylic resin (A10)”).
  • the polymerization rate of this methacrylic resin (A10) was 98%, and the weight average molecular weight of the methacrylic resin (A10) was 30,000.
  • Add 300 g (hydroxyl group 3 mol) and hydrochloric acid 1 ⁇ 56 g (35% aqueous solution, 0.015 mol as HCl component) and stir, then add 600 g (3 mol) of methacrylic acid 2- (binary oxychhetoxy) ethyl.
  • the solution was slowly added dropwise while paying attention to heat generation.
  • Tris (polyoxypropylene) glyceryl ether (Mwl 500) (manufactured by Wako Pure Chemical Industries, Ltd., in the above formula (5)) was added to a 3 liter flask equipped with a stirrer, thermometer, condenser and nitrogen gas inlet tube.
  • ( ⁇ 8 ⁇ l)
  • this polyfunctional (meth) atalylate (B5) was analyzed by IR, the peak near 3500 cm 1 due to the hydroxyl group almost disappeared.
  • a support film two sheets of polyethylene terephthalate (PET) film (width 200mm, length 30m, thickness 50m) that had been pre-released were prepared, and the photosensitive paste was placed on each of these support films.
  • PET polyethylene terephthalate
  • the photosensitive paste was placed on each of these support films.
  • the photosensitive resin layers formed on the two PET films were bonded to each other 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. In this way, a photosensitive film having a photosensitive resin layer (thickness 18011 m) containing inorganic particles was prepared.
  • the photosensitive resin layer containing inorganic particles was subjected to ultraviolet exposure with an ultrahigh pressure mercury lamp with an output of 25 mj / cm 2 from the top surface. .
  • the exposure dose was 200 mj / cm 2 .
  • the inorganic particle-containing photosensitive resin layer after the exposure was subjected to sodium carbonate kept at 23 ° C.
  • a 0.5% aqueous solution was developed by applying 180 seconds in a shower. Thereafter, it was washed with water using a shower spray, photocured, and the space was removed to form a lattice-shaped photosensitive resin pattern containing inorganic particles on the glass substrate for the panel.
  • the developed noise was evaluated by the above evaluation method. The results are shown in Table 1.
  • PGME Indicates propylene glycol monomethyl ether.
  • Comparative Example 7 a defective pattern such as an insufficient aspect ratio or development residue was observed in the pattern evaluation after development. In addition, a pattern with insufficient aspect ratio was observed in the pattern evaluation after firing.
  • TMP Trimethylolpropane triacrylate
  • DTMPTA Ditrimethylolpropane tetraacrylate
  • PETTA Pentaerythritol triacrylate
  • MTPMP 2-methyl 1 1 [4 1 (methylthio) phenyl] 1 2-morpholino 1 1 pro / 1 1 1
  • Ag (specific surface area: 1.5 m 2 / g, average particle size (D50): 1 ⁇ 5 m), Cu (average particle size (D50): 0.6 111), Ni (average particle size (D50): 0 4), Sn (average particle size (D50): 0.5 ⁇ ⁇ ⁇ (average particle size (D50): 2 ⁇ 111), Ag—Pt (average particle size (D50): 2. S ⁇ m Pt (average particle size (D50): 2.2 111), Au (average particle size (D50): 0 ⁇ 6 m), or A1 (average particle size (D50): 2.0 m) Was used.
  • PET films Two polyethylene terephthalate (PET) films (width 200mm, length 30m, thickness 50m) that had been pre-released were prepared as support films, and the above-mentioned photosensitive paste was rolled onto the support film.
  • coating film was formed by coating by, by removing the solvent the formed coating film was dried for 5 minutes at 1 00 ° C, to form a photosensitive resin layer having a thickness of 10 ⁇ .
  • a PET film that had been subjected to release treatment in advance was bonded and thermocompression bonded with a heating roller. Bonding conditions, the surface temperature of 90 ° C (194 ° F) of the heating roller, roll pressure of 4 kg / cm 2, the moving speed of the heating roller was set to the speed 0. 5 m / min. In this way, a photosensitive film having an inorganic powder-containing photosensitive resin layer (thickness 10 m) was produced.
  • the photosensitive resin layer was overlaid on the surface of a glass test piece (150 mm X 150 mm X 2.8 mm), and the remaining support film was peeled off.
  • the photopolymer layer was 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.
  • the inorganic powder-containing photosensitive resin layer was transferred to and adhered to the surface of the glass substrate.
  • the thickness of the transferred inorganic powder-containing photosensitive resin layer was measured, it was in the range of 10 / m ⁇ 1 m in Examples 13 to 27.
  • the photosensitive resin layer containing inorganic particles was violetd using an ultrahigh pressure mercury lamp with an output of 25 mj / cm 2 from the top surface. External exposure. Exposure amount was 1000 mj / cm 2.
  • the inorganic powder-containing photosensitive resin layer after exposure was developed by applying a 0.5% aqueous solution of sodium carbonate maintained at 23 ° C for 60 seconds in a shower. Thereafter, it was washed with water using a shower spray, photocured, and the space portion was removed to form a lattice-shaped photosensitive resin pattern containing inorganic particles on the glass substrate for panels.
  • the pattern after this development was evaluated by the above evaluation method. The results are 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 a range of 2 to 100 ⁇ -cm, and were at a level that could be used as an electrode.
  • photosensitive paste a photosensitive resin composition containing inorganic particles (hereinafter also referred to as “photosensitive paste”).
  • the above photosensitive paste was printed on a glass substrate (150 mm square, 2.8 mm thick) with a size of 100 mm square using a 325 mesh screen, dried at 100 ° C. for 10 minutes. All of Examples 28 to 34 were in the range of 10 mm ⁇ 1 m.
  • the photosensitive resin layer containing inorganic particles was subjected to ultraviolet exposure using an ultrahigh pressure mercury lamp with an output of 25 mj / cm 2 from the top surface. .
  • the exposure dose was 1000 mj / cm 2 .
  • the inorganic powder-containing photosensitive resin layer after exposure was developed by applying a 0.5% aqueous solution of sodium carbonate maintained at 23 ° C. for 60 seconds in a shower. Thereafter, it was washed with water using a shower spray, photocured, and the space portion was removed to form a lattice-shaped photosensitive resin pattern containing inorganic particles on the glass substrate for panels. After this development, The turn was evaluated by the above evaluation method. The results are 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.
  • Examples 28 and 29 were particularly excellent in pattern evaluation after firing.
  • Examples 30 to 34 were good, and no chipping or peeling of the pattern after firing was observed.
  • Examples 28 to 34 are in the range of 3 to; 100 ⁇ 'cm, and can be used as electrodes.
  • 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 showed poor results. Further, in the pattern evaluation after firing, Comparative Examples 8 to 11 were defective, and the chipping or peeling of the pattern after firing was observed. In the evaluation of the volume resistance, Comparative Examples 8 to 11 were all in the range of 6 to 50 ⁇ ′cm, and could be used as electrodes.
  • 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 evaluation of the pattern after development, Comparative Examples 12 to 15 showed poor results. Further, in the pattern evaluation after firing, Comparative Examples 12 to 15 were poor, and the chipping or peeling of the pattern after firing was observed. In the volume resistance evaluation, Comparative Examples 12 to 15 and 15 were all in the range of 3 to 50 ⁇ ′cm, and could be used as electrodes.
  • A-60 represents Emargen A-60 (trade name, manufactured by Kao Corporation, polyoxyethylene distyrenylated phenyl ether), and TNOL represents tubineol.
  • MnCo O— CoMn O— CuMn O and Cu Mn O pigments ratio table
  • the inorganic powder-containing resin composition (I) prepared in the above step (1) was applied onto a support film made of a PET film having a film thickness of 38 Hm, which had been subjected to a release treatment, using a blade coater.
  • the transfer film of the present invention in which an organic powder-containing resin layer having a thickness of 6111 was formed on a support film by drying at 100 ° C. for 1 minute 30 seconds to remove the solvent was produced. [0197] (3) Transfer process of transfer film
  • the transfer film produced in the above step (2) was superposed on the surface of the glass substrate so that the surface of the inorganic powder-containing resin layer was in contact with the glass substrate, and thermocompression bonded with a heating roller.
  • 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.
  • the inorganic powder-containing resin layer was transferred and adhered to the surface of the glass substrate.
  • the support film After the support film is peeled off from the inorganic powder-containing resin layer formed on the glass substrate in the above step (3), it is passed through an exposure mask (5 cm x 5 cm, pattern width 50 m, pattern interval 150 m).
  • a latent image of the pattern was formed on the resin layer containing inorganic powder by irradiating i-line (ultraviolet with a wavelength of 365 nm) with an ultra-high pressure mercury lamp.
  • the irradiation dose was 800 mj / cm 2 .
  • the film After exposure, the film was developed for 20 seconds by a shower method using a 0.5 mass% aqueous sodium carbonate solution at a liquid temperature of 25 ° C. as a developer, and then washed with ultrapure water. As a result, the resin was irradiated with ultraviolet rays, and the resin contained in the inorganic powder was removed, forming an inorganic powder-containing resin pattern.
  • the glass substrate having the inorganic powder-containing resin pattern formed in the above 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 am was formed on the surface of the glass substrate.
  • composition and black matrix obtained in the above steps were evaluated by the following methods.
  • i-line (ultraviolet light with a wavelength of 365 nm) is emitted from the glass substrate side toward the inorganic powder-containing resin layer with an ultra-high pressure mercury lamp. Irradiation was performed to cure the inorganic powder-containing resin layer. 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 using ultrapure water. And washed with water. In this way, the inorganic part of the part not irradiated with ultraviolet rays The powder-containing resin was removed.
  • AA Residual film thickness exceeds 6 ⁇ m
  • Remaining film thickness is less than 4 ⁇ 111
  • the substrate obtained in the above step (5) was observed with a scanning electron microscope, and the patterning property was evaluated by observing whether or not warping had occurred.
  • the occurrence of warpage is indicated by AA, BB and CC.
  • the results are shown in Table 4.
  • 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.
  • spectrophotometer UV-2450PC manufactured by Shimadzu Corporation
  • MPC- multipurpose large sample chamber unit
  • 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.
  • Cyclohexyl methacrylate / 2—Phenoxyethyl acrylate / 2-hydroxypropyl methacrylate / methacrylic acid copolymer ( 40/30/10/20 (mass ratio)) 15 parts, trimethylolpropane ⁇ -modified triatalylate (trade name: ⁇ 320, manufactured by Toagosei Co., Ltd.) 5 parts, tripropylene glycol ditalylate (product name: ⁇ 220, manufactured by Toagosei Co., Ltd.) 5 parts, 2-benzyl 2-dimethylamino 1- (4-morpholinophenyl) 1-butane 1-one 1 part, 2, 2 Dimethoxy 1 1, 2 Diphenyl 1-one 1-one 0.4 part, propylene glycol monomethyl ether acetate A 25 am thick layer was formed by the object.
  • This layer was irradiated with i-rays (ultraviolet light with a wavelength of 365 nm) with an ultrahigh pressure mercury lamp through an exposure mask (5 cm x 5 cm, pattern width 50 m, pattern interval 200 in), and an inorganic powder A latent image of the pattern was formed on the containing resin layer.
  • the irradiation dose was 800 mj / cm 2 .
  • 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. This removed the inorganic powder containing resin of the part which was not irradiated with the ultraviolet ray, and obtained the lamination pattern.
  • the laminated pattern was baked for 30 minutes in a temperature atmosphere of 520 ° C. As a result, a laminated structure was formed on the surface of the glass substrate.
  • the patterning evaluation after firing was performed by the same method and standard as in Example 35. The results are shown in Table 5.
  • Example 41 The same procedure as in Example 41 was performed except that the composition shown in Table 5 was used. Table 5 shows the results of patterning evaluation after firing.
  • Example 4 1
  • Example 42 Comparative Example 1 9 types Pigment 1 Pigment 1 Pigment 1 Pigment 1 Pigment 1 Pigment

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Abstract

Disclosed is a photosensitive resin composition which can form a highly precise pattern, has excellent thermal degradability of an organic component, and shows less shrinking after firing. The composition comprises an alkali-soluble resin (A) having at least one SH group, a polyfunctional (meth)acrylate (B), a photopolymerization initiator (C) and an inorganic particle (D). Also disclosed is a method for forming a pattern by using the composition.

Description

明 細 書  Specification
感光性樹脂組成物、感光性フィルムおよびパターン形成方法  Photosensitive resin composition, photosensitive film and pattern forming method
技術分野  Technical field
[0001] 本発明は、感光性樹脂組成物、感光性フィルムおよびパターン形成方法に関する The present invention relates to a photosensitive resin composition, a photosensitive film, and a pattern forming method.
。より詳細には、誘電体、電極、抵抗体、蛍光体、隔壁、カラーフィルターおよびブラ ックマトリクスから構成される表示セルを有する、フラットパネルディスプレイなどのディ スプレイパネルや、電子部品の高度実装材料に用いられる微細な回路パターンを有 する回路基板の製造において、有機成分の熱分解性に優れ、精度の高いパターン を形成する場合に好適に使用することができる感光性樹脂組成物、該組成物からな る感光性樹脂層を有する感光性フィルム、および該組成物もしくは感光性フィルムを 用いたパターン形成方法に関する。 . More specifically, it is used for display panels such as flat panel displays having display cells composed of dielectrics, electrodes, resistors, phosphors, barrier ribs, color filters, and black matrices, and advanced mounting materials for electronic components. In the production of a circuit board having a fine circuit pattern, a photosensitive resin composition excellent in the thermal decomposability of organic components and suitable for forming a highly accurate pattern, comprising the composition. The present invention relates to a photosensitive film having a photosensitive resin layer and a pattern forming method using the composition or the photosensitive film.
背景技術  Background art
[0002] 近年、回路基板やディスプレイパネルにおけるパターン加工に対して、高密度化お よび高精細化の要求が高まってレ、る。このような要求が高まって!/、るディスプレイパネ ルの中でも、特にプラズマディスプレイパネル（以下「PDP」ともいう。）やフィールドェ ミッションディスプレイ（以下「FED」ともいう。）などのフラットパネルディスプレイ（以下 「FPD」とも!/、う。 )が注目されて!/、る。  In recent years, there has been an increasing demand for higher density and higher definition for pattern processing in circuit boards and display panels. Among such display panels, there is a growing demand for flat panel displays such as plasma display panels (hereinafter also referred to as “PDP”) and field emission displays (hereinafter also referred to as “FED”). The following "FPD"! /, U.
[0003] 図 1は交流型の PDPの断面形状を示す模式図である。図 1において、 101および 1 02は対抗配置されたガラス基板、 103および 111は隔壁であり、ガラス基板 101、ガ ラス基板 102、背面隔壁 103および前面隔壁 111によりセルが区画形成されている。  FIG. 1 is a schematic diagram showing a cross-sectional shape of an AC type PDP. In FIG. 1, 101 and 102 are opposing glass substrates, 103 and 111 are partition walls, and cells are defined by the glass substrate 101, the glass substrate 102, the rear partition wall 103, and the front partition wall 111.
104はガラス基板 101に固定された透明電極であり、 105は透明電極 104の抵抗を 下げる目的で該透明電極 104上に形成されたバス電極であり、 106はガラス基板 10 2に固定されたアドレス電極である。 107はセル内に保持された蛍光物質であり、 10 8は透明電極 104およびバス電極 105を被覆するようガラス基板 101の表面に形成 された誘電体層であり、 109はアドレス電極 106を被覆するようガラス基板 102の表 面に形成された誘電体層であり、 110は例えば酸化マグネシウムよりなる保護膜であ る。また、カラー FPDにおいては、コントラストの高い画像を得るため、ガラス基板と誘 電体層との間に、カラーフィルター（赤色 ·緑色 ·青色）やブラックマトリックスなどを設 けること力 Sfcる。 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 fixed to the glass substrate 102. Electrode. 107 is a fluorescent substance held in the cell, 10 8 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 covers 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 color FPD, a glass substrate is used to obtain a high-contrast image. The ability to install color filters (red, green, blue) or a black matrix between the electrical layers is necessary.
[0004] FPD部材である隔壁、電極、抵抗体、蛍光体、カラーフィルターおよびブラックマト リックス等の形成方法としては、（1)基板上に、非感光性樹脂を所望のパターンとなる ようにスクリーン印刷し、これを焼成するスクリーン印刷法、（2)基板上に感光性樹脂 層を形成し、所望のパターンが描かれたフォトマスクを介して、前記感光性樹脂層に 赤外線または紫外線を照射した上で現像することにより、基板上に所望のパターンを 残存させ、これを焼成するフォトリソグラフィ一法などが知られている（たとえば、特許 文献 1参照)。  [0004] As methods for forming FPD members such as barrier ribs, electrodes, resistors, phosphors, color filters, and black matrices, (1) a non-photosensitive resin is formed on a substrate so as to form a desired pattern. (2) Forming a photosensitive resin layer on the substrate, and irradiating the photosensitive resin layer with infrared rays or ultraviolet rays through a photomask on which a desired pattern is drawn A photolithography method is known in which a desired pattern is left on a substrate by developing the substrate, and this is baked (see, for example, Patent Document 1).
[0005] しかしながら、前記スクリーン印刷法ではパネルの大型化および高精細化に伴い、 パターン精度の要求が非常に厳しくなり、通常のスクリーン印刷では対応できないと いう問題がある。また、前記フォトリソグラフィ一法ではパターンの精度には優れてい るものの、膜厚が厚い場合には深さ方法の感度が不足してパターン精度が悪化した り、焼成工程における感光性樹脂組成物の熱分解性不良や大幅な収縮が観察され るという問題があった。  [0005] However, the screen printing method has a problem that the demand for pattern accuracy becomes very strict as the panel size increases and the definition becomes high, and cannot be handled by normal screen printing. In addition, 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 photosensitive resin composition in the baking process is deteriorated. There were problems of poor thermal degradability and significant shrinkage.
[0006] 感光性樹脂組成物の感度を向上させるために、光照射によって光硬化剤と反応す る樹脂を用いることが知られている（たとえば、特許文献 2参照）。このような樹脂とし て、エチレン性不飽和結合を有する樹脂が知られている力 S、この樹脂を得るためには [0006] In order to improve the sensitivity of the photosensitive resin composition, it is known to use a resin that reacts with a photocuring agent when irradiated with light (for example, see Patent Document 2). As such a resin, a resin S having an ethylenically unsaturated bond is known S, in order to obtain this resin
、たとえば、カルボキシル基または水酸基を有する樹脂にイソシァネート基含有 (メタ )アタリレートを反応させる工程が必要となる。 For example, a process of reacting an isocyanate group-containing (meth) acrylate with a resin having a carboxyl group or a hydroxyl group is required.
[0007] しかし、この方法を用いる場合、カルボキシル基または水酸基を有する樹脂とイソシ ァネート基含有 (メタ）アタリレートとの付加反応が精密にできないことや、その付加反 応で生成した樹脂の保存安定性の悪化に加えて、イソシァネート基含有 (メタ）アタリ レートが毒性を有するとレ、つたデメリットがある。 [0007] However, when this method is used, the addition reaction between a carboxyl group- or hydroxyl group-containing resin and an isocyanate group-containing (meth) acrylate cannot be precisely performed, and the storage stability of the resin formed by the addition reaction is not possible. In addition to the deterioration of properties, there are disadvantages when isocyanate group-containing (meth) acrylates are toxic.
特許文献 1：特開平 11 44949号公報  Patent Document 1: Japanese Patent Laid-Open No. 11 44949
特許文献 2：特開 2005— 275071号公報  Patent Document 2: Japanese Patent Laid-Open No. 2005-250771
発明の開示  Disclosure of the invention
発明が解決しょうとする課題 [0008] 本発明は、上記のような従来技術に伴う問題を解決しょうとするものであって、精度 の高いパターンを形成することができるとともに、有機成分の熱分解性に優れ、かつ 、焼成後に収縮の少ない感光性樹脂組成物を提供することを目的とする。 Problems to be solved by the invention [0008] The present invention is intended to solve the problems associated with the prior art as described above, and can form a highly accurate pattern, is excellent in the thermal decomposability of organic components, and is fired. An object of the present invention is to provide a photosensitive resin composition with less shrinkage later.
[0009] また、本発明は、上記感光性樹脂組成物から形成され、精度の高いパターンを形 成すること力 Sできるとともに、有機成分の熱分解性に優れる感光性樹脂層を有する感 光性フィルムを提供すること、ならびに、本発明の組成物もしくは感光性フィルムを用 いたパターン形成方法および該パターン形成方法を含むフラットパネルディスプレイ の製造方法を提供することも目的とする。  [0009] Further, the present invention is a photosensitivity having a photosensitive resin layer which is formed from the above-described photosensitive resin composition and can form a highly accurate pattern and has excellent thermal decomposability of organic components. It is another object of the present invention to provide a film, and 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.
課題を解決するための手段  Means for solving the problem
[0010] 本発明者らは、上記問題点を解決すべく鋭意研究した結果、 SH基を有するアル力 リ可溶性樹脂と多官能 (メタ）アタリレートを含む感光性樹脂組成物が精度の高!/、バタ ーンを形成することができ、有機成分の熱分解性に優れ、かつ、焼成後に収縮の少 ないことを見出し、本発明を完成するに至った。  [0010] As a result of intensive studies to solve the above problems, the present inventors have found that a photosensitive resin composition containing an SH-containing alkyl-soluble resin and a polyfunctional (meth) acrylate is highly accurate! The present inventors have found that a pattern can be formed, the organic component is excellent in thermal decomposability, and there is little shrinkage after firing, and the present invention has been completed.
[0011] すなわち、本発明に係る感光性樹脂組成物は、少なくとも 1つの SH基を有するァ ルカリ可溶性樹脂 (A)、多官能 (メタ）アタリレート (B)、光重合開始剤（C)、および無 機粒子 (D)を含有することを特徴とする。上記感光性樹脂組成物は、無機粒子 (D) の少なくとも一部がガラス粉末であることが好ましい。  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.
[0012] 前記アルカリ可溶性樹脂 (A)は、 1分子中に少なくとも 2つの SH基を有する化合物  [0012] The alkali-soluble resin (A) is a compound having at least two SH groups in one molecule.
(A1)の存在下で、アルカリ可溶性官能基含有モノマー (A2)と (メタ）アクリル酸誘導 体 (A3)とを重合して得られる（メタ）アクリル樹脂であることが好ましく、前記化合物（ A1)は、 SH基含有カルボン酸と多価アルコールとのエステルであることが好ましい。  It is preferably a (meth) acrylic resin obtained by polymerizing an alkali-soluble functional group-containing monomer (A2) and a (meth) acrylic acid derivative (A3) in the presence of (A1). ) Is preferably an ester of an SH group-containing carboxylic acid and a polyhydric alcohol.
[0013] 前記多官能 (メタ）アタリレート（B)は下記式（1)で表される基を有することが好まし い。  [0013] The polyfunctional (meth) acrylate (B) preferably has a group represented by the following formula (1).
[0014] [化 1]  [0014] [Chemical 1]
( 1 )
Figure imgf000005_0001
[0015] 〔式（1)中、 R1は水素原子またはメチル基を表し、 R2は 2価の有機基を表し、 R3は 1価の有機基を表す〕 (1)
Figure imgf000005_0001
[In the 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.]
また、前記多官能 (メタ）アタリレート（B)は下記式（2)で表される化合物であること が好ましい。  Further, the polyfunctional (meth) acrylate (B) is preferably a compound represented by the following formula (2).
[0016] ZOCH (CH OZ) (2)  [0016] ZOCH (CH OZ) (2)
[式（2)中、 Zは下記式（3)で表される。  [In formula (2), Z is represented by the following formula (3).
[0017] [化 2] [0017] [Chemical 2]
Figure imgf000006_0001
Figure imgf000006_0001
[0018] 〔式（3)中、 nは;!〜 10の実数である〕]  [In formula (3), n is a real number from !! to 10]]
本発明に係る感光性フィルムは、上記感光性樹脂組成物から得られる感光性樹脂 組成物層を有することを特徴とする。  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.
[0019] 本発明に係るパターン形成方法は、（I)請求項 1〜6のいずれかに記載の感光性 樹脂組成物から得られる感光性樹脂組成物層を基板上に形成する工程、 (Π)該感 光性樹脂組成物層を露光処理してパターンの潜像を形成する工程、 (III)露光後の 感光性樹脂組成物層を現像処理してパターンを形成する工程、および (IV)該パタ ーンを焼成処理する工程を含むことを特徴とする。前記工程 (I)において、上記感光 性フィルムを用いて、基板上に感光性樹脂組成物層を形成することが好ましい。  [0019] 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. ) 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) The method includes a step of firing the pattern. In the step (I), it is preferable to form a photosensitive resin composition layer on a substrate using the photosensitive film.
[0020] 本発明に係るフラットパネルディスプレイの製造方法は、上記パターン形成方法に より、誘電体、電極、抵抗体、蛍光体、隔壁、カラーフィルターおよびブラックマトリス クから選ばれる少なくとも 1種のディスプレイパネル用部材を形成する工程を含むこと を特徴とする。前記ディスプレイパネルはプラズマディスプレイパネルであることが好 ましい。  [0020] The flat panel display manufacturing method according to the present invention includes at least one display panel selected from a dielectric, an electrode, a resistor, a phosphor, a partition, a color filter, and a black matrix by the pattern forming method. A step of forming a member for use. The display panel is preferably a plasma display panel.
発明の効果  The invention's effect
[0021] 本発明の感光性樹脂組成物および感光性フィルムは、精度の高いパターンを形成 すること力 Sできるとともに、有機成分の熱分解性に優れ、かつ、焼成後に収縮の少な V、ことから、フラットパネルディスプレイの各表示セルを構成する部材の形成ならびに 電子部品の高度実装材料の部材の形成に好適に使用することができる。 [0021] The photosensitive resin composition and the photosensitive film of the present invention are capable of forming a highly accurate pattern, are excellent in the thermal decomposability of organic components, and have little shrinkage after firing. V. Therefore, it can be suitably used for forming a member constituting each display cell of a flat panel display and forming a member for an advanced mounting material for electronic components.
図面の簡単な説明  Brief Description of Drawings
[0022] [図 1]図 1は、交流型 FPD (具体的には、 PDP)の断面形状を示す模式図である。  FIG. 1 is a schematic diagram showing a cross-sectional shape of an AC type FPD (specifically, a PDP).
[図 2]図 2は、実施例;!〜 34、比較例 1〜； 15におけるパターンの評価において、評価 箇所を示す模式図である。  [FIG. 2] FIG. 2 is a schematic diagram showing evaluation points in pattern evaluation in Examples;! -34 and Comparative Examples 1-;
[図 3]図 3は SH基含有メタクリル樹脂 (A1)の IRスペクトルである。  FIG. 3 is an IR spectrum of SH group-containing methacrylic resin (A1).
符号の説明  Explanation of symbols
[0023] 101 ガラス基板  [0023] 101 glass substrate
102 ガラス基板  102 Glass substrate
103 背面隔壁  103 Rear bulkhead
104 透明電極  104 Transparent electrode
105 バス電極  105 bus electrode
106 アドレス電極  106 Address electrode
107 蛍光物質  107 Fluorescent substance
108 誘電体層  108 Dielectric layer
109 誘電体層  109 Dielectric layer
110 保護層  110 Protective layer
111 前面隔壁  111 Front bulkhead
A 隔壁パターン  A Bulkhead pattern
B 切断面詳細  B Cut surface details
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0024] 以下、本発明に係る感光性樹脂組成物、感光性フィルムおよびパターン形成方法 について、詳細に説明する。  Hereinafter, the photosensitive resin composition, the photosensitive film and the pattern forming method according to the present invention will be described in detail.
[0025] 〔感光性樹脂組成物〕  [Photosensitive resin composition]
本発明の感光性樹脂組成物は、少なくとも 1つの SH基を有するアルカリ可溶性樹 脂 (A)、多官能 (メタ)アタリレート (B)、光重合開始剤 (C)、および無機粒子 (D)を含 有する。本発明の感光性樹脂組成物は、前記無機粒子（D)の少なくとも一部がガラ ス粉末であることが好ましレ、。 The photosensitive resin composition of 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). Is included. In the photosensitive resin composition of the present invention, at least a part of the inorganic particles (D) is glassy. It is preferred to be a powder.
[0026] < SH基を有するアルカリ可溶性樹脂 (A) >  [0026] <Alkali-soluble resin having SH group (A)>
本発明の組成物に用いられる SH基を有するアルカリ可溶性樹脂 (A) (以下、「SH 基含有樹脂 (A)」とも記す）は、少なくとも 1つの SH基を有し、アルカリ可溶性であれ ば、特に限定されないが、例えば、 SH基を有する（メタ）アクリル樹脂が好ましい。な お、本発明において「アルカリ可溶性」とは、 目的とする現像処理が可能な程度に、 アルカリ性の現像液に溶解する性質をいう。  The alkali-soluble resin (A) having an SH group used in the composition of the present invention (hereinafter also referred to as “SH group-containing resin (A)”) has at least one SH group and is alkali-soluble. Although not particularly limited, for example, a (meth) acrylic resin having an SH group is preferable. In the present invention, “alkali-soluble” means a property of being dissolved in an alkaline developer to such an extent that the intended development processing is possible.
[0027] 上記 SH基含有樹脂 (A)は、光照射により、後述する多官能 (メタ）アタリレート (B) とェンーチオール反応して樹脂 (A)自体がさらに重合するため、 SH基を有しない樹 脂に比べて高感度であり、さらに、この重合により樹脂の分子量が大きくなるため、現 像後のパターン形状が良好となる。  [0027] The SH group-containing resin (A) does not have an SH group because the resin (A) itself further polymerizes by reacting with a polyfunctional (meth) acrylate (B), which will be described later, by en-thiol reaction by light irradiation. The sensitivity is higher than that of resin, and the molecular weight of the resin is increased by this polymerization, so that the pattern shape after image formation is good.
[0028] 上記 SH基を有する (メタ）アクリル樹脂は、 1分子中に少なくとも 2つの SH基を有す る化合物 (A1)の存在下で、アルカリ可溶性官能基含有モノマー (A2)と (メタ）アタリ ル酸誘導体 (A3)とを共重合することにより製造すること力 Sできる。  [0028] The (meth) acrylic resin having an SH group described above contains an alkali-soluble functional group-containing monomer (A2) and (meth) in the presence of a compound (A1) having at least two SH groups in one molecule. It is possible to manufacture by copolymerizing with allylic acid derivative (A3).
[0029] 1分子中に少なくとも 2つの SH基を有する上記化合物 (A1)としては、 SH基含有力 ルボン酸と多価アルコールとのエステルが挙げられる。 SH基含有カルボン酸として は、チォグリコール酸または 3—メルカプトプロピオン酸などが挙げられる。多価アル コールとしては、エチレングリコール、テトラエチレンダリコール、ブタンジオール、トリ メチローノレプロパン、ペンタエリスリトーノレ、ジペンタエリスリトーノレ、トリペンタエリスリト ール、ソルビトールなどが挙げられる。  [0029] Examples of the compound (A1) having at least two SH groups in one molecule include esters of SH group-containing rubonic acid and polyhydric alcohols. Examples of the SH group-containing carboxylic acid include thioglycolic acid and 3-mercaptopropionic acid. Examples of the polyhydric alcohol include ethylene glycol, tetraethylenedaricol, butanediol, trimethylololepropane, pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitol and the like.
[0030] この化合物 (A1)は上記共重合反応において、連鎖移動剤として作用し、得られる 樹脂 (A)には、好ましくは、主にその末端に SH基が形成されると考えられる。また、 作業上の臭気とレ、う観点からも上記化合物 (A1)を使用することが好まし!/、。  [0030] 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. In addition, it is preferable to use the above compound (A1) from the viewpoint of odor and work!
[0031] 上記化合物 (A1)は、 1種単独で用いてもよぐ 2種以上を併用してもよい。上記化 合物 (A1)の使用量は、上記共重合に使用する全モノマー 100重量部に対して 0. 5 〜； 10重量程度である。  [0031] The compound (A1) may be used alone or in combination of two or more. The amount of the compound (A1) used is about 0.5 to 10 weights per 100 parts by weight of the total monomers used for the copolymerization.
[0032] 上記アルカリ可溶性官能基含有モノマー（A2)としては、（メタ）アクリル酸、マレイン 酸、フマル酸、クロトン酸、ィタコン酸、シトラコン酸、メサコン酸、ケィ皮酸、コハク酸モ ノ（2—（メタ）アタリロイ口キシェチル）、 2—メタクリロイ口キシェチルフタル酸、 2—ァク ゲンフタレート、 2—アタリロイノレォキシプロピノレへキサヒドロハイドロゲンフタレート、 2 アタリロイルォキシプロピルテトラヒドロハイドロゲンフタレート、 ω—カルボキシーポ リカプロラタトンモノ（メタ）アタリレート等のカルボキシル基含有モノマー類； [0032] The alkali-soluble functional group-containing monomer (A2) includes (meth) acrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, mesaconic acid, cinnamate, and succinic acid. (2- (meth) atariloy oral kichetyl), 2-methacryloyl oral kichetyl phthalic acid, 2-alkylene phthalate, 2-atarileunoreoxypropinorehexahydrohydrogen phthalate, 2 taliloyloxypropyltetrahydrophthalate , Ω- carboxyl-containing monomers such as carboxy-polycaprolatatone mono (meth) atarylate;
(メタ）アクリル酸 2—ヒドロキシェチル、 （メタ）アクリル酸 2—ヒドロキシプロピル、 （メタ） アクリル酸 3—ヒドロキシプロピル、 -ヒドロキシメチル）アタリレート等の水酸基含有 モノマー類；  Hydroxyl-containing monomers such as (meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid 2-hydroxypropyl, (meth) acrylic acid 3-hydroxypropyl, -hydroxymethyl) acrylate;
ο ヒドロキシスチレン、 m ヒドロキシスチレン、 p ヒドロキシスチレン等のフエノール 性水酸基含有モノマー類  ο Phenolic hydroxyl group-containing monomers such as hydroxystyrene, m-hydroxystyrene, and p-hydroxystyrene
などのアルカリ可溶性官能基と不飽和結合を有するモノマーが挙げられる。これらの モノマーのうち、 （メタ）アクリル酸、 2—メタクリロイ口キシェチルフタル酸、 2—アタリ口 ィルォキシェチルハイドロゲンフタレート、 2—アタリロイルォキシプロピルハイドロゲン フタレート、 2—アタリロイノレォキシプロピノレへキサヒドロハイドロゲンフタレート、 2—ァ クリロイルォキシプロピルテトラヒドロハイドロゲンフタレート、 （メタ）アクリル酸 2—ヒドロ キシェチルが好ましい。  And a monomer having an alkali-soluble functional group and an unsaturated bond. Among these monomers, (meth) acrylic acid, 2-methacryloyl oral xichetyl phthalic acid, 2-atari oral oxyxetyl hydrogen phthalate, 2-atallyloyloxypropyl hydrogen phthalate, 2-ataliroyoleoxypropinole Hexahydrohydrogen phthalate, 2-acryloyloxypropyl tetrahydrohydrogen phthalate, and (meth) acrylic acid 2-hydroxychetyl are preferred.
[0033] アルカリ可溶性官能基含有モノマー (A2)を共重合することにより、樹脂 (A)にアル カリ可溶性を付与することができる。このアルカリ可溶性官能基含有モノマー (A2)由 来の構成単位の含有量は、樹脂 (A)の全構成単位中、通常、 5〜90重量％、好まし くは 10〜80重量％、特に好ましくは 15〜70重量％である。  [0033] 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 in all the structural units of the resin (A). Is 15 to 70% by weight.
[0034] 上記 (メタ）アクリル酸誘導体 (A3)としては、上記アルカリ可溶性官能基含有モノマ 一 (A2)と共重合可能な (メタ）アクリル酸誘導体であれば特に限定されなレ、が、たと えば、メチル (メタ）アタリレート、ェチル (メタ）アタリレート、 n ブチル (メタ）アタリレー ト、ラウリル (メタ）アタリレート、ベンジル (メタ）アタリレート、フエノキシェチル (メタ）ァク リレート、トチル（メタ）アタリレート、シクロへキシル（メタ）アタリレート、イソポロニル（メ タ）アタリレート、グリシジル（メタ）アタリレート、ジシクロペンタニル（メタ）アタリレート等 の上記モノマー (A2)以外の (メタ）アタリレート類などが挙げられる。  [0034] 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, phenoxychetyl (meth) acrylate, totyl (meth) (Meth) atalylates other than the above monomer (A2) such as attalylate, cyclohexyl (meth) acrylate, isopolonyl (meth) acrylate, glycidyl (meth) acrylate, dicyclopentanyl (meth) acrylate And the like.
[0035] また、本発明では、上記 (メタ）アクリル酸誘導体 (A3)の代わりに、あるいは上記 (メ タ）アクリル酸誘導体 (A3)に加えて、たとえば、スチレン、メチル (メタ）アタリレート、 ェチル (メタ）アタリレート、ベンジル (メタ）アタリレート等から得られるポリマーの一方 の鎖末端に、（メタ）アタリロイル基、ァリル基、ビュル基などの重合性不飽和基を有す るマクロモノマーなどを用いてもょレ、。 [0035] In the present invention, instead of the (meth) acrylic acid derivative (A3), or In addition to (a) acrylic acid derivative (A3), for example, at one chain end of a polymer obtained from styrene, methyl (meth) acrylate, ethyl (meth) acrylate, benzyl (meth) acrylate, etc. ) Macromonomer with polymerizable unsaturated group such as attalyloyl group, aryl group, bur group, etc.
[0036] (ラジカル重合開始剤）  [0036] (Radical polymerization initiator)
上記共重合の際、ラジカル重合開始剤を使用することが好ましい。ラジカル重合開 始剤としては、ビュル単量体の重合に用いられるラジカル重合開始剤を使用できる。 例えば、 2, 2，ーァゾビスイソブチロニトリル、 2, 2，ーァゾビス（2—メチルブチル二トリ ノレ）、 2, 2'—ァゾビス（2, 4 ジメチルバレロニトリル）、 1 , 1 '—ァゾビス（1—シクロ へキサンカルボ二トリル）、ジメチルー 2, 2，ーァゾビスイソブチレート、 4, 4' ァゾビ ス（4 シァノバレリック酸）等のァゾ化合物； t ブチルパーォキシビバレート、 tーブ チノレノ 一才キシ 2—ェチノレへキサノエート、クミノレノ 一才キシ 2—ェチノレへキサノエ一 ト等のパーォキシエステル類の有機過酸化物等を挙げることができる。これらのラジ カル重合開始剤は、 1種単独で用いてもよぐ 2種以上を併用してもよい。これらのラ ジカル重合開始剤の使用量は、上記共重合に使用する全モノマー 100重量部に対 して 0. ；!〜 10重量程度である。  In the copolymerization, it is preferable to use a radical polymerization initiator. As the radical polymerization initiator, a radical polymerization initiator used for the polymerization of the bull monomer can be used. For example, 2, 2, -azobisisobutyronitrile, 2, 2, -azobis (2-methylbutyl nitrinole), 2, 2'-azobis (2,4 dimethylvaleronitrile), 1, 1'-azobis Azo compounds such as (1-cyclohexanecarbonitryl), dimethyl-2,2, -azobisisobutyrate, 4,4 'azobis (4 cyanoberic acid); t butyl peroxybivalate, t- Examples thereof include organic peroxides of peroxyesters such as butinoreno 1-year-old xyl-2-ethinorehexanoate and cuminoreno 1-year-old xeno 2-hexenorehexanoate. These radical polymerization initiators may be used alone or in combination of two or more. The amount of these radical polymerization initiators used is about 0.;! To about 10 weights with respect to 100 parts by weight of all monomers used in the copolymerization.
[0037] このようにして得られた SH基含有樹脂 (A)の重量平均分子量 (以下「Mw」ともレ、う 。）は、ゲルパーミエーシヨンクロマトグラフィー（GPC)により測定したポリスチレン換 算値で、好まし <は 5, 000—100, 000、より好まし <は 10, 000—50, 000である。 Mwは、上記モノマーの共重合割合、組成、連鎖移動剤、重合温度などの条件を適 宜選択することにより制御すること力できる。 Mwが前記範囲よりも低いと、現像後の 膜荒れが発生しやすくなり、また、 Mwが前記範囲を超えると、未露光部の現像液に 対する溶解性が低下し、解像度が低下する場合がある。  [0037] The weight average molecular weight (hereinafter referred to as "Mw") of the SH group-containing resin (A) thus obtained is a polystyrene conversion value measured by gel permeation chromatography (GPC). The preferred <is 5,000-100,000, and the more preferred <is 10,000-50,000. 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.When Mw exceeds the above range, the solubility in the unexposed portion of the developer may be reduced and resolution may be reduced. is there.
[0038] 上記 (メタ）アクリル樹脂のガラス転移温度 (Tg)は、 0〜120°C、好ましくは 10〜10 0°Cである。ガラス転移温度が前記範囲よりも低いと、塗膜にタックを生じやすぐハン ドリングがしにくい傾向にある。また、ガラス転移温度が前記範囲を超えると、支持体 であるガラス基板との密着性が悪くなつたり、転写できないことがある。なお、前記ガラ ス転移温度は、上記化合物 (A1)、モノマー (A2)、（メタ）アクリル酸誘導体 (A3)の 量を変更することによって適宜調節することがでる。 [0038] The glass transition temperature (Tg) of the (meth) acrylic resin is 0 to 120 ° C, preferably 10 to 100 ° C. If the glass transition temperature is lower than the above range, the coating tends to be tacky or difficult to handle. If the glass transition temperature exceeds the above range, the adhesion to the glass substrate as a support may be deteriorated or transfer may not be possible. The glass transition temperature of the compound (A1), monomer (A2), and (meth) acrylic acid derivative (A3) It can be adjusted as appropriate by changing the amount.
[0039] 上記 SH基含有樹脂（A)の酸価は、好ましくは 20〜200mgKOH/g、より好ましく は 30〜； 160mgKOH/gの範囲である。酸価が 20mgKOH/g以下では露光後の 未露光部分が速やかにアルカリ現像液で除去しにくぐ高精細なパターン形成が困 難となる傾向にある。また、酸価が 200mgKOH/g以上になると、露光光によって硬 化した部分もアルカリ現像液に浸食されやすくなり、高精細なパターン形成が困難と なる #1向にある。  [0039] 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, it tends to be difficult to form a high-definition pattern in which the unexposed part after exposure is difficult to remove quickly with an alkaline developer. In addition, when the acid value is 200 mgKOH / g or more, the portion hardened by the exposure light is easily eroded by the alkali developer, and it is in the # 1 direction that makes it difficult to form a high-definition pattern.
[0040] <多官能（メタ）アタリレート（B) >  [0040] <Multifunctional (meth) acrylate (B)>
本発明の組成物に用いられる多官能 (メタ）アタリレート（B)は、二官能以上の (メタ） アタリレートであれば良い。  The polyfunctional (meth) acrylate (B) used in the composition of the present invention may be any bifunctional or higher (meth) acrylate.
[0041] 具体的には、ァリル化シクロへキシルジ（メタ）アタリレート、 2, 5 へキサンジ（メタ） アタリレート、 1 , 4 ブタンジオールジ（メタ）アタリレート、 1 , 3—ブチレングリコール ジ（メタ）アタリレート、エチレングリコールジ（メタ）アタリレート、ジエチレングリコールジ (メタ）アタリレート、トリエチレングリコールジ（メタ）アタリレート、ポリエチレングリコール ジ（メタ）アタリレート、グリセロールジ（メタ）アタリレート、メトキシ化シクロへキシルジ（メ タ）アタリレート、ネオペンチルグリコールジ（メタ）アタリレート、プロピレングリコールジ (メタ）アタリレート、ポリプロピレングリコールジ（メタ）アタリレート、トリグリセロールジ（ メタ）アタリレート等のジ (メタ）タクリレート類；  [0041] Specifically, arylated cyclohexyl di (meth) acrylate, 2, 5 hexane di (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, methoxy Cyclohexyl di (meth) acrylate, neopentyl glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, triglycerol di (meth) acrylate (Meth) tacrylates;
ペンタエリスリトールトリ（メタ）アタリレート、トリメチロールプロパン（メタ）アタリレート、ト リメチロールプロパン PO変性トリ（メタ）アタリレート、トリメチロールプロパン EO変性トリ (メタ）アタリレート、ジペンタエリスリトールへキサ（メタ）アタリレート、ジペンタエリスリト ールモノヒドロキシペンタ（メタ）アタリレート、ジトリメチロールプロパンテトラ（メタ）ァク リレート、トリメチロールプロパントリ（メタ）アタリレート、ベンジルメルカプタン（メタ）ァク リレート等の多官能 (メタ）アタリレート類；  Pentaerythritol tri (meth) acrylate, trimethylolpropane (meth) acrylate, trimethylol propane PO modified tri (meth) acrylate, trimethylol propane EO modified tri (meth) acrylate, dipentaerythritol hexa (meta ) Atallate, dipentaerythritol monohydroxypenta (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, benzyl mercaptan (meth) acrylate Sensory (meth) atarylates;
上記化合物中の芳香環の水素原子のうち、；!〜 5個を塩素もしくは臭素原子に置換 した (メタ）アタリレート等があげられる。  Among the hydrogen atoms in the aromatic ring in the above compound, there may be mentioned; (meth) atalylate in which !!-5 are substituted with chlorine or bromine atoms.
[0042] 多官能 (メタ）アタリレート（B)は好ましくは下記式（1) [0042] The polyfunctional (meth) acrylate (B) is preferably represented by the following formula (1):
[0043] [化 3]
Figure imgf000012_0001
[0043] [Chemical 3]
Figure imgf000012_0001
[0044] 〔式（1)中、 R1は水素原子またはメチル基を表し、 R2は 2価の有機基を表し、 R3は 1価 の有機基を表す〕 [In the 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.]
で表される基を少なくとも 1つ、より好ましくは少なくとも 3つ有する化合物、特に好まし くは下記式（2)  A compound having at least one group, more preferably at least three groups represented by the formula (2):
ZOCH (CH OZ) (2)  ZOCH (CH OZ) (2)
[式（2)中、 Zは下記式（3)で表される。  [In formula (2), Z is represented by the following formula (3).
[0045] [化 4] [0045] [Chemical 4]
Figure imgf000012_0002
Figure imgf000012_0002
[0046] 〔式（3)中、 nは;!〜 10の実数である〕]  [In formula (3), n is a real number from;! To 10]]
で表される化合物が挙げられる。  The compound represented by these is mentioned.
[0047] nが上記範囲にある化合物を用いることによって、現像や焼成による寸法変化の少 なレ、パターンを形成することができる。 [0047] By using a compound in which n is in the above range, a pattern and a pattern with little dimensional change due to development or baking can be formed.
[0048] 多官能 (メタ）アタリレート（B)として上記化合物を用いることにより、パターン焼成後 に大幅な収縮が生じず、高精細のパターンを形成することができるとともに、熱分解 性に優れた感光性樹脂組成物が得られる。  [0048] By using the above-mentioned compound as the polyfunctional (meth) acrylate (B), there is no significant shrinkage after pattern firing, a high-definition pattern can be formed, and thermal decomposition is excellent. A photosensitive resin composition is obtained.
[0049] 上記式（2)で表される化合物は、下記式 (4)で示されるように、トリス（ポリオキシプ ロピレン）グリセリルエーテルとメタクリル酸 2—（ビニロキシエトキシ）ェチルとを付加反 応させることによって得られる。 [0049] The compound represented by the above formula (2) undergoes an addition reaction of tris (polyoxypropylene) glyceryl ether and 2- (vinyloxyethoxy) methacrylic acid as represented by the following formula (4). Can be obtained.
[0050] [化 5]
Figure imgf000013_0001
[0050] [Chemical 5]
Figure imgf000013_0001
~~— ZOCH(CH2OZ)2 (4)~~ — ZOCH (CH 2 OZ) 2 (4)
[0051] [式（4)中、 Zは上記式（3)で表され、 Rは下記式（5)で表される。 [0051] [In the formula (4), Z is represented by the above formula (3), and R is represented by the following formula (5).
[0052] [化 6] [0052] [Chemical 6]
Figure imgf000013_0002
Figure imgf000013_0002
[0053] 〔式（5)中、 nは;!〜 10の実数である〕]  [In the formula (5), n is a real number from !! to 10]]
なお、式（3)中の nは、上記式（2)で表される化合物のゲルパーミエ一： グラフィー（GPC)により測定したポリスチレン換算の重量平均分子量 (Mw)から、下 記式により求めたポリオキシプロピレンの平均重合度である。  In addition, n in the formula (3) is a polyperoxide obtained by the following formula from the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation: graphy (GPC) of the compound represented by the formula (2). It is the average degree of polymerization of oxypropylene.
[0054] 式（3)の平均重合度（n) = { (Mw—ポリオキシプロピレン以外の部位の また、式（5)中の nは、トリス（ポリオキシプロピレン）グリセリルエーテルのゲルパーミ エーシヨンクロマトグラフィー（GPC)により測定したポリスチレン換算の重量平均分子 量 (Mw)から、下記式により求めたポリオキシプロピレンの平均重合度である。 [0054] Average polymerization degree of formula (3) (n) = {(Mw—in a portion other than polyoxypropylene, and n in formula (5) is a gel permeation chromatography of tris (polyoxypropylene) glyceryl ether. This is the average degree of polymerization of polyoxypropylene determined by the following formula from the weight average molecular weight (Mw) in terms of polystyrene measured by chromatography (GPC).
[0055] 式（5)の平均重合度（n) = { (Mw—ポリオキシプロピレン以外の部位の 上記トリス（ポリオキシプロピレン）グリセリルエーテルの重量平均分子量（Mw)は 2 70〜； 1800力 S好ましい。トリス（ポリオキシプロピレン）グリセリルエーテルの重量平均 分子量が上記範囲にあると、現像や焼成による寸法変化の少ないパターンを形成す ること力 Sでさる。 [0055] Average polymerization degree of formula (5) (n) = {(Mw—weight average molecular weight (Mw) of the above tris (polyoxypropylene) glyceryl ether other than polyoxypropylene is from 2 70 to 1800 force S When the weight average molecular weight of tris (polyoxypropylene) glyceryl ether is in the above range, the force S can be formed to form a pattern with little dimensional change by development or baking.
[0056] 上記付加反応に用いられる触媒としては、酸が好適である。酸としては、例えば、ギ 酸、酢酸、プロピオン酸、ブタン酸、トリクロ口酢酸、ジクロロ酢酸、ピルビン酸、グリコ ール酸等の脂肪族モノカルボン酸；シユウ酸、マレイン酸、ォキサ口酢酸、マロン酸、 フマル酸、酒石酸、クェン酸等の脂肪族多価カルボン酸;安息香酸、テレフタル酸等 の芳香族カルボン酸；ベンゼンスルホン酸、 p—トルエンスルホン酸、 p—トルエンスル ホン酸ピリジニゥム塩、 p—トルエンスルホン酸キノリニゥム塩等の芳香族スルホン酸ま たはその塩;硫酸ナトリウム、硫酸カリウム、硫酸マグネシウム、硫酸カルシウム、硫酸 ニッケル、硫酸銅、硫酸ジルコニウム等の硫酸塩;硫酸水素ナトリウム、硫酸水素カリ ゥム等の硫酸水素塩;硫酸、塩酸、リン酸、ポリリン酸等の鉱酸；リンバナドモリブデン 酸、リンタンダストモリブデン酸、ケィタンダストモリブデン酸等のへテロポリ酸；酸性ゼ オライト;ベースレジンがフエノール系樹脂またはスチレン系樹脂であり、ゲル型、ポ 一ラス型またはマクロポーラス型の何れかの形態を示し、かつ、スルホン酸基および アルキルスルホン酸基からなる群より選ばれる少なくとも一種のイオン交換基を有す る酸性イオン交換樹脂などが挙げられる。 [0056] 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, trichloro oral acetic acid, dichloroacetic acid, pyruvic acid and glycolic acid; oxalic acid, maleic acid, oxa oral acetic acid, malon acid, Aliphatic polycarboxylic acids such as fumaric acid, tartaric acid and citrate; aromatic carboxylic acids such as benzoic acid and terephthalic acid; benzenesulfonic acid, p-toluenesulfonic acid, p-toluenesulfonic acid pyridinium salt, p-toluene Aromatic sulfonic acids such as quinolinium sulfonate or salts thereof; sulfates such as sodium sulfate, potassium sulfate, magnesium sulfate, calcium sulfate, nickel sulfate, copper sulfate, zirconium sulfate; sodium hydrogen sulfate, potassium hydrogen sulfate Hydrogen sulfate such as sulfuric acid, mineral acids such as sulfuric acid, hydrochloric acid, phosphoric acid and polyphosphoric acid; heteropoly acids such as phosphovanadmolybdic acid, phosphorus dust molybdic acid and ketan dust molybdic acid; acidic zeolite; base resin is phenolic Resin or styrenic resin, either gel type, porous type or macroporous type And an acidic ion exchange resin having at least one ion exchange group selected from the group consisting of a sulfonic acid group and an alkylsulfonic acid group.
[0057] 上記触媒は 1種単独で用いてもよぐ 2種以上を併用してもよい。上記の中でも、シ ユウ酸、マレイン酸、硫酸水素カリウム、塩酸、硫酸、リン酸が好ましい。他の酸触媒 の場合、付加反応の触媒として作用するほか、ビュルエーテルのカチオン重合開始 剤として作用することがある。したがって、温度コントロールを厳密に行う必要がある 力 なかでも塩酸の場合、カチオン重合開始剤としては作用せず、付加反応にのみ 選択的に効くため、温度コントロール幅が広ぐ製造面で非常に有利であり、特に好 ましい触媒である。  [0057] The above catalysts may be used alone or in combination of two or more. 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 an addition reaction catalyst, it may act as a cationic polymerization initiator for butyl ether. Therefore, hydrochloric acid does not act as a cationic polymerization initiator, but it works selectively only for addition reactions, and it is very advantageous in terms of production with a wide temperature control range. It is a particularly preferred catalyst.
[0058] 上記触媒の使用量としては、付加反応に用いるトリス（ポリオキシプロピレン)グリセリ ルエーテルとメタクリル酸 2—（ビニロキシエトキシ）ェチルの使用量ゃトリス（ポリオキ シプロピレン）グリセリルエーテルの種類に応じて適宜設定すればよいが、収率、触 媒の安定性、生産性および経済性の点から、例えば、メタクリル酸 2—（ビニ口キシェ トキシ)ェチル 100重量部に対して、好ましくは 0. 0005重量部以上、より好ましくは 0 . 001重量部以上である。また、好ましくは 3重量部以下、より好ましくは 1重量部以下 である。  [0058] The amount of the catalyst used depends on the type of tris (polyoxypropylene) glyceryl ether and tris (polyoxypropylene) glyceryl ether used in the addition reaction and the amount of 2- (vinyloxyethoxy) methacrylic acid used. However, from the viewpoints of yield, catalyst stability, productivity, and economy, for example, it is preferably 0.100 parts by weight with respect to 100 parts by weight of methacrylic acid 2- (vinyl chloride) ethyl ester. 0005 parts by weight or more, more preferably 0.001 part by weight or more. Further, it is preferably 3 parts by weight or less, more preferably 1 part by weight or less.
[0059] 上記多官能 (メタ）アタリレート（B)は、 1種単独で用いても、 2種以上を組み合わせ て用いてもよ!/、。本発明の組成物における上記多官能 (メタ）アタリレート（B)の含有 量は、上記 SH基含有樹脂 (A) 100重量部に対して、通常 20〜200重量部、好まし くは 30〜； 100重量部の範囲である。多官能（メタ）アタリレート（B)の含有量が少なす ぎると、露光部が現像液によって浸食されやすくなり、パターンを形成することができ ない。含有量が多すぎると、長時間の現像工程となり生産上好ましくない。さらに、焼 成時に収縮が大きくなり、剥れの原因となる。 [0059] The polyfunctional (meth) acrylate (B) may be used singly or in combination of two or more! /. The content of the polyfunctional (meth) acrylate (B) in the composition of the present invention is usually 20 to 200 parts by weight, preferably 100 to parts by weight of the SH group-containing resin (A). Or 30 to 100 parts by weight. If the content of the polyfunctional (meth) acrylate (B) is too small, the exposed portion is easily eroded by the developer, 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. In addition, shrinkage increases during firing, causing peeling.
[0060] <光重合開始剤（C) >  [0060] <Photoinitiator (C)>
本発明の組成物に用いられる光重合開始剤（C)としては、後述する露光工程にお V、てラジカルを発生し、上記 SH基含有樹脂 (A)と多官能 (メタ）アタリレート (B)との 重合反応を開始せしめる化合物である限り特に限定されない。  As the photopolymerization initiator (C) used in the composition of the present invention, radicals are generated in the exposure process described later, and the SH group-containing resin (A) and the polyfunctional (meth) acrylate (B) are used. As long as it is a compound that initiates the polymerization reaction with
[0061] 具体的には、ベンゾフエノン、 o ベンゾィル安息香酸メチル、 4, 4 ビス（ジメチル ァミン）ベンゾフエノン、 4, 4—ビス（ジェチルァミノ）ベンゾフエノン、 4, 4—ジクロロべ ンゾフエノン、 4一べンゾィルー 4ーメチルジフエ二ルケトン、ジベンジルケトン、フルォ レノン、 2, 2—ジエトキシァセトフエノン、 2, 2—ジメトキシー2—フエニノレー 2—フエ二 ノレァセトフエノン、 2—ヒドロキシー2—メチルプロピオフエノン、 p— t ブチルジクロ口 ァセトフエノン、チォキサントン、 2—メチルチオキサントン、 2—クロ口チォキサントン、 2—イソプロピルチォキサントン、 4 イソプロピルチォキサントン、 1 クロロー 4ープ ロピルチオキサントン、 2, 4 ジェチルチ才キサントン、ベンジルジメチルケタノ一ノレ 、ベンジルメトキシェチルァセタール、ベンゾイン、ベンゾインメチルエーテル、ベンゾ インブチルエーテル、アントラキノン、 2— t ブチルアントラキノン、 2—アミルアントラ キノン、 β クロノレアントラキノン、アントロン、ベンズアントロン、ジベンゾスベロン、メ チレンアントロン、 4 アジドベンザノレァセトフエノン、 2, 6 ビス（ρ アジドベンジリ デン）シクロへキサノン、 2, 6 ビス（ρ アジドベンジリデン） 4ーメチルシクロへキ サノン、 2—フエニノレー 1 , 2—ブタジオンー2—（ο メトキシカルボ二ノレ）ォキシム、 1 フエ二ループロパンジオン一 2—（ο エトキシカルボ二ノレ）ォキシム、 1 , 3 ジフエ 二ループロパントリオン 2—（ο エトキシカルボ二ノレ）ォキシム、 1 フエニノレー 3— エトキシ一プロパントリオン一 2— (ο ベンゾィル）ォキシム、ミヒラーケトン、 2—メチ ノレ 1 [4 （メチルチオ）フエニル] 2 モルフオリノー 1 プロパン 1 オン、 2 -ベンジルー 2 -ジメチルァミノ一 1 (4—モルフオリノフエ二ノレ）ブタノン一 1、 2—ヒ ドロキシ一 2—メチル 1—フエニル一プロパン一 1—オン、 2, 2'—ジメトキシ一 1 , 2 —ジフエニルェタン一 1—オン、ビス（2, 6—ジメトキシベンゾィル） 2, 4, 4—トリメ チルーペンチルフォスフィンオキサイド、 2, 4, 6 トリメチルベンゾィルージフエニル フォスフィンオキサイド、ビス（2, 4, 6 トリメチルベンゾィル）一フエニルフォスフィン オキサイド、ナフタレンスルホユルク口ライド、キノリンスルホユルク口ライド、 N フエ二 ノレチオアタリドン、 4, 4ーァゾビスイソブチロニトリル、ジフエユルジスルフイド、ベンズ チアゾールジスルフイド、トリフエニルホルフィン、カンファーキノン、四臭素化炭素、ト リブロモフエニルスルホン、過酸化べンゾイン、および、ェオシンゃメチレンブルーな どの光還元性の色素とァスコルビン酸やトリエタノールァミンなどの還元剤との組合せ などが挙げられる。 [0061] Specifically, benzophenone, o methyl benzoylbenzoate, 4,4 bis (dimethylamine) benzophenone, 4,4-bis (jetylamino) benzophenone, 4,4-dichlorobenzophenone, 4-benzoyl 4-methyldiphene Di-ketone, dibenzylketone, fluorenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenenole 2-phen-2-enocetophenone, 2-hydroxy-2-methylpropiophenone, p-t Butyldichloroacetophenone, thixanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 4 isopropylthioxanthone, 1 chloro-4-propylthioxanthone, 2, 4 jettyxanthone, benzyldimethylketanol , Benzylmethoxy Ruacetal, benzoin, benzoin methyl ether, benzoin butyl ether, anthraquinone, 2-t butylanthraquinone, 2-amylanthraquinone, β chronoleanthraquinone, anthrone, benzanthrone, dibenzosuberone, methylanthanthrone, 4 azidobenzanolasetof Enone, 2, 6 bis (ρ azidobenzylidene) cyclohexanone, 2, 6 bis (ρ azidobenzylidene) 4-methylcyclohexanone, 2—Phenenoleyl 1, 2—Butadione-2 -— (ο methoxycarboninole) oxime, 1 2-Propane Dione 1- (ο ethoxycarboninole) oxime, 1, 3 Diphenyl Propanetrione 2— (ο ethoxycarboninole) oxime, 1 Phenoline 3—Ethoxy-propanetrione 2— (ο Benzyl) ) Ximeme, Michler's ketone, 2-methylol 1 [4 (methylthio) phenyl] 2 morpholino 1 propane 1 on, 2-benzyl-2-dimethylamino 1 1 (4-morpholinofenole) butanone 1, 2-hydroxyl-2-methyl 1-phenyl monopropane 1-one, 2, 2'-dimethoxy mono 1, 2 —Diphenylethane 1-one, bis (2,6-dimethoxybenzoyl) 2, 4, 4-trimethyl-pentylphosphine oxide, 2, 4, 6 Trimethylbenzoyldiphenylphosphine oxide, bis (2, 4, 6-trimethylbenzoyl) monophenylphosphine oxide, naphthalenesulfurol chloride, quinolinesulfurol chloride, N-phenolethioatalidone, 4,4-azobisisobutyronitrile, diphenyl Photoreductive dyes such as disulfide, benzthiazole disulfide, triphenylformine, camphorquinone, carbon tetrabromide, tribromophenylsulfone, benzoin peroxide, and eosin methylene blue, ascorbic acid and And combinations with reducing agents such as triethanolamine.
[0062] 上記光重合開始剤（C)は、 1種単独で用いても、 2種以上を組み合わせて用いても よい。上記光重合性開始剤 (C)は、上記 SH基含有樹脂 (A)および多官能 (メタ)ァ クリレー HB)の合計量 100重量部に対して、通常 0. ；!〜 50重量部、好ましくは 0. 5 〜40重量部の範囲で用いられる。 0. 1重量部未満では、光感度を向上させる効果 が発揮されないことがあり、 50重量部を超えると、露光部の残存率が小さくなりすぎる こと力 sある。 [0062] The photopolymerization initiator (C) may be used alone or in combination of two or more. The photopolymerizable initiator (C) is usually 0.;! 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) alkyl relay HB). Is used in the range of 0.5 to 40 parts by weight. 0.1 is less than 1 part by weight, the effect of improving light sensitivity is not exerted, and when it exceeds 50 parts by weight, this a force s residual rate of exposed portions may be too small.
[0063] <無機粒子（D)〉  [0063] <Inorganic particles (D)>
本発明の組成物に用いられる無機粒子（D)は、形成材料の種類によって異なる。 特に FPDを構成する誘電体および隔壁形成材料に使用される無機粒子としては、 無機粒子（D)の少なくとも一部がガラス粉末であることが好ましい。  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 for the dielectric and the partition wall forming material constituting the FPD, at least a part of the inorganic particles (D) is preferably glass powder.
[0064] 本発明の組成物に用いられるガラス粉末としては、熱軟化点が 300〜650°C、好ま しくは 350〜600°Cの低融点ガラス粉末を挙げることができる。ガラス粉末の熱軟化 点が上記範囲よりも低!/、と、上記組成物から形成された感光性樹脂層の焼成工程に ぉレ、て、樹脂などの有機物質が完全に分解除去されなレ、段階でガラス粉末が溶融し てしまう。そのため、形成される部材中に有機物質の一部が残留し、その結果、誘電 体層や隔壁などの部材が着色されて、その光透過率が低下するおそれがある。一方 [0064] Examples of the glass powder used in the composition of the present invention include a low-melting glass powder having a heat softening point of 300 to 650 ° C, preferably 350 to 600 ° C. When the thermal softening point of the glass powder is lower than the above range! /, During the baking process of the photosensitive resin layer formed from the above composition, the organic substance such as resin is not completely decomposed and removed. At this stage, the glass powder melts. Therefore, a part of the organic substance remains in the formed member, and as a result, the members such as the dielectric layer and the partition are colored, and the light transmittance may be reduced. on the other hand
、ガラス粉末の熱軟化点が上記範囲を超えると、高温で焼成する必要があるために、 ガラス基板に歪みなどが発生しやすレ、。 When the thermal softening point of the glass powder exceeds the above range, the glass substrate needs to be fired at a high temperature.
[0065] 上記ガラス粉末としては、たとえば、（l) Bi O -ZnO-B O系、（2) Bi O—SiO -B O系、（3) Bi O - SiO -B O—Li O系、（4) Bi O—SiO—B O -Na O系[0065] Examples of the glass powder include (l) BiO-ZnO-BO system and (2) BiO-SiO. -BO system, (3) Bi O-SiO -BO-Li O system, (4) Bi O-SiO-BO -Na O system
、 (5) Bi O— Si〇2— B O— K2〇系、（6) Bi O— S ^— L^O系、（7) Bi2〇3— S ^ — Na2〇系、（8) Bi2〇3— SiO— I^O系、（9) Bi O - SiO^B O— ZnO系、（10) S iO B O Li O系、（11) SiO— B O Ν&2〇系、（12) S ^— B2〇3— I^O系、（ 13) Si〇2— B2〇3— ZrO— MgO系、 (14) SiO^B^-ZrO— CaO系、（15) SiO 2— B O— Zr〇2— MaO系、（16) S ^— B203— Zr〇2— SrO系、（17) SiO -B^ -ZrO -Li O系、（18) SiO—B O—ZrO -Na O系、（19) SiO—B O—ZrO(5) Bi O— Si ○ 2 — BO— K 2 system, (6) Bi O— S ^ — L ^ O system, (7) Bi 2 ○ 3 — S ^ — Na 2 system, (8 ) Bi 2 〇 3 - SiO- I ^ O system, (9) Bi O - SiO ^ bO- ZnO system, (10) S iO BO Li O system, (11) SiO- BO Ν & 2 〇 system, (12) S ^ — B 2 ○ 3 — I ^ O, (13) Si ○ 2 — B 2 ○ 3 — ZrO— MgO, (14) SiO ^ B ^ -ZrO— CaO, (15) SiO 2— BO — Zr〇 2 — MaO system, (16) S ^ — B 2 0 3 — Zr〇 2 — SrO system, (17) SiO —B ^ -ZrO —Li O system, (18) SiO—BO—ZrO —Na O type, (19) SiO-BO-ZrO
— K2〇系、（20)Α1 Ο— B2〇3— SiO— BaO— CaO— L^O— MgO— Ν&2〇— SrO — Ti〇2— ZnO系、（21)A1 0— B^— S ^— BaO— CaO LyD MgO— Na O-TiO—ZnO系、（22)A1 0 -B^- SiO— BaO— CaO— L^O— MgO— Na O— Fe2〇3— Ti〇2— ZnO系などのガラス分末を挙げることができる。 — K 2 〇 system, (20) Ο1 Ο— B 2 〇 3 — SiO— BaO— CaO— L ^ O— MgO— Ν & 2 〇— SrO — Ti〇 2 — ZnO system, (21) A1 0— B ^ — S ^ — BaO— CaO LyD MgO— Na O—TiO—ZnO system, (22) A1 0 -B ^-SiO— BaO— CaO— L ^ O— MgO— Na O— Fe 2 0 3 — Ti 0 2 — Examples include ZnO-based glass powders.
[0066] 上記ガラス粉末の形状としては特に限定されな!/、。上記ガラス粉末は 1種単独で用 いても、異なるガラス粉末組成、異なる軟化点、異なる形状、異なる平均粒子径を有 するガラス粉体を 2種以上組み合わせて用いてもよ!/、。  [0066] 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 sizes.
[0067] 上記ガラス粉末は、より高精細化のパターユングを得るために、酸化珪素を 5〜50 重量％の範囲で含有することが好ましぐ 10〜30重量％の範囲で含有することがよ り好ましい。酸化珪素は、ガラスの緻密性、強度および安定性を向上させる働きを有 するとともに、ガラスの低屈折率化にも効果がある。また、熱膨張係数をコントロール してガラス基板とのミスマッチによる剥離等を防ぐこともできる。酸化珪素の含有量が 5重量％以上であることにより、熱膨張係数を小さく抑え、ガラス基板に焼き付けた時 に起こるクラックの発生を低減すること力できるとともに、屈折率を低く抑えることがで きる。また、酸化珪素の含有量が 50重量％以下であることにより、ガラス転移点およ び荷重軟化点を低く抑え、ガラス基板への焼き付け温度を低くすることができる。  [0067] The glass powder preferably contains silicon oxide in the range of 5 to 50% by weight in order to obtain a higher-definition patterning. More preferable. Silicon oxide has a function of improving the denseness, strength and stability of the glass, and is also effective in lowering 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 silicon oxide content is 5% by weight or more, the coefficient of thermal expansion can be kept small, the generation of cracks occurring when baked on a glass substrate can be reduced, and the refractive index can be kept low. . Further, 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.
[0068] 上記ガラス粉末は、酸化ホウ素を 10〜50重量％の範囲で含有することが好ましぐ  [0068] The glass powder preferably contains boron oxide in the range of 10 to 50 wt%.
20〜45重量％の範囲で含有することがより好ましい。酸化ホウ素の含有量が 10重 量％以上であることにより、ガラス転移点および荷重軟化点を低く抑え、ガラス基板 への焼き付けを容易にすることができる。また、酸化ホウ素の含有量が 50重量％以 下であることにより、ガラスの化学的安定性を維持することができる。なお、酸化ホウ 素は低屈折率化にも有効である。 More preferably, it is contained in the range of 20 to 45% by weight. When the boron oxide content 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 boron oxide content is 50% by weight or less, the chemical stability of the glass can be maintained. In addition, boron oxide Elemental is also effective for lowering the refractive index.
[0069] 上記ガラス粉末は、酸化バリウムおよび酸化ストロンチウムのうち少なくとも 1種を、 その合計量が 1〜30重量％の範囲となるように含有することが好ましぐ 2〜20重量 %の範囲となるように含有することがより好ましい。これらの成分は、熱膨張係数の調 整に有効であり、焼成時の基板の変形を防止する効果、電気絶縁性を付与する効果 、形成される隔壁の安定性および緻密性を向上する効果などを有する。これらの含 有量が 1重量％以上であることにより、ガラスの結晶化による失透を防ぐこともでき、ま た、 30重量％以下であることにより、熱膨張係数および屈折率を小さく抑えることが できるとともに、化学的安定性を維持することができる。  [0069] 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 in the range of 2 to 20% by weight. It is more preferable to contain it. These components are effective in adjusting the thermal expansion coefficient, prevent the substrate from being deformed during firing, provide electrical insulation, improve the stability and denseness of the partition walls 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 are kept small. And maintain chemical stability.
[0070] 上記ガラス粉末は、酸化アルミニウムを 1〜40重量％の範囲で含有することが好ま しい。酸化アルミニウムは、ガラス化範囲を広げてガラスを安定化する効果があり、組 成物のポットライフ延長にも有効である。酸化アルミニウムの含有量が前記範囲内で あることにより、ガラス転移点および荷重軟化点を低く保ち、基板への密着性を向上 すること力 Sでさる。  [0070] The glass powder preferably contains aluminum oxide in the range of 1 to 40% by weight. Aluminum oxide has the effect of expanding the vitrification range and stabilizing the glass, and is also effective in extending the pot life of the composition. When the aluminum oxide content is within the above range, the glass transition point and the load softening point are kept low and the adhesion to the substrate is improved with the force S.
[0071] 上記ガラス粉末は、酸化カルシウムおよび酸化マグネシウムのうち少なくとも 1種を、 その合計量が 1〜20重量％となるように含有することが好ましい。これらの成分は、ガ ラスを溶融しやすくするとともに、熱膨張係数を制御する効果を有する。これらの含有 量が 1重量％以上であることにより、ガラスの結晶化による失透を防ぐことができ、また 、 15重量％以下であることにより、ガラスの化学的安定性を維持することができる。  [0071] 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 an effect of making glass easily 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. .
[0072] 上記ガラス粉末は、酸化リチウム、酸化ナトリウムおよび酸化カリウムのアルカリ金属 酸化物を 1〜20重量％の範囲で含有することが好ましい。アルカリ金属酸化物は、ガ ラスの熱軟化点および熱膨張係数のコントロールを容易にするとともに、ガラス粉末と しての屈折率を低くする効果を有する。アルカリ金属酸化物は、イオンのマイグレー シヨンや拡散を促進することがあるので、合計量を 20重量％以下とすることにより、ガ ラスの化学的安定性を維持するとともに熱膨張係数を小さく抑えることができる。  [0072] The glass powder preferably contains an alkali metal oxide of lithium oxide, sodium oxide and potassium oxide in a 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. Alkali metal oxides may promote ion migration and diffusion, so the total amount should be 20% by weight or less to maintain the chemical stability of the glass and keep the thermal expansion coefficient small. be able to.
[0073] 上記ガラス粉末は、上記成分に加えて、酸化亜鉛、酸化チタン、酸化ジルコニウム 等を含有してもよい。  [0073] The glass powder may contain zinc oxide, titanium oxide, zirconium oxide and the like in addition to the above components.
[0074] 上記ガラス粉末の平均粒子径は、作製しょうとするパターンの形状を考慮して選ば れるカ S、パターン形成上、好ましくは 0· 01〜； 10 m、より好ましくは 0. 1〜5 111で ある。また、ガラス粉末の比表面積は 0. ；!〜 300m2/gであること力 パターン形 成上好ましい。 [0074] The average particle size of the glass powder is selected in consideration of the shape of the pattern to be produced. In view of pattern formation, S is preferably from 0.01 to 10 m, more preferably from 0.1 to 5111. The specific surface area of the glass powder 0.5;! That force pattern shape Naruue preferably ~ 300m 2 / g.
[0075] 上記ガラス粉末は、 FPDの誘電体および隔壁以外の構成要素（例えば電極 '抵抗 体 ·蛍光体 'カラーフィルター ·ブラックマトリスク）を形成するための組成物中に含有さ れていてもよい。この場合のガラス粉末の含有量は、用途によって異なるが、ガラス粉 末を含む無機粒子（D)全量 100重量部に対して、通常;!〜 90重量部であり、好ましく は；!〜 80重量部である。  [0075] The glass powder may be contained in a composition for forming components other than the FPD dielectric and barrier ribs (eg, electrode 'resistor · phosphor' color filter · black matrix). Good. The content of the glass powder in this case varies depending on the application, but it is usually from! To 90 parts by weight, preferably from! Part.
[0076] FPD、 LCD,有機 EL、プリント回路基板、多層回路基板、モジュール、インダクタ および LSIなどの電極形成材料に使用される無機粒子（D)としては、 Al、 Ag、 Ag- Pd合金、 Au、 Ni、 Cr、 Cuなどを挙げることができる。これらの中では、大気中で焼成 した場合においても酸化による導電性の低下が生じず、比較的安価な Agを用いるこ とが好ましい。電極形成材料に使用される無機粒子（D)の形状としては、粒状、球状 、フレーク状等、特に限定されず、同じ形状の無機粒子（D)を用いても、異なる 2種 以上の形状の無機粒子（D)を混合して用いてもよい。また、平均粒径としては、好ま しく ίま 0. 01— lO ^ m,より好ましく (ま 0. 05〜5〃111であり、異なる平均粒径を有する 無機粒子（D)を混合して使用することもできる。  [0076] Inorganic particles (D) used in electrode forming materials such as FPD, LCD, organic EL, printed circuit board, multilayer circuit board, module, inductor and LSI include Al, Ag, Ag-Pd alloy, Au , Ni, Cr, Cu, etc. Among these, it is preferable to use Ag which is relatively inexpensive because it 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, or flaky. Even if inorganic particles (D) having the same shape are used, two or more different shapes are used. Inorganic particles (D) may be mixed and used. Further, the average particle size is preferably ί or 0.01—lO ^ m, more preferably (0.05 to 5 to 111 mm, mixed with inorganic particles (D) having different average particle sizes. You can also
[0077] これらの電極形成材料に使用される無機粒子（以下「導電性粉体」ともいう。）とガラ ス粉末とを併用する場合、導電性粉体の種類にもよるが、ガラス粉末の含有量は、通 常、無機粒子（D)全量 100重量部に対して、通常 1〜30重量部である。  [0077] When inorganic particles used in these electrode forming materials (hereinafter also referred to as "conductive powder") and glass powder are used in combination, depending on the type of conductive powder, The content is usually 1 to 30 parts by weight with respect to 100 parts by weight of the total amount of inorganic particles (D).
[0078] 具体例を挙げると、導電性粉体として Ag、 Cu、 Ni、 Sn、 Znを用いる場合には無機 粒子（D)全量 100重量部に対して、ガラス粉末を 1〜； 10重量部、好ましくは 2〜7重 量部用いる。  [0078] To give a specific example, when Ag, Cu, Ni, Sn, Zn is used as the conductive powder, 1 to 10 parts by weight of the glass powder with respect to 100 parts by weight of the total amount of inorganic particles (D). Preferably, 2 to 7 parts by weight are used.
Ag— Ptを用いる場合には、無機粒子（D)全量 100重量部に対して、ガラス粉末を 1 〜； 10重量部、好ましくは 1〜5重量部用いる。  When Ag—Pt is used, 1 to 10 parts by weight, preferably 1 to 5 parts by weight of glass powder is used with respect to 100 parts by weight of the total amount of inorganic particles (D).
Au、 Ptを用いる場合には、無機粒子（D)全量 100重量部に対して、ガラス粉末を 1 〜5重量部、好ましくは 1〜4重量部用いる。  When Au or Pt is used, the glass powder is used in an amount of 1 to 5 parts by weight, preferably 1 to 4 parts by weight, based on 100 parts by weight of the total amount of inorganic particles (D).
A1を用いる場合には、無機粒子（D)全量 100重量部に対して、ガラス粉末を 5〜30 重量部、好ましくは 9〜20重量部用いる。 When A1 is used, 5 to 30 glass powder is added to 100 parts by weight of the total amount of inorganic particles (D). Part by weight, preferably 9 to 20 parts by weight is used.
[0079] FPD、 LCD、有機 EL素子などの透明電極形成材料に使用される無機粒子（D)と しては、酸化インジウム、酸化錫、錫含有酸化インジウム（ITO)、アンチモン含有酸 化錫 (ATO)、フッ素添加酸化インジウム（FIO)、フッ素添加酸化錫（FTO)、フッ素 添加酸化亜鉛（FZO)、ならびに、 Al、 Co、 Fe、 In、 Snおよび Tiから選ばれた 1種も しくは 2種以上の金属を含有する酸化亜鉛微粒子などを挙げることができる。 PDPの 抵抗体形成材料に使用される無機粒子（D)としては、 RuOなどからなる粒子を挙げ ること力 Sでさる。 [0079] 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), fluorine-doped indium oxide (FIO), fluorine-doped tin oxide (FTO), fluorine-doped zinc oxide (FZO), and one or two selected from Al, Co, Fe, In, Sn and Ti Examples thereof include zinc oxide fine particles containing at least one kind of metal. As the inorganic particles (D) used for the resistor-forming material of PDP, mention is made of particles made of RuO or the like with the force S.
[0080] FPD、 PDPの蛍光体形成材料に使用される無機粒子（D)は、  [0080] The inorganic particles (D) used in the phosphor forming materials of FPD and PDP are
赤色用としては、 Y O： Eu3+、 Y SiO： Eu3+、 Y Al O ： Eu \ YVO： Eu3+、（Y, Gd For red, YO: Eu 3+ , Y SiO: Eu 3+ , Y Al O: Eu \ YVO: Eu 3+ , (Y, Gd
2 3 2 5 3 5 12 4  2 3 2 5 3 5 12 4
) BO： Eu3+、Zn (PO ) ： Mnなどが挙げられ、 ) BO: Eu 3+ , Zn (PO): Mn, etc.
3 3 4 2  3 3 4 2
緑色用としては、 Zn SiO : Mn、 BaAl O ： Mn, BaMgAl O ： Mn、LaPO : (Ce  For green, Zn SiO: Mn, BaAl O: Mn, BaMgAl O: Mn, LaPO: (Ce
2 4 12 19 14 23 4 2 4 12 19 14 23 4
, Tb)、 Y (Al, Ga) O ： Tbなどが挙げられ、 , Tb), Y (Al, Ga) O: Tb, etc.
3  Three
青色用としては、 Y ： Eu2+、 (Ca, Sr,For blue, Y: Eu 2+ , (Ca, Sr,
Figure imgf000020_0001
Figure imgf000020_0001
Ba) (PO ) CI： Eu2+、 (Zn, Cd) S :Agなどが挙げられる。 Ba) (PO) CI: Eu2 + , (Zn, Cd) S: Ag, and the like.
10 4 6 2  10 4 6 2
[0081] FPD、 PDP、 LCD,有機 EL素子などのカラーフィルター形成材料に使用される無 機粒子（D)は、赤色用としては Fe Oなど、緑色用としては Cr Oなど、青色用として  [0081] Inorganic particles (D) used in color filter forming materials such as FPD, PDP, LCD, and organic EL devices are Fe O for red, Cr O for green, and blue for green.
2 3 2 3  2 3 2 3
は CoO'Al Oなどを挙げることができる。  Can include CoO'AlO.
2 3  twenty three
[0082] FPD、 PDP、 LCD,有機 EL素子などのブラックストライプ（マトリックス）形成材料に 使用される無機粒子（D)としては、例えば、 Co、 Cr、 Cu、 Fe、 Mn、 Ni、 Ti、 Znなど の金属およびその酸化物、複合酸化物、炭化物、窒化物、硫化物、けい化物、ほう 化物やカーボンブラック、グラフアイトなどを挙げることができ、 1種単独で用いても、 2 種以上を混合して用いてもよい。これらの中では、 Co、 Cr、 Cu、 Fe、 Mn、 Niおよび Tiの群から選ばれた金属粒子、金属酸化物粒子および複合酸化物粒子が好まし!/、 。また、平均粒径としては、好ましくは 0. 01— 10 μ m、より好ましくは 0· 05—5 μ m、 特に好ましくは 0. l〜2〃mである。  [0082] Examples of inorganic particles (D) used in black stripe (matrix) forming materials such as FPD, PDP, LCD, and organic EL elements include Co, Cr, Cu, Fe, Mn, Ni, Ti, Zn And their oxides, composite oxides, carbides, nitrides, sulfides, silicides, borides, carbon black, graphite, etc., even if used alone or in combination of two or more. You may mix and use. 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 preferred! / ,. The average particle diameter is preferably 0.01 to 10 μm, more preferably 0.05 to 5 μm, and particularly preferably 0.1 to 2 μm.
[0083] これらの無機粒子とガラス粉末とを併用する場合、ガラス粉末の含有量は、通常、 無機粒子（D)全量 100重量部に対して、通常 60〜90重量部であり、好ましくは 70〜 90、さらに好ましくは 73〜86重量きである。 [0083] 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 100 parts by weight of the total amount of inorganic particles (D). ~ 90, more preferably 73 to 86 weight.
[0084] 本発明の組成物における無機粒子（D)の含有量は、上記 SH基含有樹脂 (A) 100 重量部に対して、 100〜2000重量部、好ましくは 130〜1000重量部の範囲である 。無機粒子（D)の含有量が前記範囲内であることにより、形状が良好なパターンを形 成すること力 Sでさる。  [0084] The content of the inorganic particles (D) in the composition of the present invention is in the range of 100 to 2000 parts by weight, preferably 130 to 1000 parts by weight, with respect to 100 parts by weight of the SH group-containing resin (A). is there . When the content of the inorganic particles (D) is within the above range, a force S can be formed to form a pattern having a good shape.
[0085] <紫外線吸収剤〉  [0085] <Ultraviolet absorber>
本発明の感光性樹脂組成物には、紫外線吸収剤を添加することも有効である。紫 外線吸収効果の高い化合物を添加することによって、高アスペクト比、高精細、高解 像度が得られる。紫外線吸収剤としては、有機系染料または無機系顔料を用いること ができ、中でも 350〜450nmの波長範囲で高 UV吸収係数を有する有機系染料ま たは無機顔料が好ましく用いられる。具体的には、ァゾ系染料、アミノケトン系染料、 キサンテン系染料、キノリン系染料、キノン系染料、アミノケトン系染料、アントラキノン 系、ベンゾフエノン系、ジフエ二ルシアノアクリレート系、トリアジン系、 p ァミノ安息香 酸系染料などの有機系染料、酸化亜鉛、酸化チタン、酸化セリウムなどの無機顔料 を用いること力 Sできる。これらにおいて、有機系染料は、焼成後の絶縁膜中に残存し ないため、絶縁膜特性の低下を少なくできるので好ましいが、フラットディスプレイパ ネルの信頼性の観点から酸化亜鉛、酸化チタン、酸化セリウムのような無機顔料がよ り好ましい。  It is also effective to add an ultraviolet absorber to the photosensitive resin composition of the present invention. By adding a compound with a high ultraviolet absorption effect, a high aspect ratio, high definition, and high resolution can be obtained. As the ultraviolet absorber, organic dyes or inorganic pigments can be used, and among them organic dyes or inorganic pigments having a high UV absorption coefficient in the wavelength range of 350 to 450 nm are preferably used. Specific examples include 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. It is possible to use organic dyes such as dyes and inorganic pigments such as zinc oxide, titanium oxide, and cerium oxide. Of these, organic dyes are preferred because they do not remain in the insulating film after firing, and can reduce deterioration of insulating film characteristics. However, from the viewpoint of flat display panel reliability, zinc oxide, titanium oxide, and cerium oxide are preferable. Inorganic pigments such as are more preferred.
[0086] 上記無機顔料は、多官能（メタ）アタリレート（B) 100重量部に対して、 0. 01 - 10 重量部、好ましくは 0. 03〜5重量部の範囲となる量で添加することができる。無機顔 料の添加量が少なすぎると、紫外線吸光剤の添加効果が減少し、添加量が多すぎる と、焼成後の絶縁膜特性が低下することや、成膜強度が保てないことがある。  [0086] The inorganic pigment is added in an amount ranging from 0.01 to 10 parts by weight, preferably from 0.03 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 inorganic pigment added is too small, the effect of adding the UV light absorber will be reduced. If the amount added is too large, the insulating film properties after firing may be deteriorated or the film strength may not be maintained. .
[0087] <増感剤〉  [0087] <Sensitizer>
本発明の感光性樹脂組成物には、感度を向上させるために、増感剤を添加しても よい。増感剤としては、たとえば、 2—メチルチオキサントン、 2—クロ口チォキサントン 、 2—イソプロピルチォキサントン、 4 イソプロピルチォキサントン、 1 クロロー 4 プロピルチォキサントン、 2, 4 ジェチルチオキサントン、 2, 3 ビス（4 ジェチノレ ァミノベンザノレ）シクロペンタノン、 2, 6 ビス（4ージメチルアミ二ベンザノレ）シクロへ キサノン、 2, 6 ビス（4ージメチルァミノべンザル）ー4ーメチルシクロへキサノン、ミヒ ラーケトン、 4, 4 ビス（ジェチルァミノ）一べンゾフエノン、 4, 4 ビス（ジメチルァミノ )カルコン、 4, 4 ビス（ジェチルァミノ）カルコン、 p ジメチルァミノシンナミリデンィ ンダノン、 p ジメチルァミノべンジリデンインダノン、 2—（p ジメチルァミノフエニル ビニレン） イソナフトチアゾール、 1 , 3—ビス（4ージメチルァミノベンザル）アセトン、 1 , 3—カルボ二ルービス（4ージェチルァミノベンザル）アセトン、 3, 3—カルボニル ビス（7—ジェチルァミノクマリン）、 N フエ二ルー N ェチルエタノールァミン、 N フエニルエタノールァミン、 N—トリルジエタノールアミン、 N—フエニルエタノール ァミン、ジメチルァミノ安息香酸イソァミル、ジェチルァミノ安息香酸イソァミル、 3—フ ェニノレ 5—ベンゾイノレチォテトラゾーノレ、 1 フエニノレ 5—エトキシカノレポニノレチ ォテトラゾールなどが挙げられる。 A sensitizer may be added to the photosensitive resin composition of the present invention in order to improve sensitivity. Examples of sensitizers include 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 4 isopropylthioxanthone, 1 chloro-4-propylthioxanthone, 2, 4 jetylthioxanthone, 2, 3 bis (4 Getinoreaminobenzanol) cyclopentanone, 2, 6 bis (4-dimethylaminibenzanol) cycloto Xanone, 2, 6 bis (4-dimethylaminobenzal) -4-methylcyclohexanone, Michler's ketone, 4, 4 bis (jetylamino) monobenzophenone, 4, 4 bis (dimethylamino) chalcone, 4, 4 bis (jetylamino) chalcone, p dimethylaminocinnamylidindanone, p dimethylaminobenzylideneindanone, 2- (p dimethylaminophenyl vinylene) isonaftothiazole, 1,3-bis (4-dimethylaminobenzal) acetone, 1, 3-Carbonyl bis (4-Jetylaminobenzal) acetone, 3,3-Carbonyl bis (7-Jetylaminocoumarin), N-phenyl-N-ethylethanolamine, N-phenylethanolamine , N-tolyldiethanolamine, N-phenylethanolamine, dimethylaminobenzoic acid Le, Jechiruamino benzoate Isoamiru, 3- full Eninore 5- benzo Ino les Chio tetra Eaux Honoré, like 1 Fueninore 5-ethoxy Kano repo Nino retinyl Otetorazoru.
[0088] 上記増感剤は、 1種単独で用いても、 2種以上を組み合わせて用いてもよい。なお 、増感剤の中には光重合開始剤としても使用できるものがある。上記増感剤は、上記 多官能（メタ）アタリレート（B) 100重量部に対して、通常 0. 01〜； 10重量部、より好ま しくは 0. 05〜5重量部の範囲となる量で添加することができる。増感剤の量が少な すぎると、光感度を向上させる効果が発揮されないことがあり、増感剤の量が多すぎ ると、露光部の残存率が小さくなりすぎることがある。  [0088] The above sensitizers may be used alone or in combination of two or more. Some sensitizers can also be used as photopolymerization initiators. The amount of the sensitizer is usually 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). Can be added. If the amount of the sensitizer is too small, the effect of improving the photosensitivity may not be exhibited. If the amount of the sensitizer is too large, the residual ratio of the exposed area may be too small.
[0089] <重合禁止剤〉  [0089] <Polymerization inhibitor>
本発明の感光性樹脂組成物には、保存時の熱安定性を向上させるために、重合 禁止剤を添加してもよい。重合禁止剤としては、例えば、ヒドロキノン、ヒドロキノンの モノエステル化物、 N ニトロソジフエニルァミン、フエノチアジン、 p— t ブチルカテ コーノレ、 N—フエニルナフチルァミン、 2, 6 ジ tーブチルー p メチルフエノーノレ、 クロラニール、ピロガロールなどが挙げられる。重合禁止剤は、組成物中に、通常 0. 00；!〜 5重量％の範囲となる量で添加することができる。  A polymerization inhibitor may be added to the photosensitive resin composition of the present invention in order to improve thermal stability during storage. Examples of the polymerization inhibitor include hydroquinone, monoesterified hydroquinone, N-nitrosodiphenylamine, phenothiazine, p-t-butylcatenole, N-phenylnaphthylamine, 2,6-di-tert-butyl-p-methylphenol. , Chloranil, pyrogallol and the like. The polymerization inhibitor can be added to the composition in an amount usually ranging from 0.00;! To 5% by weight.
[0090] <酸化防止剤〉  [0090] <Antioxidant>
本発明の感光性樹脂組成物には、保存時における SH基含有樹脂 (A)、特に SH 基含有 (メタ）アクリル樹脂の酸化を防ぐために、酸化防止剤を添加してもよい。酸化 防止剤としては、例えば、 2, 6 ジー tーブチルー p クレゾール、ブチル化ヒドロキ シァニソール、ステアリル一 β - (3, 5—ジ一 t ブチル 4—ヒドロキシフエニル）プ 口ピオネート、 2, 6 ジ一 t— 4 ェチルフエノール、 2, 2 メチレン一ビス一（4 メ チルー 6— t ブチルフエノール）、 2, 2 メチレン ビス一（4ーェチルー 6—t ブ チルフエノール）、 4, 4ーブチリデンビス一（3—メチルー 6— t ブチルフエノーノレ）、 4, 4ーチォビス一（3—メチルー 6— t ブチルフエノール）、 4, 4 ビスー（3—メチル — 6— t ブチルフエノール）、 1 , 1 , 3 トリス一（2 メチル 6— t ブチルフエノー ノレ）、 1 , 1 , 3 トリス一（2 メチル 4 ヒドロキシ一 t ブチルフエ二ノレ）ブタン、ビス [3, 3—ビス一（4ーヒドロキシー3— t ブチルフエ二ノレ）ブチリックアシッド]グリコー ルエステル、ジラウリルチオジプロピオナート、トリフエニルホスファイトなどが挙げられ る。酸化防止剤は、組成物中に、通常 0. 00；!〜 5重量％の範囲となる量で添加する こと力 Sでさる。 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. Antioxidants include, for example, 2,6-di-tert-butyl-p-cresol, butylated hydroxy. Cyanisole, stearyl mono-β- (3,5-di-tert-butyl 4-hydroxyphenyl) propionate, 2,6 di-tert-ethyl ether, 2,2 methylene mono-bis (4-methyl-6-tert-butyl) Phenol, 2,2 methylene bis (4-ethyl-6-t butylphenol), 4,4-butylidenebis (3-methyl-6-t butylphenol), 4,4-thiobis (3-methyl-6-t) 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-hydroxyl) t-Butylphenol) butane, bis [3,3-bis-1- (4-hydroxy-3-butylphenol) butyric acid] glycol ester, dilauryl thiodipropionate, triphenyl phosphite Etc. is Ru and the like. The antioxidant is added to the composition in an amount usually ranging from 0.00 ;! to 5% by weight.
<有機溶媒〉  <Organic solvent>
本発明の感光性樹脂組成物には、溶液の粘度を調整するために、有機溶媒をカロ えてもよい。有機溶媒としては、例えば、エチレングリコールモノメチルエーテル、ェ チレングリコーノレモノェチノレエーテノレ、エチレングリコーノレモノブチノレエーテノレ、プロ ピレンダリコールモノメチルエーテルアセテート、ェチルー 3—エトキシプロピオネート 、プロピレングリコーノレモノメチノレエーテノレ、プロピレングリコーノレモノェチノレエーテノレ 、メチノレセロソノレブ、ェチノレセロソノレブ、ブチノレセロソノレブ、メトキシプロピノレアセテー ト、ジェチルケトン、メチルブチルケトン、ジプロピルケトン、メチルェチルケトン、ジォ キサン、アセトン、シクロへキサノン、シクロペンタノン、 n—ペンタノ一ノレ、ジアセトンァ ノレコーノレ、 4ーメチノレー 2 ペンタノ一ノレ、 シクロへキサノーノレ、イソブチノレアノレコーノレ 、イソプロピルアルコール、テトラヒドロフラン、ジメチルスルフォキシド、 γ ブチロラタ トン、ブロモベンゼン、クロ口ベンゼン、ジブロモベンゼン、ジクロロベンゼン、ブロモ安 息香酸、クロ口安息香酸、酢酸 η ブチル、酢酸アミル、乳酸ェチル、乳酸 η— ブチル、タービネオール、ジヒドロタ一ビネオール、ジヒドロタ一ビネニルアセテート、リ モネン、力ノレべォーノレ、カノレビニノレアセテート、シトロネローノレ、ジエチレングリコーノレ モノェチルエーテルアセテート、ジエチレングリコールモノブチルエーテルアセテート In order to adjust the viscosity of the solution, an organic solvent may be added to the photosensitive resin composition of the present invention. Examples of the organic solvent include ethylene glycol monomethyl ether, ethylene glycol monomethino enoate, ethylene glycol monobutino enoate, propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, propylene glycol Noremonomethinoreethenole, Propyleneglycolenoremonoechinoreetenore, MethinorecelloSoreolev, Echinorecerosonoreb, Butinorecerosonoreb, Methoxypropinoreacetate, Jetylketone, Methylbutylketone, Dipropyl Ketone, Methyl ethyl ketone, Dioxane, Acetone, Cyclohexanone, Cyclopentanone, n-Pentanolol, Diacetone alcohole, 4-Methanole 2 Pentanolol, Cyclohexanol Tinoleanolo Cornole, Isopropyl alcohol, Tetrahydrofuran, Dimethyl sulfoxide, γ-Butyrolatathone, Bromobenzene, Black-mouthed benzene, Dibromobenzene, Dichlorobenzene, Bromobenzoic acid, Black-mouthed benzoic acid, η-Butyl acetate, Amyl acetate , Ethyl lactate, η-butyl lactate, terbinol, dihydrotabinol acetate, dihydrotabinenyl acetate, limonene, force nobelonore, canolevininoacetate, citronellonore, diethyleneglycolone monoethyl ether acetate, diethylene glycol monobutyl ether acetate
、ジメチルスルフォキシドなどが挙げられる。上記有機溶媒は、 1種単独で用いても、 2種以上を混合して用いてもょレ、。 And dimethyl sulfoxide. Even if the above organic solvent is used alone, You can use a mixture of two or more.
<密着助剤〉  <Adhesion aid>
本発明の感光性樹脂組成物には、支持体との密着性を向上させるために、密着助 剤を加えてもよい。密着助剤としては、シラン化合物が好適に用いられる。シラン化合 物の具体例としては、 n—プロピルジメチルメトキシシラン、 n-
Figure imgf000024_0001
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 silane compounds include n-propyldimethylmethoxysilane, n-
Figure imgf000024_0001
Figure imgf000024_0002
Figure imgf000024_0002
シラン、 n ィコサンジプロピルメトキシシラン、 n プロピルジメチルエトキシシラン、 n ーブチノレジメチノレエトキシシラン、 n デシノレジメチノレエトキシシラン、 n へキサデシ ノレジメチルエトキシシラン、 n ィコサンジメチルエトキシシラン、 n プロピルジェチ ノレエトキシシラン、 n ブチノレジェチノレエトキシシラン、 n デシノレジェチノレエトキシシ ラン、 n へキサデシノレジェチノレエトキシシラン、 n ィコサンジェチノレエトキシシラン 、 n ブチルジプロピルエトキシシラン、 n デシルジプロピルエトキシシラン、 n へ キサデシルジプロピルエトキシシラン、 n ィコサンジプロピルエトキシシラン、 n プ Silane, n-icosanedipropylmethoxysilane, n-propyldimethylethoxysilane, n-butinoresimethino ethoxysilane, n decinoresimethino ethoxysilane, n-hexadecinole dimethylethoxysilane, n-icosane dimethylethoxysilane, n-propyljetino Ethoxy silane, n butino lesino ethoxy silane, n decino lesino ethoxy silane, n hexa deceno lesino ethoxy silane, n icosantino ethoxy silane, n butyldipropyl ethoxy silane, n Decyldipropylethoxysilane, n-hexadecyldipropylethoxysilane, n-icosanedipropylethoxysilane, n
Figure imgf000024_0003
Figure imgf000024_0003
ロポキシシラン、 n n へキサデシノレジプロピ ノレプロポキシシラ tiメトキシシラン、 n Lopoxysilane, n n hexadesinoresin propipropenosiloxy ti methoxysilane, n
n へキサ n Hexa
口ピルェ Mouth pirou
ll一へキサデシノレェ till プロピルメチルジェトキシシラン、 n ブチルメチルジェトキシシラン、 n デシルメ チノレジェトキシシラン、 n へキサデシノレメチノレジェトキシシラン、 n ィコサンメチノレ ジエトキシシラン、 n プロピノレエチノレジェトキシシラン、 n ブチノレエチノレジェトキシ シラン、 n デシノレエチノレジェトキシシラン、 n へキサデシノレエチノレジェトキシシラン n ィコサンェチノレジェトキシシラン、 n ブチノレプロピノレジェトキシシラン、 n デシ ルプロピルジェトキシシラン、 n へキサデシルプロピルジェトキシシラン、 n ィコサ ll one hexadesinore till propylmethyl jetoxy silane, n butyl methyl jetoxy silane, n decyl methinolegetoxy silane, n hexadeceno retino retoxy silane, n icosano methino rea diethoxy silane, n propino retino retino oxy silane, n butino retino Rectoxy silane, n Decino retino retoxy silane, n Hexa decino retino retoxy silane n Icosan echino lesoxy silane, n Butino repeno lesoxy silane, n Decyl propyl methoxy silane, n Hexa Decylpropyljetoxysilane, nicosa
Figure imgf000025_0001
Figure imgf000025_0001
ン、 n—プロピルトリエトキシシラン、 n ブチルトリエトキシシラン、 n—デシルトリエトキ シシラン、 n へキサデシノレトリエトキシシラン、 n ィコサントリエトキシシラン、 n プ N-propyltriethoxysilane, n-butyltriethoxysilane, n-decyltriethoxysilane, n-hexadecinoletriethoxysilane, n-icosanetriethoxysilane, n-propyl
ルトリメトキシシラン、ビュルトリエトキシシラン、 N— (2 アミノエチル） 3 ァミノプロピ 3—ァミノプロピルトリメトキシシラン、 3—ァミノプロピルトリエトキシシラン、 3—グリシ Rutrimethoxysilane, butyltriethoxysilane, N— (2 aminoethyl) 3 aminopropyl 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glyci
(3, 4—エポキシシクロへキシル）ェチルトリメトキシシラン、 3—メタクリロキシプロピル トリメトキシシラン、 3—メルカプトプロピルトリメトキシシラン、 N—(l , 3—ジメチルブチ リデン） 3—（トリェトキシシリノレ） 1 プロパンァミン、 N, N ビス [3- キシシリル)プロピル]エチレンジァミンなどが挙げられる。これらは、 1種単独で用い ても、 2種以上を組み合わせて用いてもよい。 (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, N- (l, 3-dimethylbutylidene) 3- (triethoxysilanol) ) 1 Propanamine, N, N bis [3- Xylyl) propyl] ethylenediamine. These may be used alone or in combination of two or more.
[0093] 上記感光性樹脂組成物における接着助剤の含有量としては、上記 SH基含有樹脂  [0093] The content of the adhesion assistant in the photosensitive resin composition is the SH group-containing resin.
(A) 100重量部に対して、好ましくは 0. 05〜； 15重量部、より好ましくは 0. ；!〜 10重 量部である。  (A) The amount is preferably from 0.05 to 15 parts by weight, more preferably from 0.;! To 10 parts by weight with respect to 100 parts by weight.
[0094] <溶解促進剤〉  [0094] <Solubility promoter>
本発明の組成物は、後述する現像液への十分な溶解性を発現させる目的で、溶解 促進剤を含有することが好ましい。溶解促進剤としては、界面活性剤が好ましく用い られる。このような界面活性剤としては、たとえば、フッ素系界面活性剤、シリコーン系 界面活性剤、ノユオン系界面活性剤などが挙げられる。  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 noion-based surfactants.
[0095] 上記フッ素系界面活性剤としては、たとえば、 BM CHIMIE社製「： BM—1000」、 「： BM—1100」、大日本インキ化学工業（株）社製「メガファック F142D」、「同 F172」 、「同 F173」、「同 F183」、住友スリーェム（株）社製「フロラード FC— 135」、「同 FC 170C」、「同 FC— 430」、「同 FC— 431」、旭硝子（株）社製「サーフロン S— 112」 、「同 S— 113」、「同 S— 131」、「同 S— 141」、「同 S— 145」、「同 S— 382」、「同 SC — 101」、「同 SC— 102」、「同 SC— 103」、「同 SC— 104」、「同 SC— 105」、「同 SC 106」等の市販品を挙げることができる。  [0095] Examples of the fluorosurfactant include BM CHIMIE ": BM-1000", ": BM-1100", Dainippon Ink & Chemicals "Megafac F142D", " F172, F173, F183, FLORAD FC-135, FC 170C, FC-430, FC-431, Asahi Glass Co., Ltd. ) “Surflon S-112”, “S-113”, “S-131”, “S-141”, “S-145”, “S-382”, “SC-101” , “SC-102”, “SC-103”, “SC-104”, “SC-105”, “SC106”, and the like.
[0096] 上記シリコーン系界面活性剤としては、たとえば、東レ 'ダウコーユング 'シリコーン（ 株）社製「SH— 28PA」、「SH— 190」、「SH— 193」、「SZ— 6032」、「SF— 8428」 、「DC— 57」、「DC— 190」、信越化学工業 (株)社製「KP341」、新秋田化成 (株） 社製「エフトップ EF301」、「同 EF303」、「同 EF352」等の市販品を挙げることができ  [0096] Examples of the silicone surfactants include "SH-28PA", "SH-190", "SH-193", "SZ-6032", "SF" manufactured by Toray 'Dowcoung' Silicone Co., Ltd. — 8428, DC-57, DC-190, Shin-Etsu Chemical KP341, Shin-Akita Kasei F-top EF301, EF303, EF352 ”And other commercial products
[0097] 上記ノニオン系界面活性剤としては、たとえば、ポリオキシエチレンラウリルエーテ ル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンォレイルエーテル等 のポリオキシエチレンアルキルエーテル類；ポリオキシエチレンジスチレン化フエニル エーテル、ポリオキシエチレンォクチルフエニルエーテル、ポリオキシエチレンノニル フエニルエーテル等のポリオキシエチレンァリールエーテル類；ポリオキシエチレンジ ラウレート、ポリオキシエチレンジステアレートなどのポリオキシエチレンジアルキルェ ステル類などが挙げられる。 [0097] Examples of the nonionic surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene distyrenylated phenyl ether Polyoxyethylene aryl ethers such as polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether; polyoxyethylene dialkyl ethers such as polyoxyethylene dilaurate and polyoxyethylene distearate Examples include stealth.
[0098] 上記ノニオン系界面活性剤の市販品としては、たとえば、花王 (株)社製「エマルゲ ン A—60」、「A— 90」、「A— 550」、「B— 66」、「PP— 99」、共栄社化学（株）社製「 (メタ）アクリル酸系共重合体ポリフロー No. 57」、「同 No. 90」などを挙げることがで きる。 [0098] Examples of commercially available nonionic surfactants include "Emulgen A-60", "A-90", "A-550", "B-66", "B-66" manufactured by Kao Corporation. PP-99 ”,“ (Meth) acrylic acid copolymer polyflow No. 57 ”and“ No. 90 ”manufactured by Kyoeisha Chemical Co., Ltd. can be mentioned.
[0099] 上記界面活性剤の中では、現像時に未露光部の感光性樹脂層の除去が容易であ ること力、ら、ノニオン系界面活性剤が好ましぐポリオキシエチレンァリールエーテル 類がより好ましぐ特に下記式（6)で表される化合物が好ましい。  [0099] Among the above surfactants, polyoxyethylene aryl ethers that are preferred for nonionic surfactants are the ability to easily remove the unexposed photosensitive resin layer during development. More preferred is a compound represented by the following formula (6).
[0100] [化 7]  [0100] [Chemical 7]
Figure imgf000027_0001
Figure imgf000027_0001
[0101] 上記式（6)中、 R1は炭素数 1〜5のアルキル基、好ましくはメチル基であり、 pは 1〜 5の整数であり、 sは;!〜 5の整数、好ましくは 2であり、 tは 1〜； 100の整数、好ましくは 10〜20の整数である。 [0101] 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 of 1 to 5, s is an integer of !! to 5, preferably 2 and t is an integer from 1 to 100, preferably an integer from 10 to 20.
[0102] 本発明の組成物における溶解促進剤の含有量は、上記 SH基含有樹脂 (A) 100 重量部に対して、好ましくは 0. 00；!〜 20重量部、より好ましくは 0. 01〜； 15重量部、 特に好ましくは 0. ；!〜 10重量部である。溶解促進剤の含有量が上記範囲にあること により、現像液への溶解性に優れた組成物が得られる。  [0102] The content of the dissolution accelerator in the composition of the present invention is preferably from 0.00;! To 20 parts by weight, more preferably 0.01 to 100 parts by weight of the SH group-containing resin (A). ~; 15 parts by weight, particularly preferably 0.;! ~ 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.
[0103] <感光性樹脂組成物の調製〉  <Preparation of photosensitive resin composition>
本発明の感光性樹脂組成物は、上記 SH基含有樹脂 (A)、多官能 (メタ）アタリレー ト（B)、光重合開始剤（C)および無機粒子（D)、必要に応じてその他の各種成分を 所定の組成比となるように調合した後、 3本ロールや混練機で均質に混合分散して 調製される。  The photosensitive resin composition of the present invention comprises the above-mentioned SH group-containing resin (A), polyfunctional (meth) atrelate (B), photopolymerization initiator (C) and inorganic particles (D), as required. It is prepared by blending various components to a predetermined composition ratio and then uniformly mixing and dispersing them with a three roll or kneader.
[0104] 上記組成物の粘度は、無機粒子（D)、増粘剤、有機溶媒、可塑剤および沈殿防止 剤などの添加量によって適宜調整することができる力 その範囲は 100〜500, 000 cps (センチ ·ボイズ）である。 [0104] The viscosity of the above composition is a force that can be appropriately adjusted depending on the addition amount of inorganic particles (D), thickeners, organic solvents, plasticizers, precipitation inhibitors, and the like. cps (centimeter boise).
[0105] 〔感光性フィルム〕  [Photosensitive film]
本発明の感光性フィルムは、通常、支持フィルムと、この上に形成された感光性樹 脂層とを有し、該感光性樹脂層の表面に保護フィルムが設けられていてもよい。  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.
[0106] <支持フィルム〉  [0106] <Support film>
上記感光性フィルムを構成する支持フィルムは、耐熱性および耐溶剤性を有すると ともに可撓性を有する樹脂フィルムであることが好ましい。支持フィルムが可撓性を有 することにより、ロールコータによってペースト状組成物を塗布することができ、感光 性フィルムをロール状に巻回した状態で保存および供給することができる。なお、支 持フィルムの厚さとしては、使用に適した範囲であればよぐたとえば 20〜； lOO ^ m である。  The support film constituting the photosensitive film is preferably a resin film having heat resistance and solvent resistance and flexibility. Since 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 in a roll shape. The thickness of the supporting film is, for example, 20˜; lOO ^ m as long as it is in a range suitable for use.
[0107] 支持フィルムを形成する樹脂としては、たとえば、ポリエチレンテレフタレート、ポリエ ステル、ポリエチレン、ポリプロピレン、ポリスチレン、ポリイミド、ポリビュルアルコール 、ポリ塩化ビュル、ポリフロロエチレンなどの含フッ素樹脂、ナイロン、セルロースなど が挙げられる。  [0107] Examples of the resin forming the support film include polyethylene terephthalate, polyester, polyethylene, polypropylene, polystyrene, polyimide, polybutyl alcohol, polychlorinated butyl, polyfluoroethylene, and other fluorine-containing resins, nylon, and cellulose. Can be mentioned.
[0108] 上記支持フィルムにおける感光性樹脂層が形成される面には、離型処理が施され ていることが好ましい。これにより、ディスプレイパネル用部材および電子部品用部材 を形成する際に、支持フィルムの剥離操作を容易に行うことができる。  [0108] 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.
[0109] さらに、感光性樹脂層の表面に設けられていてもよい保護フィルム層としては、上 記支持フィルムと同様の可撓性を有する樹脂フィルムを用いることができ、その表面（ 感光性樹脂層と接する面）には離型処理が施されて!/、てもよ!/、。  [0109] Further, as the protective film layer that may be provided on the surface of the photosensitive resin layer, a resin film having flexibility similar to that of the support film can be used, and the surface (photosensitive resin) can be used. The surface that is in contact with the layer) has been subjected to a mold release process!
[0110] <感光性フィルムの製造方法〉  [0110] <Method for producing photosensitive film>
上記感光性フィルムは、上記支持フィルム上に、上記感光性樹脂組成物を塗布し て塗膜を形成し、該塗膜を乾燥させて感光性樹脂層を形成することにより得られる。 乾燥後は、ロール状に巻くか、保護フィルムをラミネートする。また、上記感光性フィ ルムは、支持フィルムおよび保護フィルムのそれぞれに感光性樹脂組成物を塗布し て感光性樹脂層を形成し、互いの樹脂層面を重ね合わせて圧着する方法によっても 、好適に形成することができる。 [0111] 上記組成物を支持フィルム上に塗布する方法としては、膜厚が大きく（例えば 10 m以上）、かつ、均一性に優れた塗膜を効率よく形成することができる方法であれば 特に限定されない。例えば、ナイフコーターによる塗布方法、ロールコータによる塗 布方法、ドクターブレードによる塗布方法、カーテンコータによる塗布方法、ダイコー タによる塗布方法、ワイヤーコータによる塗布方法などが挙げられる。 The photosensitive film can be obtained by applying the photosensitive resin composition on the support film to form a coating film, and drying the coating film to form a photosensitive resin layer. After drying, it is rolled or laminated with a protective film. The photosensitive film can also be suitably applied 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 be formed. [0111] As a method of applying the above composition on a support film, any method can be used as long as it can efficiently form a coating film having a large film thickness (for example, 10 m or more) and excellent uniformity. It is not limited. Examples thereof 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.
[0112] 塗膜の乾燥条件は、乾燥後における溶剤の残存割合力 ¾重量％以内となるように 適宜調整すればよぐ例えば、 50〜； 150°Cの乾燥温度で 0. 5〜60分間程度である [0112] The drying condition of the coating film may be adjusted as appropriate so that the residual ratio force of the solvent after drying is within ¾% by weight, for example, 50 to; at a drying temperature of 150 ° C for 0.5 to 60 minutes. Is about
〇 Yes
[0113] 上記のようにして形成された感光性樹脂層の厚みは、 30〜300 H m、好ましくは 5 0〜200 111である。  [0113] The thickness of the photosensitive resin layer formed as described above is 30 to 300 Hm, preferably 50 to 200 111.
[0114] 〔パターン形成方法〕  [0114] [Pattern Formation Method]
本発明のパターン形成方法は、上記感光性樹脂組成物からなる感光性樹脂層を 基板上に形成する工程 (樹脂層形成工程）、該感光性樹脂層を露光処理してパター ンの潜像を形成する工程 (露光工程）、該感光性樹脂層を現像処理してパターンを 形成する工程 (現像工程）、および該パターンを焼成処理する工程 (焼成工程)を含 むことを特徴とする。  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. It includes a step of forming (exposure step), a step of developing the photosensitive resin layer to form a pattern (development step), and a step of baking the pattern (baking step).
[0115] 本発明では、上記樹脂層形成工程において、上記感光性樹脂組成物を基板上に 塗布して塗膜を形成し、該塗膜を乾燥して感光性樹脂層を形成してもよいし、上記 感光性フィルムを用いて、該感光性フィルムを構成する感光性樹脂層を基板上に転 写することにより、基板上に感光性樹脂層を形成してもよい。  [0115] 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. The photosensitive resin layer may be formed on the substrate by transferring the photosensitive resin layer constituting the photosensitive film onto the substrate using the photosensitive film.
[0116] <樹脂層形成工程〉  [0116] <Resin layer forming step>
この工程では、上記感光性樹脂組成物からなる感光性樹脂層を基板上に形成する 。感光性樹脂層の形成方法としては、たとえば、上記感光性樹脂組成物を基板上に 塗布して塗膜を形成し、該塗膜を乾燥させて形成する方法や、上記感光性フィルム を用いて、該感光性フィルムを構成する感光性樹脂層を基板上に転写して形成する 方法などが挙げられる。  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 onto 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.
[0117] 上記組成物を基板上に塗布する方法としては、膜厚が大きく（例えば 10 m以上） 、かつ、均一性に優れた塗膜を効率よく形成することができる方法であれば特に限定 されない。例えば、ナイフコーターによる塗布方法、ロールコータによる塗布方法、ド クタ一ブレードによる塗布方法、カーテンコータによる塗布方法、ダイコータによる塗 布方法、ワイヤーコータによる塗布方法などが挙げられる。 [0117] The method of applying the above composition on a substrate is not particularly limited as long as it is a method capable of efficiently forming a coating film having a large film thickness (eg, 10 m or more) and excellent uniformity. Not. Examples thereof 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.
[0118] 塗膜の乾燥条件は、乾燥後における溶剤の残存割合力 ¾重量％以内となるように 適宜調整すればよぐ例えば、 50〜； 150°Cの乾燥温度で 0. 5〜60分間程度である[0118] The drying condition of the coating film may be adjusted as appropriate so that the residual ratio force of the solvent after drying is within ¾% by weight, for example, 50 to; at a drying temperature of 150 ° C for 0.5 to 60 minutes. Is about
〇 Yes
[0119] 上記のようにして形成された感光性樹脂層の厚みは、 30〜300 H m、好ましくは 5 0—200 μ mである。なお、組成物を塗布を n回繰り返すことで、 n層（nは 2以上の整 数を示す）の樹脂層を有する積層体を形成してもよレ、。  The thickness of the photosensitive resin layer formed as described above is 30 to 300 Hm, preferably 50 to 200 μm. A laminate having n layers (n is an integer of 2 or more) may be formed by repeating application of the composition n times.
[0120] 一方、上記感光性フィルムを基板上にラミネートして、感光性樹脂層を基板上に転 写することにより、基板上に膜厚均一性に優れた樹脂層を容易に形成することができ 、形成されるパターンの膜厚均一化を図ることができる。感光性樹脂層を転写する際 、上記感光性フィルムを用いて n回転写を繰り返すことにより、 n層 (nは 2以上の整数 を示す）の樹脂層を有する積層体を形成してもよい。あるいは、 n層の樹脂層からなる 積層体が支持フィルム上に形成された感光性フィルムを用いて基板上に一括転写す ることにより、前記積層体を形成してもよい。  On the other hand, by laminating the photosensitive film on a 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. In addition, the thickness of the pattern to be formed 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 transfer n times using the photosensitive film. Alternatively, the laminate may be formed by collectively transferring a laminate comprising n resin layers onto a substrate using a photosensitive film formed on a support film.
[0121] 感光性フィルムを用いた転写工程の一例を示せば以下のとおりである。必要に応じ て用いられる感光性フィルムの保護フィルム層を剥離した後、基板の表面に感光性 樹脂層の表面が当接するように感光性フィルムを重ね合わせ、この感光性フィルムを 加熱ローラなどにより熱圧着した後、樹脂層から支持フィルムを剥離除去する。これ により、基板の表面に感光性樹脂層が転写されて密着した状態となる。  [0121] 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 contacts 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.
[0122] 転写条件としては、例えば、加熱ローラの表面温度が 40〜； 140°C、加熱ローラによ るロール圧が 0. l ~ 10kg/cm2,加熱ローラの移動速度が 0.；!〜 10m/分である。 また、基板は予熱されていてもよぐ予熱温度は、例えば 40〜； 140°Cである。 [0122] 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. ~ 10m / min. The preheating temperature at which the substrate may be preheated is, for example, 40 to 140 ° C.
[0123] 本発明で用いられる基板材料としては、例えば、ガラス、シリコーン、ポリカーボネー ト、ポリエステル、芳香族アミド、ポリアミドイミド、ポリイミドなどの絶縁性材料からなる 板状部材が挙げられる。この板状部材の表面には、必要に応じて、シランカップリン グ剤などによる薬品処理；プラズマ処理；イオンプレーティング法、スパッタリング法、 気相反応法、真空蒸着法などによる薄膜形成処理などの前処理が施されて!/、てもよ い。本発明においては、基板として、耐熱性を有するガラス基板を用いることが好まし い。このようなガラス基板としては、例えば、旭硝子 (株)製「PD200」などが挙げられ [0123] 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 is treated with chemicals such as silane coupling agent; plasma treatment; ion plating method, sputtering method, Pre-treatment such as thin film formation by vapor phase reaction or vacuum deposition may be applied! /. 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.
[0124] <露光工程〉 [0124] <Exposure process>
上記樹脂層形成工程により基板上に感光性樹脂層を形成後、露光装置を用いて 露光を行う。露光は通常のフォトリソグラフィ一で行われるように、フォトマスクを用いて マスク露光する方法を採用することができる。用いるマスクは、感光性樹脂層の有機 成分の種類によって、ネガ型もしくはポジ型のどちらかを選定する。露光用マスクの 露光パターンは、 目的によって異なる力 たとえば、 10〜500 111幅のストライプもし くは格子である。  After forming the photosensitive resin layer on the substrate by the resin layer forming step, exposure is performed using an exposure apparatus. The exposure can be performed by a mask exposure method using a photomask, as is done in ordinary photolithography. The mask used should be either negative or positive depending on the type of organic component in the photosensitive resin layer. The exposure pattern of the exposure mask varies depending on the purpose, for example, a stripe or grid of 10 to 500 111 widths.
[0125] また、フォトマスクを用いずに、赤色や青色の可視光レーザー光、 Arイオンレーザ 一などで直接描画する方法を用いてもょレ、。  [0125] 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.
[0126] 感光性樹脂層の表面に、露光用マスクを介して、紫外線などの放射線を選択的に 照射 (露光）して、樹脂層にパターンの潜像を形成する。なお、樹脂層上に被覆され てレ、る支持フィルムを剥離しな!/、状態で露光を行うのが好ましレ、。  [0126] The surface of the photosensitive resin layer is selectively irradiated (exposed) with radiation such as ultraviolet rays through an exposure mask to form a latent image of the pattern on the resin layer. Do not peel off the support film that is coated on the resin layer!
[0127] 露光装置としては、平行光露光機、散乱光露光機、ステッパー露光機、プロキシミ ティ露光機等を用いることができる。また、大面積の露光を行う場合は、ガラス基板な どの基板上に感光性樹脂組成物を塗布した後に、搬送しながら露光を行うことによつ て、小さな露光面積の露光機で、大きな面積を露光することができる。  [0127] 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. In addition, when exposing a large area, the photosensitive resin composition is applied on a substrate such as a glass substrate and then exposed while being conveyed. Can be exposed.
[0128] 露光の際に使用される活性光源は、たとえば、可視光線、近紫外線、紫外線、電子 線、 X線、レーザー光などが挙げられるが、これらの中で紫外線が好ましぐその光源 としては、たとえば、低圧水銀灯、高圧水銀灯、超高圧水銀灯、ハロゲンランプなど が使用できる。これらの中では超高圧水銀灯が好適である。  [0128] Examples of the active light source used for exposure include visible light, near ultraviolet light, ultraviolet light, electron beam, X-ray, and laser light. Among these, ultraviolet light is preferred as the light source. For example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, or a halogen lamp can be used. Among these, an ultra high pressure mercury lamp is preferable.
[0129] 露光条件は、塗布厚みによって異なる力 ；!〜 100mW/cm2の出力の超高圧水 銀灯を用いて 0. 05〜1分間露光を行なう。この場合、波長フィルターを用いて露光 光の波長領域を狭くすることによって、光の散乱を抑制し、パターン形成性を向上さ せること力 Sできる。具体的には、 i線（365nm)の光をカットするフィルター、あるいは、 i 線および h線（405nm)の光をカットするフィルターを用いて、パターン形成性を向上 させること力 Sでさる。 [0129] The exposure conditions, different forces by the coating thickness; performing 0.05 to 1 min exposure using an ultra high pressure water silver lamp with an output of ~ 100mW / cm 2!. In this case, by narrowing the wavelength region of the exposure light using a wavelength filter, it is possible to suppress light scattering and improve pattern formation. Specifically, a filter that cuts off i-line (365 nm) light, or i Using a filter that cuts off the light of h-line and h-line (405 nm), improve the pattern formability with force S.
[0130] <現像工程〉 [0130] <Development process>
上記露光後、感光部分と非感光部分の現像液に対する溶解度差を利用して、樹脂 層を現像して樹脂層のパターンを形成する。現像方法 (例えば、浸漬法、揺動法、シ ャヮ一法、スプレー法、パドル法、ブラシ法など）および現像処理条件（例えば、現像 液の種類 '組成'濃度、現像時間、現像温度など)などは、樹脂層の種類に応じて適 宜選択、設定すればよい。  After the exposure, the resin layer is developed using the difference in solubility in the developer between the photosensitive part and the non-photosensitive part to form a resin layer pattern. Development method (eg, dipping method, rocking method, shutter method, spray method, paddle method, brush method, etc.) and development processing conditions (eg, developer type 'composition' concentration, development time, development temperature, etc.) These may be selected and set appropriately according to the type of resin layer.
[0131] 現像工程で用いられる現像液としては、樹脂層中の有機成分を溶解可能な有機溶 媒が使用できる。また、前記有機溶媒にその溶解力が失われない範囲で水を添加し てもよい。樹脂層中にカルボキシル基等の酸性基を持つ化合物が存在する場合、ァ ルカリ水溶液で現像できる。 [0131] As the developer used in the development step, an organic solvent capable of dissolving the organic components 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 aqueous alkaline solution.
[0132] 上記樹脂層に含まれる無機粒子 (D)は SH基含有樹脂 (A)により均一に分散され ているため、該樹脂 (A)を現像液で溶解させて洗浄することにより、無機粒子（D)も 同時に除去される。 [0132] Since the inorganic particles (D) contained in the resin layer are uniformly dispersed in the SH group-containing resin (A), the inorganic particles (D) are dissolved in a developer and washed to obtain inorganic particles. (D) is also removed at the same time.
[0133] 上記アルカリ水溶液としては、たとえば、水酸化リチウム、水酸化ナトリウム、水酸化 カリウム、リン酸水素ナトリウム、リン酸水素二アンモニゥム、リン酸水素二カリウム、リン 酸水素ニナトリウム、リン酸二水素アンモニゥム、リン酸二水素カリウム、リン酸二水素 ナトリウム、ケィ酸リチウム、ケィ酸ナトリウム、ケィ酸カリウム、炭酸水素リチウム、炭酸 水素ナトリウム、炭酸水素カリウム、炭酸リチウム、炭酸ナトリウム、炭酸カリウム、ホウ 酸リチウム、ホウ酸ナトリウム、ホウ酸カリウム、アンモニア水溶液、テトラメチルアンモ ユウムヒドロキシド、トリメチルヒドロキシェチルアンモニゥムヒドロキシド、モノメチルアミ ン、ジメチルァミン、トリメチルァミン、モノェチルァミン、ジェチルァミン、トリェチルアミ ン、モノイソプロピルァミン、ジイソプロピルァミン、エタノールァミン、ジエタノールアミ ン、トリエタノールァミンなどが挙げられる。  [0133] Examples of the alkaline aqueous solution include lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium hydrogen phosphate, dihydrogen ammonium phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, dihydrogen phosphate. Ammonium, potassium dihydrogen phosphate, sodium dihydrogen phosphate, lithium silicate, sodium silicate, potassium silicate, lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, lithium carbonate, sodium carbonate, potassium carbonate, lithium borate Sodium borate, potassium borate, aqueous ammonia, tetramethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, jetylamine, triethyl Amin, monoisopropyl § Min, diisopropyl § Min, ethanol § Min, diethanolamine emissions, such as triethanolamine § Min and the like.
[0134] 上記アルカリ水溶液の濃度は、通常 0. 01〜； 10重量％、より好ましくは 0. ；!〜 5重 量％である。アルカリ濃度が低すぎると可溶部が除去されず、アルカリ濃度が高すぎ ると、パターン部を剥離させ、また非可溶部を腐食させるおそれがあることから好まし くない。また、現像時の現像温度は、 20〜50°Cで行うことが工程管理上好ましい。 The concentration of the alkaline aqueous solution is usually 0.01 to 10% by weight, more preferably 0.! To 5% by weight. If the alkali concentration is too low, the soluble portion will not be removed, and if the alkali concentration is too high, the pattern portion may be peeled off and the non-soluble portion may be corroded. It ’s not. The development temperature during development is preferably 20 to 50 ° C. in terms of process control.
[0135] 上記アルカリ水溶液には、ノユオン系界面活性剤や有機溶剤などの添加剤が含有 されていてもよい。なお、アルカリ現像液による現像処理がなされた後は、通常、水洗 処理が施される。 [0135] The alkaline aqueous solution may contain additives such as a noion surfactant and an organic solvent. In addition, after the development process with an alkali developer, a washing process is usually performed.
[0136] <焼成工程〉 [0136] <Firing process>
上記現像後の樹脂層残留部 (樹脂層のパターン）における有機物質を焼失させる ために、焼成炉にて樹脂層のパターンを焼成処理する。  In order to burn off the organic substance in the resin layer residual portion (resin layer pattern) after the development, the resin layer pattern is baked in a baking furnace.
[0137] 焼成雰囲気は、組成物や基板の種類によって異なる力 空気、オゾン、窒素、水素 等の雰囲気中で焼成する。焼成炉としては、バッチ式の焼成炉ゃベルト式の連続型 焼成炉を用いることができる。 [0137] Firing is performed in an atmosphere of air, ozone, nitrogen, hydrogen, or the like, which varies depending on the composition and the type of substrate. As the firing furnace, a batch-type firing furnace or a belt-type continuous firing furnace can be used.
[0138] 焼成処理条件は、樹脂層残留部中の有機物質が焼失されることが必要であるため[0138] The baking treatment condition requires that the organic substance in the resin layer residual portion is burned off.
、通常、焼成温度が 300〜； 1000°C、焼成時間が 10〜90分間である。例えば、ガラ ス基板上にパターン形成する場合は、 350〜600°Cの温度で 10〜60分間保持して 焼成を行う。 Usually, the firing temperature is 300 to 1000 ° C, and the firing time is 10 to 90 minutes. For example, when forming a pattern on a glass substrate, firing is performed at a temperature of 350 to 600 ° C for 10 to 60 minutes.
[0139] これらの工程を含む本発明のパターン形成方法により、誘電体、電極、抵抗体、蛍 光体、隔壁、カラーフィルター、ブラックマトリックス等のディスプレイパネル用部材ゃ 、電子部品の回路パターン等を形成することができる。なお、上記転写、露光、現像 、焼成の各工程中に、乾燥または予備反応の目的で、 50〜300°C加熱工程を導入 してもよい。  [0139] By the pattern forming method of the present invention including these steps, a display panel member such as a dielectric, an electrode, a resistor, a phosphor, a partition, a color filter, a black matrix, a circuit pattern of an electronic component, etc. Can be formed. A heating step of 50 to 300 ° C. may be introduced for the purpose of drying or preliminary reaction during the transfer, exposure, development and firing steps.
[0140] 本発明のフラットディスプレイパネルの製造方法は、上記のようにして誘電体、電極 、抵抗体、蛍光体、隔壁、カラーフィルターおよびブラックマトリックスから選ばれる少 なくとも 1種のディスプレイパネル用部材を形成する工程を含み、プラズマディスプレ ィパネルの製造方法に適してレ、る。  [0140] The method for producing a flat display panel of the present invention comprises at least one kind of 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. Suitable for the method of manufacturing a plasma display panel.
[0141] [実施例]  [0141] [Example]
以下、実施例に基づいて本発明をより具体的に説明するが、本発明は、これらの実 施例により何ら限定されるものではない。なお、実施例および比較例における「部」お よび「％」は、特に断りのない限り、それぞれ「重量部」および「重量％」を示す。  Hereinafter, the present invention will be described more specifically based on examples. However, the present invention is not limited to these examples. In the examples and comparative examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively, unless otherwise specified.
[0142] まず、物性の測定方法および評価方法について説明する。 [0143] 〔重量平均分子量 (Mw)および重量平均分子量 (Mw) /数平均分子量 (Mn) (以 下、 Mw/Mnと呼称する。 )の測定方法〕 [0142] First, methods for measuring and evaluating physical properties will be described. [Method of measuring weight average molecular weight (Mw) and weight average molecular weight (Mw) / number average molecular weight (Mn) (hereinafter referred to as Mw / Mn)]
Mwおよび Mw/Mnは、ゲルパーミエーシヨンクロマトグラフィー（GPC) (東ソー株 式会社製「HLC— 8220GPC」）により測定したポリスチレン換算の値である。なお、 Mw and Mw / Mn are values in terms of polystyrene measured by gel permeation chromatography (GPC) (“HLC-8220GPC” manufactured by Tosoh Corporation). In addition,
GPC測定は、 GPCカラムとして東ソー株式会社製「TSKguardcolumn SuperHZFor GPC measurement, "TSKguardcolumn SuperHZ" manufactured by Tosoh Corporation
M— M」を用い、テトラヒドロフラン (THF)溶媒、測定温度 40°Cの条件で行った。 M—M ”was used under the conditions of a tetrahydrofuran (THF) solvent and a measurement temperature of 40 ° C.
[0144] 〔現像後のパターンの評価方法 （実施例;!〜 12、比較例;!〜 7)〕 [Method for evaluating pattern after development (Examples;! To 12, Comparative examples;! To 7)]
現像後のパネル試験片（150mm X I 50mm X 2· 8mm)を切断して、図 2に示す 位置のパターン切断面を走査型電子顕微鏡（日立製作所製「S4200」）で観察して ノ ターンの幅および高さを計測し、それぞれを下記基準で評価した。なお、所望の規 格は、パターンの幅が 50〃 m、高さ力 80〃 111、間隔が 200〃 mである。  Cut the panel test piece after development (150mm XI 50mm X 2 · 8mm) and observe the pattern cut surface at the position shown in Fig. 2 with a scanning electron microscope (Hitachi "S4200"). And height was measured and each was evaluated according to the following criteria. The desired standard is that the pattern width is 50 mm, the height force is 80 mm, and the interval is 200 mm.
A：所望の規格 ± 3 m以内のもの。  A: Desired standard within ± 3 m.
B：所望の規格 ± 3 mを超えて ± 5 m以内。  B: Within ± 5 m exceeding the desired standard ± 3 m.
C：所望の規格 ± 5 mを超えて ± 10 m以内のもの。  C: Those exceeding the desired standard ± 5 m and within ± 10 m.
D：所望の規格土 10 μ mを超えるもの。  D: The desired standard soil exceeds 10 μm.
[0145] 〔焼成後のパターンの評価方法 （実施例;!〜 12、比較例;!〜 7)〕 [Method for evaluating pattern after firing (Examples;! To 12, Comparative examples;! To 7)]
焼成後のパネル試験片（150mm X I 50mm X 2· 8mm)を切断して、図 2に示す 位置のパターン切断面を走査型電子顕微鏡（日立製作所製「S4200」）で観察して ノ ターンの幅および高さを計測し、それぞれを下記基準で評価した。なお、所望の規 格は、パターンの幅が 50〃 m、高さ力 80〃 111、間隔が 200〃 mである。  Cut the panel specimen (150mm XI 50mm X 2 · 8mm) after firing, and observe the pattern cut surface at the position shown in Fig. 2 with a scanning electron microscope (Hitachi "S4200"). And height was measured and each was evaluated according to the following criteria. The desired standard is that the pattern width is 50 mm, the height force is 80 mm, and the interval is 200 mm.
A：所望の規格のもの。  A: The desired standard.
B：所望の規格 ± 3 m以内のもの。  B: Desired standard within ± 3 m.
C：所望の規格 ± 3 mを超えて ± 5 m以内のもの。  C: Those exceeding the desired standard ± 3 m and within ± 5 m.
D：所望の規格 ± 5 mを超えるもの。  D: Desired standard exceeds ± 5 m.
[0146] 〔電気抵抗測定の評価方法 （実施例 13〜34、比較例 8〜； 15)〕 [Evaluation Method of Electrical Resistance Measurement (Examples 13 to 34, Comparative Examples 8 to 15;)]
体積抵抗 [ Ω ' cm]は焼成後のパネルの試験片（150mm X 150mm X 2. 8mm Volume resistance [Ω'cm] is the panel specimen after firing (150mm X 150mm X 2.8mm
)の上に焼成後膜厚 10 mの塗膜を作製し、 NPS社製の「Resistivity Proccesso r Model∑— 5」を用いて評価した。 [0147] 〔赤外線吸収スペクトルの測定方法〕 After baking, a coating film having a film thickness of 10 m was prepared and evaluated using “Resistivity Processor Model 5” manufactured by NPS. [Measurement method of infrared absorption spectrum]
吸収スペクトル [cm—1]はアルカリ可溶性樹脂を精製、乾燥後に HORIBA製の「F T IR/フーリエ変換赤外分光光度計 FT— 720」を用いて測定した。 The absorption spectrum [cm- 1 ] was measured using a “FT IR / Fourier transform infrared spectrophotometer FT-720” manufactured by HORIBA after the alkali-soluble resin was purified and dried.
[0148] 〔硬化深度の評価方法 （実施例 13〜34、比較例 8〜； 15)〕  [Evaluation Method of Curing Depth (Examples 13 to 34, Comparative Examples 8 to 15;)]
ガラス基板上に膜厚 10 ΐηの無機粉体含有樹脂層を形成し、超高圧水銀灯により 、 i線 (波長 365nmの紫外線)をガラス基板側から無機粉体含有樹脂層に向かって 照射し、無機粉体含有樹脂層を硬化させた。ここに、照射量は 800mj/cm2とした。 露光後、液温 25°Cの 0. 5質量％炭酸ナトリウム水溶液を現像液とするシャワー法に より現像処理を 30秒間行い、続いて、超純水を用いて水洗を行った。これにより、紫 外線が照射されて、硬化されていない無機粉体含有樹脂を除去した。得られた 5cm X 5cm形状の無機粉体含有樹脂層の残膜厚を、微細柱高さ測定器 P 10 (KLA— TENCOR製）を用いて、測定した。硬化深度の良好性を A、 Bおよび Cで表記する のに、次の残膜値の範囲で規定した。結果を表に示す。 An inorganic powder-containing resin layer with a thickness of 10 ΐη is formed on a glass substrate, and an i-line (ultraviolet light with a wavelength of 365 nm) is irradiated from the glass substrate side toward the inorganic powder-containing resin layer with an ultra-high pressure mercury lamp. The powder-containing resin layer was cured. Here, the dose was 800 mj / cm 2 . After the exposure, development treatment 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 rays were irradiated to remove the uncured inorganic powder-containing resin. 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 specified in the following range of remaining film values. The results are shown in the table.
A：残膜厚が 6 mを超える  A: Residual film thickness exceeds 6 m
8 :残膜厚が5〜6〃111  8: Remaining film thickness is 5-6〃111
C :残膜厚が 5 ^ 111未満  C: Remaining film thickness is less than 5 ^ 111
〔パターンの評価方法 （実施例 13〜34、比較例 8〜； 15)〕  [Pattern Evaluation Method (Examples 13 to 34, Comparative Example 8 to 15;)]
パターン現像後および焼成後のパネル試験片（150mm X 150mm X 2. 8mm)を 切断して、パターン切断面を走査型電子顕微鏡（日立製作所製「S4200」）で観察し てパターンの幅および高さを計測し、それぞれを下記基準で評価した。なお、所望の 規格は、パターンの幅が 50〃 m、高さが 10〃111、間隔が 100〃 mである。  Cut the panel test piece (150mm x 150mm x 2.8mm) after pattern development and firing, and observe the pattern cut surface with a scanning electron microscope (Hitachi "S4200"). Were measured and evaluated according to the following criteria. The desired standard is a pattern width of 50 mm, height of 10 mm111, and spacing of 100 mm.
A：所望の規格から ± 5%以内のもの。  A: Within ± 5% of desired standard.
B：所望の規格 ± 5 %を超えて ± 10 %以内のもの。  B: Desired standard exceeding ± 5% and within ± 10%.
C :所望の規格 ± 10%を超えるもの。  C: Desired standard exceeds ± 10%.
[0149] 〔焼成後のパターン密着性評価 （実施例 13〜34、比較例 8〜； 15)〕 [Pattern adhesion evaluation after firing (Examples 13 to 34, Comparative Examples 8 to 15)]
パネルの試験片（150mm X I 50mm X 2· 8mm)上にパターン作製、焼成し、焼 成後のパターンと支持体との密着性評価を行った。なお、所望の規格は、パターンの 幅が 50 111、高さが 10 m、間隔 100 mである。セロテープ（ニチバン社製'登録 商標）を加熱ローラにより熱圧着した。圧着条件は、加熱ローラの表面温度を 23°C、 ロール圧を 4kg/cm2、加熱ローラの移動速度を 0. 5m/分とした。これにより、支持 体の表面にセロテープが転写されて密着した状態となった。このセロテープを支持体 より剥離することで評価した。 A pattern was prepared and fired on a panel test piece (150 mm XI 50 mm X 2 · 8 mm), and the adhesion between the fired pattern and the support was evaluated. The desired standard is a pattern width of 50 111, a height of 10 m, and an interval of 100 m. Cellotape (Nichiban's registration) (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 and adhered to the surface of the support. Evaluation was made by peeling the cellophane from the support.
[0150] A：パターン剥れなし。  [0150] A: No pattern peeling.
[0151] B :パターン剥れが基板上に部分的に発生。  [0151] B: Pattern peeling partially occurred on the substrate.
C :パターン剥れが基板上に全面的に発生。  C: Pattern peeling occurs on the entire surface of the substrate.
[0152] 〔合成例 Al〕  [0152] [Synthesis Example Al]
ベンジルメタタリレート 55g、 2—メタクリロイロキシェチルフタル酸 45g、ァゾビスイソ ブチロニトリル（AIBN) lg、ペンタエリスリトールテトラキス（3—メルカプトプロピオン 酸）（堺化学工業 (株)製） 5gを攪拌機付きオートクレープに仕込み、窒素雰囲気下に おいて、プロピレングリコールモノメチルエーテル 150部中で均一になるまで攪拌し た。次いで、 80°Cで 4時間重合させ、さらに 100°Cで 1時間重合反応を継続させた後 、室温まで冷却して SH基を有するメタクリル樹脂 (A1) (以下、「SH基含有メタクリノレ 樹脂 (A1)」とも記す)を得た。この SH基含有メタクリル樹脂 (A1)の重合率は 98%で あり、 SH基含有メタクリル樹脂（A1)の重量平均分子量は 20000 (Mw/Mnは 1 · 8 )であった。得られた樹脂の IRスペクトルを図 3に示す。  Benzylmetatalylate 55g, 2-methacryloyloxetylphthalic acid 45g, azobisisobutyronitrile (AIBN) lg, 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 in a 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 having SH groups (A1) (hereinafter referred to as “SH group-containing methacrylate resin ( A1) ”) was obtained. The polymerization rate of the SH group-containing methacrylic resin (A1) was 98%, and the weight average molecular weight of the SH group-containing methacrylic resin (A1) was 20000 (Mw / Mn was 1 · 8). Fig. 3 shows the IR spectrum of the obtained resin.
[0153] 〔合成例 A2〕  [Synthesis Example A2]
ペンタエリスリトールテトラキス（3—メルカプトプロピオン酸）の代わりにテトラエチレ ングリコールビス（3—メルカプトプロピオン酸）（堺化学工業 (株)製） 5gを使用した以 外は、合成例 A1と同様にして SH基を有するメタクリル樹脂 (A2) (以下、「SH基含 有メタクリル樹脂 (A2)」とも記す)を得た。この SH基含有メタクリル樹脂 (A2)の重合 率は 98%であり、 SH基含有メタクリル樹脂（A2)の重量平均分子量 15000 (Mw/ Mnは 1 · 7)であった。 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), the SH group was the same as in Synthesis Example A1. A 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).
[0154] 〔合成例 A3〕  [Synthesis Example A3]
ペンタエリスリトールテトラキス（3—メルカプトプロピオン酸）の代わりにジペンタエリ スリトールへキサキス（3—メルカプトプロピオン酸）（堺化学工業 (株)製） 5gを使用し た以外は、合成例 A1と同様にしてメタクリル樹脂 (A3) (以下、「メタクリル樹脂 (A3)」 とも記す）を得た。このメタクリル樹脂 (A3)の重合率は 98%であり、メタクリル樹脂 (A 3)の重量平均分子量 25000 (Mw/Mnは 1 · 9)であった。 A methacrylic resin in the same manner 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 referred to as `` methacrylic resin (A3) '' Also described). 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).
[0155] 〔合成例 A4〕 [Synthesis Example A4]
ペンタエリスリトールテトラキス（3 メルカプトプロピオン酸）の代わりに 2, 4 ジフエ 二ルー 4ーメチルー 1 ペンテン 5gを使用した以外は、合成例 A1と同様にしてメタク リル樹脂 (A4)を得た。このメタクリル樹脂 (A4)の重合率は 98%であり、メタタリル樹 脂（A4)の重量平均分子量 25000 (Mw/Mnは 2· 2)であった。  A methacrylic resin (A4) was obtained in the same manner as in Synthesis Example A1 except that 5 g of 2,4 diphenyl diru 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 methallyl resin (A4) was 25000 (Mw / Mn was 2.2).
〔合成例 A5〕  (Synthesis Example A5)
ペンタエリスリトールテトラキス（3—メルカプトプロピオン酸）の代わりにトリメチロー ルプロパントリス（3—メルカプトプロピオン酸）（堺化学工業 (株)製） 5gを使用した以 外は、合成例 A1と同様にして SH基を有するメタクリル樹脂 (A5) (以下、「SH基含 有メタクリル樹脂 (A5)」とも記す)を得た。この SH基含有メタクリル樹脂 (A5)の重合 率は 98%であり、 SH基含有メタクリル樹脂（A5)の重量平均分子量 15000 (Mw/ Mn 1. 7)であった。  Except for using 5 g of trimethylolpropane tris (3-mercaptopropionic acid) (manufactured by Sakai Chemical Industry Co., Ltd.) instead of pentaerythritol tetrakis (3-mercaptopropionic acid), the SH group was synthesized in the same manner as in Synthesis Example A1. 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).
[0156] 〔合成例 A6〕 [Synthesis Example A6]
ベンジノレメタタリレート 80g、メタクリノレ酸 20g、ァゾビスイソブチロニトリノレ（AIBN) 1 g、ペンタエリスリトールテトラキス（3—メルカプトプロピオン酸）（堺化学工業 (株)製） 5gを攪拌機付きオートクレープに仕込み、窒素雰囲気下において、プロピレングリコ ールモノメチルエーテル 150部中で均一になるまで攪拌した。次いで、 80°Cで 4時 間重合させ、さらに 100°Cで 1時間重合反応を継続させた後、室温まで冷却して SH 基を有するメタクリル樹脂 (A6) (以下、「SH基含有メタクリル樹脂 (A6)」とも記す)を 得た。この SH基含有メタクリル樹脂 (A6)の重合率は 99%であり、 SH基含有メタタリ ル樹脂（A6)の重量平均分子量は 30000 (Mw/Mn 1. 9)であった。  Autoclave with stirrer 80g of benzenoremethalate, 20g of methacrynolic acid, 1g of azobisisobutyronitrinole (AIBN), pentaerythritol tetrakis (3-mercaptopropionic acid) (manufactured by Sakai Chemical Industry Co., Ltd.) And stirred in a nitrogen atmosphere until uniform in 150 parts of propylene glycol monomethyl ether. Next, polymerization was carried out at 80 ° C for 4 hours, and then the polymerization reaction was continued at 100 ° C for 1 hour, followed by cooling to room temperature and methacrylic resin having SH groups (A6) (hereinafter referred to as `` SH group-containing methacrylic resin (Also referred to as (A6))). The polymerization rate of the SH group-containing methacrylic resin (A6) was 99%, and the SH group-containing methacrylate resin (A6) had a weight average molecular weight of 30000 (Mw / Mn 1.9).
〔合成例 A7〕  (Synthesis Example A7)
ペンタエリスリトールテトラキス（3—メルカプトプロピオン酸）の代わりにメチルー 3— メルカプトプロピオネート (堺化学 (株)製） 5gを使用した以外は、合成例 A1と同様に してメタクリル樹脂 (A7)を得た。このメタクリル樹脂 (A7)の重合率は 98%であり、メ タクリル樹脂（A7)の重量平均分子量 25000 (Mw/Mn 2. 3)であった。 [0157] 〔合成例 A8〕 A methacrylic resin (A7) was obtained in the same manner as in Synthesis Example A1, except that 5 g of methyl-3-mercaptopropionate (manufactured by Sakai Chemical Co., Ltd.) was 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]
2 フエノキシ ェチルメタタリレート 80g、メタクリル酸 20g、ァゾビスイソブチロニト リル (AIBN) lg、トリメチロールプロパントリス（3—メルカプトプロピオネート）（堺化学 工業 (株)製） lgを攪拌機付きオートクレープに仕込み、窒素雰囲気下において、プ ロピレンダリコールモノメチルエーテル 150部中で均一になるまで攪拌した。次いで、 80°Cで 4時間重合させ、さらに 100°Cで 1時間重合反応を継続させた後、室温まで 冷却して SH基を有するメタクリル樹脂 (A8) (以下、「SH基含有メタクリル樹脂 (A8) 」とも記す）を得た。この SH基含有メタクリル樹脂 (A8)の重合率は 98%であり、 SH 基含有メタクリル樹脂 (A8)の重量平均分子量は 33, 000であった。  2 Phenoxyethyl metatalylate 80g, Methacrylic acid 20g, Azobisisobutyronitrile (AIBN) lg, Trimethylolpropane tris (3-mercaptopropionate) (manufactured by Sakai Chemical Industry Co., Ltd.) lg with stirrer The mixture was charged into an autoclave and stirred in 150 parts of polypropylene alcohol monomethyl ether until uniform in a nitrogen atmosphere. Next, polymerization was carried out at 80 ° C. for 4 hours, and further polymerization reaction was continued at 100 ° C. for 1 hour. After cooling to room temperature, a methacrylic resin having SH groups (A8) A8) is also written). The polymerization rate of this SH group-containing methacrylic resin (A8) was 98%, and the weight average molecular weight of the SH group-containing methacrylic resin (A8) was 33,000.
[0158] 〔合成例 A9〕  [Synthesis Example A9]
2 フエノキシ一ェチルメタタリレート 70g、メタクリル酸 15g、シクロへキシルメタタリ レート 15g、ペンタエリスリトールテトラキス（3—メルカプトプロピオネート）（堺化学ェ 業 (株)製) 0. 5gを攪拌機付きオートクレープに仕込んだこと以外は、合成例 A8と同 様にして SH基を有するメタクリル樹脂 (A9) (以下、「SH基含有メタクリル樹脂 (A9) 」とも記す）を得た。この SH基含有メタクリル樹脂 (A9)の重合率は 98%であり、 SH 基含有メタクリル樹脂 (A9)の重量平均分子量 46, 000であった。  2 70 g of phenoxyethyl methacrylate, 15 g of methacrylic acid, 15 g of cyclohexyl methacrylate, pentaerythritol tetrakis (3-mercaptopropionate) (manufactured by Sakai Chemical Industry Co., Ltd.) in an autoclave with a stirrer A methacrylic resin (A9) having an SH group (hereinafter also referred to as “SH group-containing methacrylic resin (A9)”) was obtained in the same manner as in Synthesis Example A8, except that it was charged. 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.
[0159] 〔合成例 A10〕  [Synthesis Example A10]
合成例 A8においてトリメチロールプロパントリス（3—メルカプトプロピオネート）の代 わりに 2, 4 ジフエ二ルー 4ーメチルー 1 ペンテン 0. 5gを用いたこと以外は、合成 例 A8と同様にしてメタクリル樹脂 (A10) (以下、「メタクリル樹脂 (A10)」とも記す）を 得た。このメタクリル樹脂 (A10)の重合率は 98%であり、メタクリル樹脂 (A10)の重 量平均分子量 30, 000であった。  In Synthesis Example A8, a methacrylic resin (A10) was prepared 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). (Hereinafter also referred to as “methacrylic resin (A10)”). The polymerization rate of this methacrylic resin (A10) was 98%, and the weight average molecular weight of the methacrylic resin (A10) was 30,000.
[0160] 〔合成例 Al l〕  [Synthesis Example Al l]
合成例 A9においてペンタエリスリトールテトラキス（3—メルカプトプロピオネート）の 代わりに 2, 4 ジフエ二ルー 4ーメチルー 1 ペンテン 0. 5gを用いたこと以外は、合 成例 A9と同様にしてメタクリル樹脂 (Al l) (以下、「メタクリル樹脂 (Al l)」とも記す） を得た。このメタクリル樹脂 (Al l)の重合率は 98%であり、メタクリル樹脂 (Al l)の 重量平均分子量 50, 000であった。 [0161] 〔合成例 Bl〕 In the same manner 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, a methacrylic resin (Al l) (hereinafter also referred to as “methacrylic resin (Al l)”). The polymerization rate of this methacrylic resin (Al l) was 98%, and the weight average molecular weight of the methacrylic resin (Al l) was 50,000. [0161] [Synthesis Example Bl]
攪拌装置、温度計、コンデンサーおよび窒素ガス導入管を備えた 1リットルのフラス コに、トリス（ポリオキシプロピレン）グリセリルエーテル (Mw300) (和光純薬工業 (株） 製、上記式（5)において η= 1 · 2) 300g (水酸基 = 3mol)および塩酸 1 · 56g (35% 水溶液、 HCl成分として 0. 015mol)を入れて攪拌し、メタクリル酸 2— (ビニ口キシェ トキシ)ェチル 600g (3mol)を発熱に注意しながらゆっくり滴下した。発熱が緩やか になったところで 60°Cに昇温し、 4時間反応を行った。このようにして得られた反応物 を IRにより分析したところ、水酸基に起因する 3500cm 1付近のピークはほぼ消失し ており、 目的とする多官能メタアタリレート（B1)を得た。 Tris (polyoxypropylene) glyceryl ether (Mw300) (manufactured by Wako Pure Chemical Industries, Ltd., η in the above formula (5)) was added to a 1 liter flask equipped with a stirrer, thermometer, condenser and nitrogen gas inlet tube. = 1 · 2) Add 300 g (hydroxyl group = 3 mol) and hydrochloric acid 1 · 56 g (35% aqueous solution, 0.015 mol as HCl component) and stir, then add 600 g (3 mol) of methacrylic acid 2- (binary oxychhetoxy) ethyl. The solution was slowly added dropwise while paying attention to heat generation. When the exotherm became mild, the temperature was raised to 60 ° C and the reaction was carried out for 4 hours. When the reaction product thus obtained was analyzed by IR, the peak in the vicinity of 3500 cm 1 due to the hydroxyl group had almost disappeared, and the desired polyfunctional metaatalylate (B1) was obtained.
[0162] 〔合成例 B2〕  [0162] [Synthesis Example B2]
攪拌装置、温度計、コンデンサーおよび窒素ガス導入管を備えた 2リットルのフラス コに、トリス（ポリオキシプロピレン）グリセリルエーテル（Mw400) (三井ポリウレタン（ 株）製、上記式（5)において η= 1 · 8) 400g (水酸基 = 3mol)および塩酸 1 · 56g (3 5%水溶液、 HCl成分として 0. 015mol)を入れた以外は、合成例 B1と同様にして 多官能メタアタリレート (B2)を得た。この多官能 (メタ）アタリレート (B2)を IRにより分 析したところ、水酸基に起因する 3500cm 1付近のピークはほぼ消失していた。 To a 2 liter flask equipped with a stirrer, thermometer, condenser and nitrogen gas inlet tube, tris (polyoxypropylene) glyceryl ether (Mw400) (Mitsui Polyurethane Co., Ltd., in the above formula (5), η = 1 · 8) Polyfunctional metaatarylate (B2) was obtained in the same manner as in Synthesis Example B1, except that 400 g (hydroxyl group = 3 mol) and hydrochloric acid 1 · 56 g (35% aqueous solution, 0.015 mol as HCl component) were added. It was. When this polyfunctional (meth) atalylate (B2) was analyzed by IR, the peak around 3500 cm 1 due to the hydroxyl group almost disappeared.
[0163] 〔合成例 B3〕  [0163] [Synthesis Example B3]
Mw400のトリス（ポリオキシプロピレン）グリセリルエーテルの代わりに Mw700のトリ ス (ポリオキシプロピレン)グリセリルエーテル (和光純薬工業 (株)製、上記式 (5)にお いて n = 3. 5) 700g (水酸基 = 3mol)を使用した以外は、合成例 B2と同様にして多 官能メタアタリレート（B3)を得た。この多官能 (メタ）アタリレート (B3)を IRにより分析 したところ、水酸基に起因する 3500cm 1付近のピークはほぼ消失していた。 Mw700 tris (polyoxypropylene) glyceryl ether instead of Mw700 tris (polyoxypropylene) glyceryl ether (Wako Pure Chemical Industries, Ltd., n = 3.5) in the above formula (5) 700 g ( A polyfunctional metaacrylate (B3) was obtained in the same manner as in Synthesis Example B2, except that hydroxyl group = 3 mol) was used. When this polyfunctional (meth) atalylate (B3) was analyzed by IR, the peak near 3500 cm 1 due to the hydroxyl group almost disappeared.
[0164] 〔合成例 B4〕  [Synthesis Example B4]
Mw400のトリス（ポリオキシプロピレン）グリセリルエーテルの代わりに MwlOOOのト リス（ポリオキシプロピレン)グリセリルエーテル（三井ポリウレタン (株)製、上記式（5) において n= 5. 2) 1000g (水酸基 = 3mol)を使用した以外は、合成例 B2と同様に して多官能メタアタリレート (B4)を得た。この多官能メタアタリレート（B4)を IRにより 分析したところ、水酸基に起因する 3500cm 1付近のピークはほぼ消失していた。 [0165] 〔合成例 B5〕 Instead of Mw400 tris (polyoxypropylene) glyceryl ether, MwlOOO tris (polyoxypropylene) glyceryl ether (Mitsui Polyurethane Co., Ltd., in the above formula (5), n = 5.2) 1000g (hydroxyl group = 3mol) A polyfunctional metaatarylate (B4) was obtained in the same manner as in Synthesis Example B2 except that was used. When this polyfunctional metaatalylate (B4) was analyzed by IR, the peak near 3500 cm 1 due to the hydroxyl group almost disappeared. [Synthesis Example B5]
攪拌装置、温度計、コンデンサーおよび窒素ガス導入管を備えた 3リットルのフラス コに、トリス（ポリオキシプロピレン）グリセリルエーテル（Mwl 500) (和光純薬工業（ 株）製、上記式（5)において η = 8· l) 1500g (水酸基 = 3mol)および塩酸 1 · 56g ( 35%水溶液、 HC1成分として 0. 015mol)を入れた以外は、合成例 B1と同様にして 多官能メタアタリレート (B5)を得た。この多官能 (メタ）アタリレート (B5)を IRにより分 析したところ、水酸基に起因する 3500cm 1付近のピークはほぼ消失していた。 Tris (polyoxypropylene) glyceryl ether (Mwl 500) (manufactured by Wako Pure Chemical Industries, Ltd., in the above formula (5)) was added to a 3 liter flask equipped with a stirrer, thermometer, condenser and nitrogen gas inlet tube. (η = 8 · l) Polyfunctional metaarate (B5) in the same manner as in Synthesis Example B1, except that 1500 g (hydroxyl group = 3 mol) and hydrochloric acid 1 · 56 g (35% aqueous solution, 0.015 mol as HC1 component) were added Got. When this polyfunctional (meth) atalylate (B5) was analyzed by IR, the peak near 3500 cm 1 due to the hydroxyl group almost disappeared.
[0166] [実施例;!〜 12]  [0166] [Examples !! ~ 12]
表 1に示す有機成分 100g (メタクリル樹脂（60重量％)、多官能メタアタリレート（35 重量％)、光重合開始剤（4重量％)および増感剤（1重量％) )をプロピレングリコー ルモノメチルエーテル（PGME) 30gに溶解した後、この溶液に無機粒子として表 1に 示すガラス粉末 300g、界面活性剤 A— 60 (花王 (株)製） 5gおよび紫外線吸収剤 T TO— V— 4 (石原産業 (株)製） 0. 05gを添加し、混練機で混練して無機粒子含有感 光性樹脂組成物（以下「感光性ペースト」ともレ、う。 )を調製した。  100 g of the organic components shown in Table 1 (methacrylic resin (60% by weight), polyfunctional methacrylate (35% by weight), photopolymerization initiator (4% by weight) and sensitizer (1% by weight)) were mixed with propylene glycol. After dissolving in 30 g of monomethyl ether (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 T TO- V-4 ( Ishihara Sangyo Co., Ltd.) 0.05 g was added and kneaded with a kneader to prepare a photosensitive resin composition containing inorganic particles (hereinafter also referred to as “photosensitive paste”).
[0167] 支持フィルムとして、予め離型処理したポリエチレンテレフタレート（PET)フィルム（ 幅 200mm、長さ 30m、厚さ 50 m)を 2枚用意し、これらの支持フィルムそれぞれの 上に、上記感光性ペーストをロールコーターにより塗布して塗膜を形成し、形成され た塗膜を 90°Cで 10分間乾燥して溶媒を除去することにより、厚さ 90 mの感光性樹 脂層を形成した。次いで、 2枚の PETフィルム上に形成した感光性樹脂層を互いに 貼り合せて、加熱ローラにより熱圧着した。圧着条件は、加熱ローラの表面温度を 90 °C、ロール圧を 4kg/cm2、加熱ローラの移動速度を速度 0. 5m/分とした。このよ うにして、無機粒子含有感光性樹脂層（厚さ 18011 m)を有する感光性フィルムを作[0167] As a support film, two sheets of polyethylene terephthalate (PET) film (width 200mm, length 30m, thickness 50m) that had been pre-released were prepared, and the photosensitive paste was placed on each of these support films. Was coated with a roll coater to form a coating film, 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 m. Next, the photosensitive resin layers formed on the two PET films were bonded to each other 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. In this way, a photosensitive film having a photosensitive resin layer (thickness 18011 m) containing inorganic particles was prepared.
； ^^し/ ; ^^
[0168] 次に、一方の支持フィルムを剥離して、ガラス試験片（150mm X 150mm X 2. 8m m)の表面に上記感光性樹脂層を重ね合わせ、残りの支持フィルムを剥離した後、感 光性樹脂層を加熱ローラにより熱圧着した。圧着条件は、加熱ローラの表面温度を 9 0°C、ロール圧を 4kg/cm2、加熱ローラの移動速度を 0. 5m/分とした。これにより 、ガラス基板の表面に無機粒子含有感光性樹脂層が転写されて密着した状態となつ た。転写された無機粒子含有感光性樹脂層の厚みを測定したところ、実施例;!〜 12 のいずれにおいても 180〃 m± 3〃 mの範囲にあった。 [0168] Next, one support film was peeled off, the photosensitive resin layer was overlaid on the surface of a glass test piece (150 mm x 150 mm x 2.8 mm), and the remaining support film was peeled off. The photopolymer layer was 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. As a result, the photosensitive resin layer containing inorganic particles is transferred and adhered to the surface of the glass substrate. It was. When the thickness of the transferred inorganic resin-containing photosensitive resin layer was measured, all of Examples;! To 12 were in the range of 180 μm ± 3 μm.
[0169] 次に、ネガ型クロムマスク（パターン幅 50 m、パターン間隔 150 m)を用いて、 上面から 25mj/cm2出力の超高圧水銀灯により、無機粒子含有感光性樹脂層を紫 外線露光した。露光量は 200mj/cm2であった。 [0169] Next, using a negative chrome mask (pattern width 50 m, pattern interval 150 m), the photosensitive resin layer containing inorganic particles was subjected to ultraviolet exposure with an ultrahigh pressure mercury lamp with an output of 25 mj / cm 2 from the top surface. . The exposure dose was 200 mj / cm 2 .
[0170] 次に、露光後の無機粒子含有感光性樹脂層に、 23°Cに保持した炭酸ナトリウムの[0170] Next, the inorganic particle-containing photosensitive resin layer after the exposure was subjected to sodium carbonate kept at 23 ° C.
0. 5%水溶液を、シャワーで 180秒間かけることにより現像した。その後、シャワース プレーを用いて水洗浄し、光硬化して!/、な!/、スペース部分を除去してパネル用ガラ ス基板上に格子状の無機粒子含有感光性樹脂パターンを形成した。この現像後の ノ^ーンを上記評価方法により評価した。結果を表 1に示す。 A 0.5% aqueous solution was developed by applying 180 seconds in a shower. Thereafter, it was washed with water using a shower spray, photocured, and the space was removed to form a lattice-shaped photosensitive resin pattern containing inorganic particles on the glass substrate for the panel. The developed noise was evaluated by the above evaluation method. The results are shown in Table 1.
[0171] 次に、得られた感光性樹脂パターンを 580°Cで 30分間焼成して隔壁パターンを形 成した。この焼成後のパターンを上記評価方法により評価した。結果を表 1に示す。 [0171] 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.
[0172] 表 1に示すように、現像後のパターン評価では、実施例 1、 2および 6〜； 10のパター ンが特に優れていた。また、焼成後のパターン評価では実施例 1〜； 12すべてが良好 であり、焼成後のパターンの欠けや剥がれ等は見られな力、つた。 [0172] As shown in Table 1, in the pattern evaluation after development, the patterns of Examples 1, 2, and 6 to 10 were particularly excellent. Further, in the pattern evaluation after firing, all of Examples 1 to 12 were good, and the chipping and peeling of the pattern after firing were not observed.
[0173] [表 1] [0173] [Table 1]
表 1 table 1
Figure imgf000042_0001
Figure imgf000042_0001
MTPMP : 2—メチル一1— [4— (メチルチオ） フエニル] 一 2—モルフォリノ一  MTPMP: 2-Methyl-1- 1- [4- (Methylthio) phenyl] 1 2-Morpholino 1
1ープ αパンー 1一オン  1 pu alpha pan 1 1 on
DMMPB： 2—べンジ ^一 2—ジメチルァミノ一 1一 （ 4—モルフオリノフ Iニル） ブタノン一 1  DMMPB: 2-Benzene ^ 1 2-Dimethylamino 1 1 (4-Morpholinov I Nyl) Butanone 1
DETX : 2, 4—ジェチルチオキサントン  DETX: 2, 4—Jetylthioxanthone
PGME ： プロピレングリコールモノメチルエーテルを示す。  PGME: Indicates propylene glycol monomethyl ether.
括弧内の数字は質量部を示す  Numbers in parentheses indicate parts by mass
[比較例；！〜 7]  [Comparison example; ~ 7]
表 2に示す有機成分 lOOg (メタクリル樹脂（60重量。 /0)、多官能メタアタリレート（： 重量％)、光重合開始剤（4重量％)および増感剤（1重量％) )を使用した以外は、 施例 1と同様にしてパターンを作製して評価した。結果を表 2に示す。 [0175] 比較例;!〜 6では、現像後のパターン評価にぉレ、て所望するパターンを観察したが 、焼成後のパターン評価においてパターンの欠けや剥がれ等が見られた。 Organic components shown in Table 2 LOOG: using (methacrylic resin (60 wt / 0), a multifunctional meth Atari rate (.% By weight), a photopolymerization initiator (4 wt%) and sensitizer (1 wt%)) A pattern was prepared and evaluated in the same manner as in Example 1 except that. The results are shown in Table 2. [0175] In Comparative Examples;! To 6, a desired pattern was observed in the evaluation of the pattern after development. However, chipping or peeling of the pattern was observed in the evaluation of the pattern after baking.
[0176] 比較例 7では、現像後のパターン評価にぉレ、てアスペクト比不足や現像残渣が見 られる等の不良のパターンを観察した。また、焼成後のパターン評価においてァスぺ タト比不足のパターンが観察された。  In Comparative Example 7, a defective pattern such as an insufficient aspect ratio or development residue was observed in the pattern evaluation after development. In addition, a pattern with insufficient aspect ratio was observed in the pattern evaluation after firing.
[0177] [表 2] 表 2  [0177] [Table 2] Table 2
Figure imgf000043_0001
Figure imgf000043_0001
TMP： トリメチロールプロパントリァクリレート  TMP: Trimethylolpropane triacrylate
DPTA：ジペンタエリスリトー ^キサァクリレート  DPTA: Dipentaerythrito ^ xaacrylate
DTMPTA： ジトリメチロールプロパンテトラァクリ "ト  DTMPTA: Ditrimethylolpropane tetraacrylate
PETTA：ペンタエリスリトール亍トラァクリレート  PETTA: Pentaerythritol triacrylate
MTPMP： 2—メチル一1一 [4一（メチルチオ） フエニル]一 2—モルフオリノ一 1一 プロ/ ン一 1一才ン  MTPMP: 2-methyl 1 1 [4 1 (methylthio) phenyl] 1 2-morpholino 1 1 pro / 1 1 1
DETX： 2, 4一ジェチルチオキサントン  DETX: 2, 4 One Jetylthioxanthone
PGME：プロピレングリコールモノメチルェ一亍ル  PGME: Propylene glycol monomethyl ester
括弧内の数字は sawを示す  The numbers in parentheses indicate saw
[0178] [実施例 13〜27]  [Examples 13 to 27]
表 3に示す有機成分 (メタクリル樹脂、多官能アタリレート、光重合開始剤、増感剤 溶解促進剤および溶剤）とを混合した後に、この組成物に無機粉体として表 3に示す ガラス粉末と導電性粉末とを添加し、混練機で混練して無機粒子含有感光性樹脂組 成物（以下「感光性ペースト」ともいう。）を調製した。 Organic components shown in Table 3 (methacrylic resin, polyfunctional acrylate, photopolymerization initiator, sensitizer After mixing with a dissolution accelerator and a solvent, the glass powder and conductive powder shown in Table 3 are added to the composition as inorganic powder, and the mixture is kneaded with a kneader and mixed with a photosensitive resin composition containing inorganic particles. (Hereinafter also referred to as “photosensitive paste”).
[0179] なお、表 3に記載の導電性粉末として、  [0179] As the conductive powder described in Table 3,
Ag (比表面積： 1. 5m2/g、平均粒径（D50) : 1 · 5 m)、 Cu (平均粒径（D50) : 0. 6 111)、 Ni (平均粒径（D50) : 0. 4 ）、 Sn (平均粒径（D50) : 0. 5 μ ϊη ^^Χ Ζ η (平均粒径（D50) : 2· 0 111)、 Ag— Pt (平均粒径（D50) : 2. S ^ m Pt (平均粒 径（D50) : 2. 2 111)、 Au (平均粒径（D50) : 0· 6 m)、および A1 (平均粒径（D50 ) : 2. 0 m)のいずれかを用いた。 Ag (specific surface area: 1.5 m 2 / g, average particle size (D50): 1 · 5 m), Cu (average particle size (D50): 0.6 111), Ni (average particle size (D50): 0 4), Sn (average particle size (D50): 0.5 μϊη ^^ ΧΧη (average particle size (D50): 2 · 111), Ag—Pt (average particle size (D50): 2. S ^ m Pt (average particle size (D50): 2.2 111), Au (average particle size (D50): 0 · 6 m), or A1 (average particle size (D50): 2.0 m) Was used.
[0180] またガラスフリットとしては、 Bi O — SiO — B O — Al O —ZnO系ガラスフリット（不  [0180] As glass frit, Bi O — SiO — B O — Al O — ZnO glass frit (non-
2 3 2 2 3 2 3  2 3 2 2 3 2 3
定形、平均粒径（D50) : 3· O ^ m,軟化点： 520°C)を用いた。  Standard shape, average particle size (D50): 3 · O ^ m, softening point: 520 ° C) was used.
[0181] 支持フィルムとして、予め離型処理したポリエチレンテレフタレート（PET)フィルム（ 幅 200mm、長さ 30m、厚さ 50 m)を 2枚用意し、支持フィルムの上に、上記感光 性ペーストをロールコーターにより塗布して塗膜を形成し、形成された塗膜を 100°C で 5分間乾燥して溶媒を除去することにより、厚さ 10 ΐηの感光性樹脂層を形成した 。次いで、予め離型処理した PETフィルムを貼り合せて、加熱ローラにより熱圧着し た。圧着条件は、加熱ローラの表面温度を 90°C、ロール圧を 4kg/cm2、加熱ローラ の移動速度を速度 0. 5m/分とした。このようにして、無機粉末含有感光性樹脂層（ 厚さ 10 m)を有する感光性フィルムを作製した。 [0181] Two polyethylene terephthalate (PET) films (width 200mm, length 30m, thickness 50m) that had been pre-released were prepared as support films, and the above-mentioned photosensitive paste was rolled onto the support film. coating film was formed by coating by, by removing the solvent the formed coating film was dried for 5 minutes at 1 00 ° C, to form a photosensitive resin layer having a thickness of 10 ΐη. Next, a PET film that had been subjected to release treatment in advance was bonded and thermocompression bonded with a heating roller. Bonding conditions, the surface temperature of 90 ° C (194 ° F) of the heating roller, roll pressure of 4 kg / cm 2, the moving speed of the heating roller was set to the speed 0. 5 m / min. In this way, a photosensitive film having an inorganic powder-containing photosensitive resin layer (thickness 10 m) was produced.
[0182] 次に、一方の支持フィルムを剥離して、ガラス試験片（150mm X 150mm X 2. 8m m)の表面に上記感光性樹脂層を重ね合わせ、残りの支持フィルムを剥離した後、感 光性樹脂層を加熱ローラにより熱圧着した。圧着条件は、加熱ローラの表面温度を 9 0°C、ロール圧を 4kg/cm2、加熱ローラの移動速度を 0. 5m/分とした。これにより 、ガラス基板の表面に無機粉末含有感光性樹脂層が転写されて密着した状態となつ た。転写された無機粉末含有感光性樹脂層の厚みを測定したところ、実施例 13〜2 7の!/、ずれにお!/、ても 10〃 m ± 1 mの範囲にあった。 [0182] Next, one support film was peeled off, the photosensitive resin layer was overlaid on the surface of a glass test piece (150 mm X 150 mm X 2.8 mm), and the remaining support film was peeled off. The photopolymer layer was 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. As a result, the inorganic powder-containing photosensitive resin layer was transferred to and adhered to the surface of the glass substrate. When the thickness of the transferred inorganic powder-containing photosensitive resin layer was measured, it was in the range of 10 / m ± 1 m in Examples 13 to 27.
[0183] 次に、ネガ型クロムマスク（パターン幅 50 m、パターン間隔 100 m)を用いて、 上面から 25mj/cm2出力の超高圧水銀灯により、無機粒子含有感光性樹脂層を紫 外線露光した。露光量は 1000mj/cm2であった。 [0183] Next, using a negative chrome mask (pattern width 50 m, pattern interval 100 m), the photosensitive resin layer containing inorganic particles was violetd using an ultrahigh pressure mercury lamp with an output of 25 mj / cm 2 from the top surface. External exposure. Exposure amount was 1000 mj / cm 2.
[0184] 次に、露光後の無機粉末含有感光性樹脂層に、 23°Cに保持した炭酸ナトリウムの 0. 5%水溶液を、シャワーで 60秒間かけることにより現像した。その後、シャワースプ レーを用いて水洗浄し、光硬化して!/、な!/、スペース部分を除去してパネル用ガラス 基板上に格子状の無機粒子含有感光性樹脂パターンを形成した。この現像後のパ ターンを上記評価方法により評価した。結果を表 3に示す。  [0184] Next, the inorganic powder-containing photosensitive resin layer after exposure was developed by applying a 0.5% aqueous solution of sodium carbonate maintained at 23 ° C for 60 seconds in a shower. Thereafter, it was washed with water using a shower spray, photocured, and the space portion was removed to form a lattice-shaped photosensitive resin pattern containing inorganic particles on the glass substrate for panels. The pattern after this development was evaluated by the above evaluation method. The results are shown in Table 3.
[0185] 次に、得られた感光性樹脂パターンを 580°Cで 30分間焼成して隔壁パターンを形 成した。この焼成後のパターンを上記評価方法により評価した。結果を表 3に示す。  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.
[0186] 表 3に示すように、現像後のパターン評価では、実施例 13〜； 18が特に優れていた 。実施例 19〜26は良好であった。また、焼成後のパターン評価では実施例 13〜18 が特に優れていた。実施例 19〜26は良好であり、焼成後のパターンの欠けや剥が れ等は見られなかった。体積抵抗の評価では実施例 13〜27は全て 2〜； 100 Ω - c mの範囲に入り、電極として使用できるレベルであった。  [0186] 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 a range of 2 to 100 Ω-cm, and were at a level that could be used as an electrode.
[0187] [実施例 28〜34]  [0187] [Examples 28 to 34]
表 3に示す有機成分 (メタクリル樹脂、多官能アタリレート、光重合開始剤、増感剤、 溶解促進剤、および溶剤）を混合した後に、この組成物に無機粉体として表 3に示す ガラス粉末と導電性粉末とを添加し、混練機で混練して無機粒子含有感光性樹脂組 成物（以下「感光性ペースト」ともいう。）を調製した。上記感光性ペーストを 325メッシ ュのスクリーンを用いてガラス基板（150mm角で、厚み 2. 8mm)上に 100mm角の 大きさにベタに印刷し、 100°Cで 10分間保持して乾燥した。実施例 28〜34のいず れにおいても 10〃 m± 1 mの範囲にあった。  After mixing the organic components shown in Table 3 (methacrylic resin, polyfunctional acrylate, photopolymerization initiator, sensitizer, dissolution accelerator, and solvent), glass powder shown in Table 3 as inorganic powder in this composition And a conductive powder were added and kneaded with a kneader to prepare a photosensitive resin composition containing inorganic particles (hereinafter also referred to as “photosensitive paste”). The above photosensitive paste was printed on a glass substrate (150 mm square, 2.8 mm thick) with a size of 100 mm square using a 325 mesh screen, dried at 100 ° C. for 10 minutes. All of Examples 28 to 34 were in the range of 10 mm ± 1 m.
[0188] 次に、ネガ型クロムマスク（パターン幅 50 m、パターン間隔 100 m)を用いて、 上面から 25mj/cm2出力の超高圧水銀灯により、無機粒子含有感光性樹脂層を紫 外線露光した。露光量は 1000mj/cm2であった。 [0188] Next, using a negative chrome mask (pattern width 50 m, pattern interval 100 m), the photosensitive resin layer containing inorganic particles was subjected to ultraviolet exposure using an ultrahigh pressure mercury lamp with an output of 25 mj / cm 2 from the top surface. . The exposure dose was 1000 mj / cm 2 .
[0189] 次に、露光後の無機粉末含有感光性樹脂層に、 23°Cに保持した炭酸ナトリウムの 0. 5%水溶液を、シャワーで 60秒間かけることにより現像した。その後、シャワースプ レーを用いて水洗浄し、光硬化して!/、な!/、スペース部分を除去してパネル用ガラス 基板上に格子状の無機粒子含有感光性樹脂パターンを形成した。この現像後のパ ターンを上記評価方法により評価した。結果を表 3に示す。 Next, the inorganic powder-containing photosensitive resin layer after exposure was developed by applying a 0.5% aqueous solution of sodium carbonate maintained at 23 ° C. for 60 seconds in a shower. Thereafter, it was washed with water using a shower spray, photocured, and the space portion was removed to form a lattice-shaped photosensitive resin pattern containing inorganic particles on the glass substrate for panels. After this development, The turn was evaluated by the above evaluation method. The results are shown in Table 3.
[0190] 次に、得られた感光性樹脂パターンを 580°Cで 30分間焼成して隔壁パターンを形 成した。この焼成後のパターンを上記評価方法により評価した。結果を表 3に示す。  [0190] 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.
[0191] 表 3に示すように、実施例 28〜34においての現像後のパターン評価では、実施例 28および 29が特に優れていた。実施例 30〜34は良好であった。また、焼成後のパ ターン評価では実施例 28および 29が特に優れていた。実施例 30〜34は良好であ り、焼成後のパターンの欠けや剥がれ等は見られなかった。体積抵抗の評価では実 施例 28〜34は 3〜； 100 Ω ' cmの範囲に入り、電極として使用できるレベルであつ  [0191] 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. In addition, Examples 28 and 29 were particularly excellent in pattern evaluation after firing. Examples 30 to 34 were good, and no chipping or peeling of the pattern after firing was observed. In the evaluation of volume resistance, Examples 28 to 34 are in the range of 3 to; 100 Ω 'cm, and can be used as electrodes.
[比較例 8〜； 1 1] [Comparative Examples 8 ~; 1 1]
比較例 8〜11は、表 3に示す組成としたこと意外は実施例 13と同様に行い、実施 例 13と同様の評価を行った。現像後のパターン評価では、比較例 8〜； 1 1は不良の 結果となった。また、焼成後のパターン評価では比較例 8〜； 11は不良であり、焼成後 のパターンの欠けや剥がれ等が見られた。体積抵抗の評価では比較例 8〜； 11はす ベて 6〜50 Ω ' cmの範囲に入り、電極として使用できるレベルであった。  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 showed poor results. Further, in the pattern evaluation after firing, Comparative Examples 8 to 11 were defective, and the chipping or peeling of the pattern after firing was observed. In the evaluation of the volume resistance, Comparative Examples 8 to 11 were all in the range of 6 to 50 Ω′cm, and could be used as electrodes.
[比較例 12〜； 15]  [Comparative Examples 12 to 15]
比較例 12〜15は、表 3に示す組成としたこと意外は実施例 28と同様に行い、実施 例 28と同様の評価を行った。現像後のパターン評価では、比較例 12〜； 15は不良の 結果となった。また、焼成後のパターン評価では比較例 12〜； 15は不良であり、焼成 後のパターンの欠けや剥がれ等が見られた。体積抵抗の評価では比較例 12〜； 15は すべて 3〜 50 Ω ' cmの範囲に入り、電極として使用できるレベルであった。  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 evaluation of the pattern after development, Comparative Examples 12 to 15 showed poor results. Further, in the pattern evaluation after firing, Comparative Examples 12 to 15 were poor, and the chipping or peeling of the pattern after firing was observed. In the volume resistance evaluation, Comparative Examples 12 to 15 and 15 were all in the range of 3 to 50 Ω′cm, and could be used as electrodes.
[0192] [表 3] [0192] [Table 3]
Hy一^ HT MTTMP¾ί^〔〕¾ίτά、JΜΡ3 Τi093a1口:、I〜。 Hy 1 ^ HT MTTMP¾ί ^ [] ¾ίτά 、 JΜΡ3 Τi093a1 口 ： 、 I ～.
表 3
Figure imgf000047_0001
Table 3
Figure imgf000047_0001
は、 2—メチルー 1 [4 （メチルチオ）フエニル] 2—モルフオリノー 1 プロパン 1—オンを示し、 DETXは 2, 4—ジェチルチオキサントンを示し、 PGMEはプロピレ ングリコールモノメチルエーテルを示す。また A— 60はェマルゲン A— 60 (商品名、 花王（株）製、ポリオキシエチレンジスチレン化フエニルエーテル）を示し、 TNOLはタ 一ビネオールを示す。 Represents 2-methyl-1 [4 (methylthio) phenyl] 2-morpholino 1 propane 1-one, DETX represents 2,4-jetylthioxanthone, and PGME represents propylene glycol monomethyl ether. A-60 represents Emargen A-60 (trade name, manufactured by Kao Corporation, polyoxyethylene distyrenylated phenyl ether), and TNOL represents tubineol.
[0194] また、数字は質量部を示す。  [0194] The numbers indicate parts by mass.
[0195] [実施例 35]  [0195] [Example 35]
(1)無機粉体含有感光性樹脂組成物の調製  (1) Preparation of a photosensitive resin composition containing inorganic powder
無機粉体として、 MnCo O— CoMn O— CuMn O 一 Cu Mn O系顔料（比表  As inorganic powders, MnCo O— CoMn O— CuMn O and Cu Mn O pigments (ratio table)
2 4 2 4 2 4 3 3 8  2 4 2 4 2 4 3 3 8
面積： 18· 9m2/g、平均粒径（D50) : 0· 3 m、以下「顔料 1」ともいう。） 15部およ び Bi O -ZnO-B O -BaO- SiO系ガラス粉末（不定形、平均粒径（D50) : 0. Area: 18 · 9m 2 / g, average particle size (D50): 0.3 · m, hereinafter also referred to as “Pigment 1”. ) 15 parts and Bi O -ZnO-B O -BaO- SiO glass powder (indefinite shape, average particle size (D50): 0.
2 3 2 3 2  2 3 2 3 2
6〃m、軟化点： 456°C、線膨張係数： 8. 6 X 10— 6/K、以下「ガラス 1」ともいう。 ) 95 部と、アルカリ可溶性樹脂 (Α)として SH基含有メタクリル樹脂 (Α8)を 24部と、多官 能（メタ）アタリレート（Β)としてトリメチロールプロパン ΕΟ変性（η 2)トリアタリレート（ 商品名： Μ360、東亞合成 (株)製） 16部と、光重合開始剤（C)として、 2 ベンジル 一 2 ジメチルアミノー 1一 （4一モルフオリノフエニル）一ブタン一 1一オン（以下「光 重合開始剤 c l」ともいう。）2部および 2, 2—ジメトキシ—1 , 2—ジフエニルェタン 1 オン (以下「光重合開始剤 c 2」ともいう。） 1部と、密着助剤として 3 メタクリロ キシプロピルメトキシシラン 0. 22部と、溶剤としてプロピレングリコールモノメチルエー テル 20部とをビーズミルで混練りした。次いで、混練物をステンレスメッシュ（400メッ シュ、 25 m径）でフィルタリングすることにより、ブラックマトリクス形成用の無機粉体 含有樹脂組成物 (I)を調製した。 6〃M, softening point: 456 ° C, linear expansion coefficient: 8. 6 X 10- 6 / K , hereinafter referred to as "glass 1". ) 95 parts, alkali-soluble resin (Α) with SH group-containing methacrylic resin (Α8), 24 parts, multi-functional (meth) acrylate (Β) with trimethylolpropane ΕΟ modified (η 2) triatrate ( Product name: Μ360, manufactured by Toagosei Co., Ltd.) 16 parts, and as photopolymerization initiator (C), 2 benzyl 1-2 dimethylamino 1-1 (4 morpholinophenyl) 1 butane 1 1 1 Also referred to as “photoinitiator cl”.) 2 parts and 2, 2-dimethoxy-1, 2-diphenylethane 1-on (hereinafter also referred to as “photoinitiator c 2”) and 3 parts as adhesion assistant 0.22 part of methacryloxypropylmethoxysilane and 20 parts of propylene glycol monomethyl ether as a solvent were kneaded with a bead mill. Next, the kneaded product was filtered with a stainless mesh (400 mesh, 25 m diameter) to prepare an inorganic powder-containing resin composition (I) for forming a black matrix.
[0196] (2)転写フィルムの作製 [0196] (2) Preparation of transfer film
上記工程（1)で調製した無機粉体含有樹脂組成物（I)を、あらかじめ離型処理した 膜厚 38 H mの PETフィルムよりなる支持フィルム上にブレードコーターを用いて塗布 し、塗膜を 100°Cで 1分 30秒間乾燥して溶剤を除去することにより、厚さ 6 111の無 機粉体含有樹脂層が支持フィルム上に形成された本発明の転写フィルムを作製した [0197] (3)転写フィルムの転写工程 The inorganic powder-containing resin composition (I) prepared in the above step (1) was applied onto a support film made of a PET film having a film thickness of 38 Hm, which had been subjected to a release treatment, using a blade coater. The transfer film of the present invention in which an organic powder-containing resin layer having a thickness of 6111 was formed on a support film by drying at 100 ° C. for 1 minute 30 seconds to remove the solvent was produced. [0197] (3) Transfer process of transfer film
上記工程（2)で作製した転写フィルムを用い、ガラス基板の表面に無機粉体含有 樹脂層の表面が当接されるよう該転写フィルムを重ね合わせ、加熱ローラで熱圧着し た。ここで、圧着条件としては、加熱ローラの表面温度を 90°C、ロール圧を 0. 25MP aおよび加熱ローラの移動速度を 0. 5m/分とした。これにより、ガラス基板の表面に 無機粉体含有樹脂層が転写されて密着した状態となった。  Using the transfer film produced in the above step (2), the transfer film was superposed on the surface of the glass substrate so that the surface of the inorganic powder-containing resin layer was in contact with the glass substrate, and thermocompression bonded with a heating roller. 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.
[0198] (4)無機粉体含有樹脂層の露光工程および現像工程  [0198] (4) Exposure process and development process of resin layer containing inorganic powder
上記工程 (3)でガラス基板上に形成した無機粉体含有樹脂層に対して、支持フィ ルム剥離後、露光用マスク（5cm X 5cm、パターン幅 50 m、パターン間隔 150 m)を介して、超高圧水銀灯により、 i線 (波長 365nmの紫外線)を照射し、無機粉体 含有樹脂層にパターンの潜像を形成した。なお、照射量は 800mj/cm2とした。露 光後、液温 25°Cの 0. 5質量％炭酸ナトリウム水溶液を現像液とするシャワー法により 現像処理を 20秒間行い、続いて、超純水を用いて水洗を行った。これにより、紫外 線が照射されてレ、なレ、部分の無機粉体含有樹脂を除去し、無機粉体含有樹脂バタ ーンを形成した。 After the support film is peeled off from the inorganic powder-containing resin layer formed on the glass substrate in the above step (3), it is passed through an exposure mask (5 cm x 5 cm, pattern width 50 m, pattern interval 150 m). A latent image of the pattern was formed on the resin layer containing inorganic powder by irradiating i-line (ultraviolet with a wavelength of 365 nm) with an ultra-high pressure mercury lamp. The irradiation dose was 800 mj / cm 2 . After exposure, the film was developed for 20 seconds by a shower method using a 0.5 mass% aqueous sodium carbonate solution at a liquid temperature of 25 ° C. as a developer, and then washed with ultrapure water. As a result, the resin was irradiated with ultraviolet rays, and the resin contained in the inorganic powder was removed, forming an inorganic powder-containing resin pattern.
[0199] (5)焼成工程  [0199] (5) Firing process
上記工程 (4)で形成した無機粉体含有樹脂パターンを有するガラス基板を 520°C の温度雰囲気下で 30分間焼成処理した。これにより、ガラス基板の表面に厚み 2. 0 a mのブラックマトリクスが形成された。  The glass substrate having the inorganic powder-containing resin pattern formed in the above 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 am was formed on the surface of the glass substrate.
[0200] 上記の工程で得られた組成物およびブラックマトリクスについて、以下の方法により 評価した。  [0200] The composition and black matrix obtained in the above steps were evaluated by the following methods.
[0201] [硬化深度評価]  [0201] [Evaluation of curing depth]
上記工程 (3)でガラス基板上に形成した無機粉体含有樹脂層に対して、ガラス基 板側から無機粉体含有樹脂層に向かって超高圧水銀灯により、 i線 (波長 365nmの 紫外線)を照射し、無機粉体含有樹脂層を硬化させた。なお、照射量は 800mj/c m2とした。露光後、支持フィルムを剥離除去し、次いで、液温 25°Cの 0. 5質量％炭 酸ナトリウム水溶液を現像液とするシャワー法により現像処理を 30秒間行い、続いて 、超純水を用いて水洗を行った。これにより、紫外線が照射されていない部分の無機 粉体含有樹脂を除去した。 For the inorganic powder-containing resin layer formed on the glass substrate in the above step (3), i-line (ultraviolet light with a wavelength of 365 nm) is emitted from the glass substrate side toward the inorganic powder-containing resin layer with an ultra-high pressure mercury lamp. Irradiation was performed to cure the inorganic powder-containing resin layer. 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 using ultrapure water. And washed with water. In this way, the inorganic part of the part not irradiated with ultraviolet rays The powder-containing resin was removed.
[0202] 上記の工程で得られた無機粉体含有樹脂層の残膜厚を、微細柱高さ測定器 P— 1 0 (KLA— TENCOR製）を用いて測定した。測定値から硬化深度の良好性を以下 の AA、 BBおよび CCで評価した。結果を表 4に示す。 [0202] The residual film thickness of the inorganic powder-containing resin layer obtained in the above step was measured using a fine column height measuring instrument 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.
[0203] AA：残膜厚が 6 μ mを超える [0203] AA: Residual film thickness exceeds 6 μm
88 :残膜厚が4〜6 111  88: Residual film thickness 4-6 111
CC :残膜厚が 4 ^ 111未満  CC: Remaining film thickness is less than 4 ^ 111
[焼成後のパターユング評価 （実施例 35〜38、比較例 16〜； 19) ]  [Patterung evaluation after firing (Examples 35 to 38, Comparative Examples 16 to 19)]
上記工程（5)で得られた基板を、走査型電子顕微鏡にて観察し、反りが発生してい るかどうかを目視することによりパターユング性を評価した。反りの発生は、 AA、 BB および CCで表記する。結果を表 4に示す。  The substrate obtained in the above step (5) was observed with a scanning electron microscope, and the patterning property was evaluated by observing whether or not warping had occurred. The occurrence of warpage is indicated by AA, BB and CC. The results are shown in Table 4.
[0204] AA:パターンの反りおよび基板からの剥がれなし。 [0204] AA: No pattern warping or peeling from substrate.
[0205] BB :パターンの反りは発生するが BM層が基板からの剥がれなし。 [0205] BB: Pattern warpage occurs but the BM layer does not peel off from the substrate.
[0206] CC :パターンの反りが発生し、基板からの剥がれあり。 上記工程（5)で得られた 5cm X 5cm形状のブラックマトリクスを用いて、分光光度 計（(株）島津製作所製 UV— 2450PC、 （株）島津製作所製マルチパーパス大形試 料室ユニット MPC— 2200付属、以下同じ）を用いて、波長 550nmでの透過率を測 定した。結果を表 4に示す。 [0206] CC: The pattern warps and peels off from the substrate. Using the black matrix of 5cm x 5cm shape obtained in the above step (5), spectrophotometer (UV-2450PC manufactured by Shimadzu Corporation), multipurpose large sample chamber unit MPC- manufactured by Shimadzu Corporation The transmittance at a wavelength of 550 nm was measured using 2200 attachment (the same applies hereinafter). The results are shown in Table 4.
[ブラックマトリクスの反射率評価]  [Reflectance evaluation of black matrix]
上記工程（5)で得られた 5cm X 5cm形状のブラックマトリクスを用いて、分光光度 計を用いて、波長 550nmでの反射率を測定した。結果を表 4に示す。  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.
[0207] [実施例 36〜40、比較例 16〜； 18] [Examples 36 to 40, Comparative Examples 16 to 18; 18]
表 4に記載の組成を用いたこと以外は、実施例 35と同様にして、無機粉体含有樹 脂組成物の調製、転写フィルムの作製ならびにブラックマトリクスの形成および評価 を行った。結果を表 4にあわせて示す。  Except having used the composition of Table 4, it carried out similarly to Example 35, and prepared the inorganic powder containing resin composition, preparation of the transfer film, and formation and evaluation of the black matrix. The results are shown in Table 4.
[0208] [実施例 41] [0208] [Example 41]
(1)積層構造体の作製 実施例 35と同様にして実施例 35の工程（1)〜（4)を行い、ガラス基板上に無機粉 体含有樹脂パターン (線膨張係数 8. 6 X 10— 6/K)を形成した後、該無機粉体含有 樹脂パターンの上層に、 (1) Fabrication of laminated structure Perform steps (1) to (4) of Example 35 in the same manner as in Example 35, after forming the inorganic powder-containing resin pattern (linear expansion coefficient 8. 6 X 10- 6 / K) on a glass substrate In the upper layer of the resin pattern containing the inorganic powder,
Al Ο -Β Ο Bi O -Na O— SiO— ZnO系ガラス粉末（不定形、平均粒経（D5 Al Ο -Β Ο Bi O -Na O- SiO-ZnO glass powder (indefinite shape, average particle size (D5
2 3 2 3 2 3 2 2 2 3 2 3 2 3 2 2
0) : 1. O ^ rn、軟化点： 470°C、線膨張係数： 9. 2 X 10— 6/K) 100部、 0): 1. O ^ rn, softening point: 470 ° C, linear expansion coefficient: 9.2 X 10— 6 / K) 100 parts,
シクロへキシルメタタリレート /2—フエノキシ ェチルアタリレート /2—ヒドロキシプ 口ピルメタタリレート/メタクリル酸共重合体（ = 40/30/10/20 (質量比）） 15部、 トリメチロールプロパン ΡΟ変性トリアタリレート（商品名： Μ320、東亞合成 (株)製） 5 部、トリプロピレングリコールジアタリレート（商品名： Μ220、東亞合成（株）製） 5部、 2 -ベンジル 2—ジメチルァミノ一 1— (4—モルフオリノフエニル）一ブタン一 1—ォ ン 1部、 2, 2 ジメトキシ一 1 , 2 ジフエニルェタン一 1—オン 0. 4部、 プロピレングリコールモノメチルエーテルアセテートよりなる無機粉体含有組成物 によって厚さ 25 a mの層を形成した。  Cyclohexyl methacrylate / 2—Phenoxyethyl acrylate / 2-hydroxypropyl methacrylate / methacrylic acid copolymer (= 40/30/10/20 (mass ratio)) 15 parts, trimethylolpropane ΡΟ-modified triatalylate (trade name: Μ320, manufactured by Toagosei Co., Ltd.) 5 parts, tripropylene glycol ditalylate (product name: Μ220, manufactured by Toagosei Co., Ltd.) 5 parts, 2-benzyl 2-dimethylamino 1- (4-morpholinophenyl) 1-butane 1-one 1 part, 2, 2 Dimethoxy 1 1, 2 Diphenyl 1-one 1-one 0.4 part, propylene glycol monomethyl ether acetate A 25 am thick layer was formed by the object.
[0209] この層に対して露光用マスク（5cm X 5cm、パターン幅 50 m、パターン間隔 200 in)を介して、超高圧水銀灯により、 i線 (波長 365nmの紫外線)を照射し、無機粉 体含有樹脂層にパターンの潜像を形成した。なお、照射量は 800mj/cm2とした。 露光後、液温 25°Cの 0. 5質量％炭酸ナトリウム水溶液を現像液とするシャワー法に より現像処理を 20秒間行い、続いて、超純水を用いて水洗を行った。これにより、紫 外線が照射されていない部分の無機粉体含有樹脂を除去し、積層パターンを得た。 [0209] This layer was irradiated with i-rays (ultraviolet light with a wavelength of 365 nm) with an ultrahigh pressure mercury lamp through an exposure mask (5 cm x 5 cm, pattern width 50 m, pattern interval 200 in), and an inorganic powder A latent image of the pattern was formed on the containing resin layer. 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. This removed the inorganic powder containing resin of the part which was not irradiated with the ultraviolet ray, and obtained the lamination pattern.
[0210] 該積層パターンを、 520°Cの温度雰囲気下で 30分間焼成処理した。これにより、ガ ラス基板の表面に積層構造体が形成された。焼成後のパターユング評価を実施例 3 5と同様の方法および基準により行った。結果を表 5に示す。  [0210] The laminated pattern was baked for 30 minutes in a temperature atmosphere of 520 ° C. As a result, a laminated structure was formed on the surface of the glass substrate. The patterning evaluation after firing was performed by the same method and standard as in Example 35. The results are shown in Table 5.
[0211] [実施例 42、比較例 19]  [0211] [Example 42, Comparative Example 19]
(1)積層構造体の作製  (1) Fabrication of laminated structure
組成物として表 5に記載のものを用いた以外は、実施例 41と同様に行った。焼成後 のパターユング評価結果を表 5に示す。  The same procedure as in Example 41 was performed except that the composition shown in Table 5 was used. Table 5 shows the results of patterning evaluation after firing.
[0212] [表 4] 表 4 [0212] [Table 4] Table 4
Figure imgf000052_0001
Figure imgf000052_0001
5] Five]
表 5 Table 5
実施例 4 1 実施例 42 比較例 1 9 種類 顔料 1 顔料 1 顔料 1 顔料  Example 4 1 Example 42 Comparative Example 1 9 types Pigment 1 Pigment 1 Pigment 1 Pigment
部 1 5 1 5 1 5 種類 ガラス 1 ガラス 1 ガラス 1 ガラス粉体  Part 1 5 1 5 1 5 Types Glass 1 Glass 1 Glass 1 Glass powder
部 9 5 95 95 種類 A8 A9 A1 0 メタクリノレ樹脂  Part 9 5 95 95 Type A8 A9 A1 0 Methacrylate resin
部 24 24 24 光重合性モノマ一 部 1 6 1 6 1 6  Part 24 24 24 photopolymerizable monomer part 1 6 1 6 1 6
c -1/部 2. 5 2. 5 5. 0 光重合開始剤  c -1 / part 2.5 5 5 5. 0 Photopolymerization initiator
c -2/部 1. 1 1. 1 2 2 有機シラン化合物 部 0. 22 0. 22 0. 22 反りの発生 AA AA CC  c -2 / Part 1. 1 1. 1 2 2 Organosilane Compound Part 0. 22 0. 22 0. 22 Warpage AA AA CC

Claims

請求の範囲 The scope of the claims
[1] 少なくとも 1つの SH基を有するアルカリ可溶性樹脂 (A)、多官能 (メタ）アタリレート（ B)、光重合開始剤 (C)、および無機粒子 (D)を含有することを特徴とする感光性樹 脂組成物。  [1] It 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) Photosensitive resin composition.
[2] 前記無機粒子（D)の少なくとも一部がガラス粉末であることを特徴とする請求項 1に 記載の感光性樹脂組成物。  [2] The photosensitive resin composition according to claim 1, wherein at least a part of the inorganic particles (D) is a glass powder.
[3] 前記アルカリ可溶性樹脂 (A)が、 1分子中に少なくとも 2つの SH基を有する化合物 [3] The compound in which the alkali-soluble resin (A) has at least two SH groups in one molecule
(A1)の存在下で、アルカリ可溶性官能基含有モノマー (A2)と (メタ）アクリル酸誘導 体 (A3)とを重合して得られる（メタ）アクリル樹脂であることを特徴とする請求項 1また は 2に記載の感光性樹脂組成物。  2. A (meth) acrylic resin obtained by polymerizing an alkali-soluble functional group-containing monomer (A2) and a (meth) acrylic acid derivative (A3) in the presence of (A1). Or the photosensitive resin composition of 2.
[4] 前記化合物（A1)が、 SH基含有カルボン酸と多価アルコールとのエステルであるこ とを特徴とする請求項 3に記載の感光性樹脂組成物。 [4] The photosensitive resin composition according to claim 3, wherein the compound (A1) is an ester of an SH group-containing carboxylic acid and a polyhydric alcohol.
[5] 前記多官能 (メタ）アタリレート (B)が下記式（1)で表される基を有することを特徴と する請求項 1〜4のいずれかに記載の感光性樹脂組成物。 [5] The photosensitive resin composition according to any one of [1] to [4], wherein the polyfunctional (meth) acrylate (B) has a group represented by the following formula (1).
[化 1]  [Chemical 1]
Figure imgf000054_0001
Figure imgf000054_0001
〔式（1)中、 R1は水素原子またはメチル基を表し、 R2は 2価の有機基を表し、 R3は 1価の有機基を表す〕 [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.]
前記多官能 (メタ）アタリレート（B)が下記式（2)で表される化合物であることを特徴 とする請求項 1〜5のいずれかに記載の感光性樹脂組成物。  6. The photosensitive resin composition according to any one of claims 1 to 5, wherein the polyfunctional (meth) acrylate (B) is a compound represented by the following formula (2).
ZOCH (CH OZ) (2)  ZOCH (CH OZ) (2)
[式（2)中、 Zは下記式（3)で表される。  [In formula (2), Z is represented by the following formula (3).
[化 2]
Figure imgf000055_0001
[Chemical 2]
Figure imgf000055_0001
〔式（3)中、 nは 1〜； 10の実数である〕]  [In formula (3), n is a real number of 1 to 10]]
[7] 請求項;!〜 6の!/、ずれかに記載の感光性樹脂組成物から得られる感光性樹脂組成 物層を有することを特徴とする感光性フィルム。 [7] A photosensitive film comprising a photosensitive resin composition layer obtained from the photosensitive resin composition according to any one of claims 6 to 6 described above.
[8] (I)請求項 1〜6のいずれかに記載の感光性樹脂組成物から得られる感光性樹脂 組成物層を基板上に形成する工程、 [8] (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,
(II)該感光性樹脂組成物層を露光処理してパターンの潜像を形成する工程、  (II) a step of exposing the photosensitive resin composition layer to form a latent image of a pattern,
(III)露光後の感光性樹脂組成物層を現像処理してパターンを形成する工程、およ び (IV)該パターンを焼成処理する工程  (III) a step of developing the photosensitive resin composition layer after exposure to form a pattern, and (IV) a step of baking the pattern.
を含むことを特徴とするパターン形成方法。  A pattern forming method comprising:
[9] 前記工程 (I)において、請求項 7に記載の感光性フィルムを用いて、基板上に感光 性樹脂組成物層を形成することを特徴とする請求項 8に記載のパターン形成方法。  [9] The pattern forming method according to claim 8, wherein in the step (I), a photosensitive resin composition layer is formed on a substrate using the photosensitive film according to claim 7.
[10] 請求項 8または 9に記載のパターン形成方法により、誘電体、電極、抵抗体、蛍光 体、隔壁、カラーフィルターおよびブラックマトリスクから選ばれる少なくとも 1種のディ スプレイパネル用部材を形成する工程を含むことを特徴とするフラットパネルディスプ レイの製造方法。  [10] 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 is formed by the pattern forming method according to claim 8 or 9. A method for producing a flat panel display, comprising a step.
[11] 前記ディスプレイパネルがプラズマディスプレイパネルであることを特徴とする請求 項 10に記載のフラットパネルディスプレイの製造方法。  11. The method for manufacturing a flat panel display according to claim 10, wherein the display panel is a plasma display panel.
PCT/JP2007/066213 2006-08-21 2007-08-21 Photosensitive resin composition, photosensitive film, and method for formation of pattern WO2008023712A1 (en)

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