JP2008039872A - Photosensitive composition for baking and display member using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive composition for baking which is used for various members of a flat panel display, a fluorescence tube, etc., and allows fine patterning by photolithography, and a photosensitive composition for baking which suppresses shrinkage due to sintering of an inorganic component in baking and can give a fine pattern in a state closer to that before baking. <P>SOLUTION: The photosensitive composition for baking contains (A) a photosensitive organic component, (B) an inorganic component comprising bismuth-based glass powder and (C) at least one metal chelate compound selected from metal diketenates, metal alkoxides, metal alkyls and metal carboxylates. The metal chelate compound (C) is contained in an amount of 0.01-5 wt.% based on the total of solid components in the composition. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a photosensitive composition for firing used for various display members of flat panel displays, ceramic multilayer substrates for high-frequency radio, and the like. The present invention also relates to a field emission display member using the same.

  As an image display device that replaces the cathode ray tube, flat panel displays have been proposed due to the advantages of light weight and thinness, and liquid crystal displays and plasma displays have become widespread. is needed. On the other hand, an image display apparatus using an electron-emitting device has been proposed as a new self-luminous discharge type display. Compared to liquid crystal displays and plasma displays, the contrast between LCDs and plasma displays is large, low power consumption, excellent video performance, and high definition demands. It's getting on. There are two known types of electron-emitting devices, a hot cathode electron-emitting device and a cold cathode electron-emitting device. Cold cathode electron emission types include field emission type (field emission type), metal / insulating layer / metal type (MIM type), and surface conduction electron emission type (SED). An image display device using a cold cathode electron-emitting device displays an image by irradiating a phosphor with an electron beam emitted from the electron-emitting device to generate fluorescence. Among such electron emission type flat image display devices, a CNT-field emission display (FED) using carbon nanotubes (CNT) as an electron emission element is easy for electron emission characteristics and large area. Active development is underway.

  The back glass substrate of such an electron emission type flat image display device is provided with a plurality of electron emission elements and matrix-like wiring for connecting these elements. These wirings are installed in the X direction and the Y direction and intersect at the electrode portion of the electron-emitting device. In order to insulate both at the intersecting portion, a patterned insulating film is essential. In addition, the partition that forms the pixels formed on the back plate member of the plasma display is required to have the same insulating properties.

  As for the production of this insulating film, silicon oxide formed by vacuum deposition, printing, sputtering, etc. (see Patent Document 1), screen printing by overcoating a pattern, sandblasting, and photosensitive composition are screened. A method of forming a pattern by ultraviolet exposure after coating the entire surface by printing is disclosed (see Patent Document 2).

  On the other hand, as a photosensitive composition for forming a member such as an insulating layer for display, a photosensitive composition comprising a photosensitive monomer, a binder polymer, a photopolymerization initiator containing a photopolymerization initiator, and inorganic particles (Patent Document 3). 4), and a photosensitive composition composed of an alkali-soluble polyorganosiloxane resin composition and an acid generator and a photosensitive composition composed of inorganic particles (see Patent Document 5), among these, A photosensitive composition comprising a photosensitive monomer, a photosensitive organic component containing a photopolymerization initiator, and inorganic particles is preferably used because of many variations in material selection and easy control of its performance.

  In order to obtain a member such as an insulating layer for display and partition walls from a photosensitive composition comprising a photosensitive organic component and inorganic particles, a pattern is formed on the display substrate by photolithography prescription, and then baking is performed. In the firing step, shrinkage occurs due to the sintering of the inorganic particles, resulting in a dimensional change from the pattern formed before firing. In particular, when an insulating layer of a field emission display or the like is manufactured, since the pattern is as small as several microns to several tens of microns, the dimensional change of the pattern that changes before and after sintering becomes relatively larger than that when the pattern is large. As a result, the problem becomes more prominent. As means for suppressing the shrinkage, a method of applying a surface treatment to the substrate (see Patent Document 6), a method of forcibly applying an external force (see Patent Document 7), and the like have been proposed. Moreover, although the method (refer patent document 8) which adds a filler and suppresses shrinkage | contraction, the method (refer patent document 9) etc. which add an organosilane coupling agent in a paste is proposed, a calcination temperature rises, Eventually, there was a problem of insufficient firing, and the effect was not fully exhibited.

On the other hand, a technique using a metal chelate compound as a crosslinking agent in order to improve the adhesion between the organic component and the substrate is known (see Patent Document 10). Further, since the metal chelate compound becomes a metal oxide after firing, there is known a technique of giving a function like an organic component before firing and a function as a metal oxide after firing (patent document). 11).
Japanese Patent Laid-Open No. 10-12140 (paragraph 92) JP 2002-245928 A (29th-30th paragraphs) JP 2000-63151 A (Claim 6) JP 2003-104755 A (Claim 1) JP 2004-177921 A (Claim 6) JP 2006-135063 A (Claim 1) JP-A-5-283272 (Claims 11 and 13) JP 2002-214772 (paragraph 36) JP 2004-247300 A (paragraph 66) Japanese Patent Laid-Open No. 11-221977 (Claim 1) JP 2003-238573 A (paragraph 32)

  The present invention relates to a photosensitive composition for firing used for various members of flat panel displays, fluorescent light emitting device (cold cathode tube) members, etc., and enables fine pattern processing by photolithography prescription and sintering of inorganic components during firing. The photosensitive composition for firing is capable of suppressing the shrinkage accompanying the process, and can obtain a fine pattern closer to the state before firing without causing problems such as an increase in the process and an increase in the firing temperature. For the purpose.

  That is, the present invention provides at least one selected from (A) a photosensitive organic component, (B) an inorganic component having a bismuth-based glass powder, and (C) a metal diketenate, a metal alkoxide, an alkyl metal, and a metal carboxylate. A photosensitive composition for firing having a metal chelate compound, wherein the metal chelate compound of (C) is contained in an amount of 0.01% by weight or more and less than 5% by weight based on the total solid content contained in the composition. It is a thing.

  According to the present invention, shrinkage during firing can be suppressed without increasing the number of steps or raising the firing temperature. Moreover, since a fine pattern can be maintained, it can be used for an insulating layer of a field emission display or a ceramic multilayer substrate.

  The photosensitive composition for firing of the present invention is selected from (A) a photosensitive organic component, (B) an inorganic component having a bismuth-based glass powder, and (C) a metal diketenate, a metal alkoxide, an alkyl metal, and a metal carboxylate. And (C) the metal chelate compound is contained in an amount of 0.01% by weight or more and less than 5% by weight based on the total solid content in the composition.

  The photosensitive organic component (A) used in the present invention may be a negative type that is cured by light or a positive type that is solubilized by light. Further, since the present invention is used in a state where the solvent is volatilized, the organic solvent is not included in the photosensitive organic component when calculating the component ratio or the like.

  In the present invention, (A) the photosensitive organic component is one or more selected from the group consisting of a) an ethylenically unsaturated group-containing compound and a photopolymerization initiator, b) a glycidyl ether compound, an alicyclic epoxy compound, and an oxetane compound. And at least one compound selected from c) quinonediazide compounds, diazonium compounds, azide compounds, and the like are preferably used.

  The ethylenically unsaturated group-containing compound in component a) is methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-pentyl. Acrylate, allyl acrylate, benzyl acrylate, butoxyethyl acrylate, butoxytriethylene glycol acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, 2-ethylhexyl acrylate, glycerol acrylate, glycidyl acrylate, heptadecafluorodecyl acrylate, 2 -Hydroxyethyl acrylate, isobornyl acrylate, 2-hydro Cypropyl acrylate, isodecyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene glycol acrylate, methoxydiethylene glycol acrylate, octafluoropentyl acrylate, phenoxyethyl acrylate, stearyl acrylate, trifluoroethyl acrylate, allylated cyclohexyl Diacrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, dipentaerythritol hexaacrylate, dipentaerythritol Monohydr Xypentaacrylate, ditrimethylolpropane tetraacrylate, glycerol diacrylate, methoxylated cyclohexyl diacrylate, neopentyl glycol diacrylate, propylene glycol diacrylate, polypropylene glycol diacrylate, triglycerol diacrylate, trimethylolpropane triacrylate, acrylamide, amino Ethyl acrylate, phenyl acrylate, phenoxyethyl acrylate, benzyl acrylate, 1-naphthyl acrylate, 2-naphthyl acrylate, bisphenol A diacrylate, diacrylate of bisphenol A-ethylene oxide adduct, diacrylate of bisphenol A-propylene oxide adduct, Thiophenol acrylate , Benzyl mercaptan acrylate, a monomer in which 1 to 5 hydrogen atoms of these aromatic rings are substituted with chlorine or bromine atoms, or styrene, p-methylstyrene, o-methylstyrene, m-methyl Styrene, chlorinated styrene, brominated styrene, α-methylstyrene, chlorinated α-methylstyrene, brominated α-methylstyrene, chloromethylstyrene, hydroxymethylstyrene, carboxymethylstyrene, vinylnaphthalene, vinylanthracene, vinylcarbazole, And what changed a part or all of acrylate in the molecule of the above-mentioned compound into methacrylate, γ-methacryloxypropyltrimethoxysilane, 1-vinyl-2-pyrrolidone, etc., acrylic acid, methacrylic acid, itaconic acid, Crotonic acid, Maleic acid, fumaric acid, and vinyl acetate. In addition, esters of various alcohols (eg, ethanol, propanol, hexanol, octanol, cyclohexanol, glycerin, trimethylolpropane, pentaerythritol, etc.) and acrylic acid (or methacrylic acid), carboxylic acids (eg, acetic acid, propionic acid, benzoic acid) Reaction products of acid, acrylic acid, methacrylic acid, succinic acid, maleic acid, phthalic acid, tartaric acid, citric acid, etc.) with glycidyl acrylate (or glycidyl methacrylate, allyl glycidyl, or tetraglycidyl metaxylylenediamine) Amide derivatives (for example, acrylamide, methacrylamide, N-methylolacrylamide, methylenebisacrylamide, etc.), reaction product of epoxy compound and acrylic acid (or methacrylic acid), polyethylene Recall diacrylate, polypropylene glycol diacrylate, tripropylene glycol diacrylate, various urethane acrylate and rosin-modified acrylate. In the present invention, one or more of these can be used, and the content thereof is preferably 50 to 99% by weight, more preferably 60 to 90% by weight, based on the photosensitive organic component. By making it 50% by weight or more, fine pattern processing becomes possible, and by making it 99% by weight or less, the pattern shape after firing can be kept good.

  In the present invention, the photopolymerization initiator of the component a) which is a photosensitive organic component is benzophenone, methyl o-benzoylbenzoate, 4,4-bis (dimethylamine) benzophenone, 4,4-bis (diethylamino) benzophenone. 4,4-dichlorobenzophenone, 4-benzoyl-4-methyldiphenyl ketone, dibenzyl ketone, fluorenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenyl-2-phenylacetophenone, 2-hydroxy 2-methylpropiophenone, pt-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyl, benzyldimethylketanol, benzylmethoxy Ethyl acetal, benzoin, benzoin methyl ether, benzoin butyl ether, anthraquinone, 2-t-butylanthraquinone, 2-amylanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibenzosuberone, methyleneanthrone, 4-azidobenzalacetophenone, 2,6-bis (p-azidobenzylidene) cyclohexanone, 2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone, 2-phenyl-1,2-butadion-2- (o-methoxycarbonyl) oxime, 1-phenyl-propanedione-2- (o-ethoxycarbonyl) oxime, 1,3-diphenyl-propanetrione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxy-propant Lion-2- (o-benzoyl) oxime, Michler's ketone, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, naphthalenesulfonyl chloride, quinolinesulfonyl chloride, N-phenylthioacridone, 4 , 4-azobisisobutyronitrile, diphenyl disulfide, benzthiazole disulfide, triphenylphosphine, camphorquinone, carbon tetrabromide, tribromophenylsulfone, benzoin peroxide and eosin, methylene blue and other photoreductive dyes and ascorbine Examples include combinations of reducing agents such as acids and triethanolamine. In particular, it is preferable to use one having sensitivity to visible light having a wavelength of 400 to 450 nm. In the present invention, one or more of these can be used. A photoinitiator is added in 0.05-50 weight% with respect to the photosensitive organic component, More preferably, it is 1-35 weight%. Within this range, the sensitivity is good and the remaining ratio of the exposed portion can be increased.

  The component b) contains one or more cationically polymerizable compounds and a photocationic polymerization initiator selected from the group consisting of glycidyl ether compounds, alicyclic epoxy compounds, and oxetane compounds. Specific examples of the glycidyl ether compound among the components b) include bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A diglycidyl ether, bisphenol hexafluoroacetone diglycidyl ether, and tetrabromobisphenol A diglycidyl ether. 1,3-bis (1- (2,3-epoxypropoxy) -1-trifluoromethyl-2,2,2-trifluoroethyl) benzene, 1,4-bis (1- (2,3-epoxy) Propoxy) -1-trifluoromethyl-2,2,2-trifluoroethyl) cyclohexyl, 4,4′-bis (2,3-epoxypropoxy) octafluorobiphenyl, phenol novolac epoxy resin, cresol novolac epoxy resin , Trisphenor Methane type epoxy resin or the like or carboxylic acid-modified products of these epoxy resins.

  Specific examples of the alicyclic epoxy compound among the components b) which are photosensitive organic components in the present invention include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexylethyl. -8,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-m-dioxane, bis (3,4-epoxycyclohexyl) adipate, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxycyclohexyl) ether, bis (3,4-epoxycyclohexyl) diethylsiloxane, trade name “Celoxide” 2021 (epoxy equivalent 128-145 g / eq), Product name “Celoxide Bifunctional alicyclic epoxy compound manufactured by Daicel Chemical Industries, such as 2080 (epoxy equivalent 190-210), trade name “Epolide” GT-301 (epoxy equivalent 200-220 g / eq), trade name “Epolide” Tri- and tetrafunctional alicyclic epoxy compounds such as GT-401 (epoxy equivalent 210 to 235 g / eq) manufactured by Daicel Chemical Industries, Ltd., trade name “EHPE” (epoxy equivalent 170 to 190 g / eq, softening point 70) ˜90 ° C.), manufactured by Daicel Chemical Industries, Ltd., such as trade name “EHPEL3150CE”, and alicyclic epoxy compounds such as solid alicyclic epoxy compounds.

  Specific examples of the oxetane compound among the components b) which are photosensitive organic components in the present invention include 2-ethyl-3-hydroxymethyloxetane, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl And oxetane compounds such as benzene and silicon-modified oxetane compounds. The proportion of one or more cationically polymerizable compounds selected from the group consisting of glycidyl ether compounds, alicyclic epoxy compounds, and oxetane compounds in the photosensitive organic component is preferably 1 to 75% by weight, more preferably 5 to 35% by weight. By making it within this range, the pattern shape can be kept good.

  Specific examples of the photocationic polymerization initiator of the component b) which is a photosensitive organic component in the present invention include aromatic sulfonium salts such as triphenylsulfonium hexafluorophosphate and aromatic iodonium salts such as diphenyliodonium hexafluorophosphate. , Aromatic iodosyl salts, aromatic sulfoxonium salts, metallocene compounds, and the like. The amount of the cationic photopolymerization initiator used is preferably in the range of 0.01 to 15% by weight in the photosensitive organic component.

  In addition, 9,10-dimethoxy-2-ethyl-anthracene, 9,10-diethoxyanthracene, 2,4-diethylthioxanthone, etc. are preferably added as a photocationic polymerization accelerator.

  As the component c), one or more compounds selected from quinonediazide compounds, diazonium compounds, and azide compounds are preferably used. The quinonediazide compound is a compound obtained by diazotizing an aromatic compound having a hydroxyl group at the ortho or para position relative to the amino group, or a compound having a hydroxyl group at the ortho or para position relative to the diazo group with a diazonium salt of a benzene or naphthalene derivative. Is a compound obtained by heating in an aqueous alkali solution, and generally the diazo group is not ionized and does not form a salt as in the diazonium compound described below. Specific examples include benzoquinone diazide sulfonic acid and its derivatives, naphthoquinone diazide sulfonic acid and its derivatives, which are usually used in positive PS plates, wiper plates, photoresists and the like. Specifically, 1,2-benzoquinone-2-diazide-4-sulfonic acid chloride, 1,2-benzoquinone-2-diazide-4-sulfonic acid sodium salt, 1,2-benzoquinone-2-diazide-4-sulfone Acid, 1,2-naphthoquinone-2-diazide-4-sulfonic acid chloride, 1,2-naphthoquinone-2-diazide-4-sulfonic acid sodium salt, 1,2-naphthoquinone-2-diazide-4-sulfonic acid, 1,2-naphthoquinone-2-diazide-5-sulfonic acid chloride, 1,2-naphthoquinone-2-diazide-5-sulfonic acid sodium salt, 1,2-naphthoquinone-2-diazido-5-sulfonic acid, 1, 2-naphthoquinone-2-diazide-6-sulfonic acid chloride, 1,2-naphthoquinone-2-diazide-6-sulfonic acid sodium salt, 1, Examples include 2-naphthoquinone-2-diazide-6-sulfonic acid.

  Among these, 1,2-naphthoquinone-2-diazido-4-sulfonic acid and its derivatives, and 1,2-naphthoquinone-2-diazide-5-sulfonic acid and its derivatives are effective.

  These naphthoquinonediazide compounds are preferably used by being mixed or derivatized with alkali-soluble components such as polyhydroxyphenyl, pyrogallol acetone resin, parahydroxystyrene copolymer, and phenol formaldehyde novolac resin. Specific examples of preferable derivatives include esters of 1,2-naphthoquinone-2-diazidosulfonic acid with polyhydroxyphenyl, pyrogallol acetone resin, parahydroxystyrene copolymer, phenol formaldehyde novolac resin, and the like.

  The proportion of these quinonediazide compounds in the photosensitive organic component is preferably 1% by weight to 96% by weight, more preferably 3% by weight to 80% by weight. When the quinonediazide compound is less than 1% by weight, the change in solvent solubility due to the quinonediazide compound during exposure is reduced, resulting in poor pattern formation. On the other hand, when it is more than 96% by weight, the amount of low molecular weight components is increased. Dispersion becomes poor and it becomes difficult to obtain a paste state.

  In the present invention, the diazonium compound of the component c) which is a photosensitive organic component includes a condensation product of a diazo monomer and a condensing agent. Here, as the diazo monomer, 4-diazodiphenylamine, 1-diazo-4-N, N-dimethylaminobenzene, 1-diazo-4-N, N-diethylaminobenzene, 1-diazo-4-N-ethyl-N -Hydroxyethylaminobenzene, 1-diazo-4-N-methyl-N-hydroxyethylaminobenzene, 1-diazo-2,5-diethoxy-4-benzoylaminobenzene, 1-diazo-4-N-benzylaminobenzene 1-diazo-4-N, N-dimethylaminobenzene, 1-diazo-4-morpholinobenzene, 1-diazo-2,5-dimethoxy-4-p-tolylmercaptobenzene, 1-diazo-2-ethoxy- 4-N, N-dimethylaminobenzene, p-diazodimethylaniline, 1-diazo-2,5-dibutoxy-4-methyl Holinobenzene, 1-diazo-2,5-diethoxy-4-morpholinobenzene, 1-diazo-2,5-dimethoxy-4-morpholinobenzene, 1-diazo-2,5-diethoxy-4-p-tolylmercaptobenzene, 1-diazo-4-N-ethyl-N-hydroxyethylaminobenzene, 1-diazo-3-ethoxy-4-N-methyl-N-benzylaminobenzene, 1-diazo-3-chloro-4-N, N -Diethylaminobenzene, 1-diazo-3-methyl-4-pyrrolidinobenzene, 1-diazo-2-chloro-4-N, N-dimethylamino-5-methoxybenzene, 1-diazo-3-methoxy-4- Pyrrolidinobenzene, 3-methoxy-4-diazodiphenylamine, 3-ethoxy-4-diazodiphenylamine, 3- (n-propoxy) 4-diazo diphenylamine, 3- (isopropoxy) such as 4-diazo diphenylamine. Examples of the condensing agent include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, or benzaldehyde. Furthermore, water-soluble diazo resins can be obtained by using chlorine ions, tetrachlorohydrochloric acid, etc., and boron tetrafluoride, hexafluorophosphoric acid, triisopropylnaphthalenesulfonic acid, 4,4′-biphenyldisulfonic acid By using 2,5-dimethylbenzenesulfonic acid, 2-nitrobenzenesulfonic acid, 2-methoxy-4-hydroxy-5-benzoylbenzenesulfonic acid or the like, an organic solvent-soluble diazo resin can be obtained.

  An equimolar reaction product of a diazonium compound and hydroxybenzophenones can also be used. However, the pH is set to 7.5 or less so that they do not react to form an azo compound. As the diazonium compound, the same diazo resin as described above is used. Examples of the hydroxybenzophenones include 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, and 2,2′-dihydroxy-4,4′-dimethoxy-5. -Alkali salts of sulfobenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and the like are used. Particularly those containing sulfonic acid groups are excellent in stability.

  The proportion of these diazonium compounds in the photosensitive organic component is preferably 5 to 80% by weight, more preferably 10 to 50% by weight. If the amount of the diazonium compound is too small, curing may be insufficient. Conversely, if the amount is too large, a problem may occur in the storage stability of the composition.

  In the present invention, the azide compound of the component c) which is a photosensitive organic component has an azide group in the molecule, and specifically, 2,6-dichloro-4-nitroazidebenzene, azidodiphenylamine. 3,3′-dimethoxy-4,4′-diazidodiphenyl, 4′-methoxy-4-azidodiphenylamine, 4,4′-diazidodiphenylamine, 4,4′-diazidodiphenylmethane, 1-azidopyrene, 3, , 3′-dimethyl-4,4′-diazidodiphenyl, 4,4′-diazidophenylazonaphthalene, p-phenylene-bisazide, p-azidobenzophenone, 4,4′-diazidobenzophenone, 4,4 ′ -Diazidodiphenylmethane, 4,4'-diazidostilbene, 4,4'-diazide chalcone, 2,6-di- (4 ' Azidobenzal) cyclohexanone, 2,6-di - (4'-azidobenzal) such as 4-methyl cyclohexanone. These azide compounds are used alone, but in the case where the photosensitive wavelength range is short, it is preferable to spectrally sensitize the photosensitive wavelength range to the long wavelength side using a sensitizer such as 1-nitropyrene.

  The proportion of these azide compounds in the photosensitive organic component is preferably 5 to 70% by weight, more preferably 10 to 50% by weight. When the amount of the azide compound is too small, curing of the photosensitive component may be insufficient, and when the amount is too large, the stability of the composition may be adversely affected.

  As the photosensitive organic component as described above, an ethylenically unsaturated group-containing compound and a photo-radical polymerization initiator as component a) are preferred because of the wide variation in material selection and the ease of controlling the performance based thereon.

  Moreover, you may add the cage silsesquioxane to the photosensitive composition for baking to what was chosen from the component a) -c). The cage silsesquioxane may be added as it is to the baking photosensitive composition, or may be added after reacting with other compounds in advance. In the case of reacting with another compound in advance, it is preferable to react with a compound constituting the photosensitive organic component from the viewpoint of increasing the compatibility.

  In the present invention, the photosensitive organic component preferably further has a binder polymer, and can contain additives such as an ultraviolet absorber, a sensitizer, a polymerization inhibitor, a plasticizer, a dispersant, and an antioxidant. .

  As the binder polymer, various polymers such as acrylic resin, epoxy resin, polyurethane resin, polyester resin, polyamide resin, polyimide resin, silicone resin, melamine resin, phenol resin, cellulose derivative, and polyvinyl alcohol can be used. Methacrylate, polyvinyl butyral, polyvinyl alcohol, ethyl cellulose, (meth) acrylic acid ester copolymer and the like are preferable. Furthermore, from the viewpoint of dispersibility and developability of the inorganic powder, in addition, from the viewpoint of pattern formation by photosensitivity, the binder polymer has a reactive functional group such as a carboxyl group, a hydroxyl group, and an ethylenically unsaturated double bond. It is preferable.

  Moreover, it is preferable that the thermal decomposition temperature of a binder polymer is 500 degrees C or less, Furthermore, it is 450 degrees C or less, 150 degreeC or more, More preferably, it is 400 degreeC or more. When a binder polymer having a thermal decomposition temperature of 150 ° C. or higher is used, the thermal stability of the photosensitive composition for baking is maintained, and the photosensitive property is impaired in each step from coating the photosensitive composition to pattern processing. Good pattern processing is possible without any problems. If a binder polymer having a thermal decomposition temperature of 500 ° C. or lower is used, cracks, peeling, warping and deformation in the firing process can be prevented. The technique for adjusting the thermal decomposition temperature of the binder polymer can be achieved by selecting a monomer as a copolymerization component. In particular, by using a monomer that thermally decomposes at a low temperature as a copolymerization component, the thermal decomposition temperature of the copolymer can be lowered. Examples of components that thermally decompose at a low temperature include methyl methacrylate, isobutyl methacrylate, α-methylstyrene, and the like. The thermal decomposition temperature is set with a sample of about 20 mg using a TG measuring device (TGA-50, manufactured by Shimadzu Corporation), the flow rate is 20 ml / min in an air atmosphere, and the heating rate is 20 to 0.6 ° C./min. The temperature is raised to 700 ° C. As a result, a chart plotting the relationship between temperature (vertical axis) and weight change (horizontal axis) is printed, and the tangent line between the part before decomposition (part parallel to the horizontal axis) and the part under decomposition is drawn, and the intersection The temperature can be measured by a method such as the thermal decomposition temperature.

  The Tg (glass transition temperature) of the binder polymer is preferably -60 to 30 ° C. More preferably, it is -40-30 degreeC, More preferably, it is -20-30 degreeC. By setting Tg to −60 ° C. or higher, the tackiness of the sheet can be reduced, and by setting Tg to 30 ° C. or lower, the flexibility of the sheet can be maintained. The Tg of the binder polymer was measured using a DSC-50 type measuring device manufactured by Shimadzu Corporation, and the sample was heated at a heating rate of 20 ° C./min under a nitrogen stream at a rate of 20 ° C./min. The starting temperature was Tg.

  Furthermore, the binder polymer used preferably has a weight average molecular weight of 100,000 or less. More preferably, it is 5,000 to 80,000. When the weight average molecular weight is 100,000 or less, the developer solubility is maintained, and as a result, a finer pattern can be obtained. Furthermore, since the viscosity of the binder polymer increases in proportion to the weight average molecular weight, in order to reduce the viscosity of the photosensitive composition for baking and maintain the workability in the filtration, deaeration and coating processes, the binder polymer It is preferable to lower the weight average molecular weight. The weight average molecular weight of the binder polymer was measured by size exclusion chromatography using tetrahydrofuran as a mobile phase. The column was Shodex KF-803, and the weight average molecular weight was calculated in terms of polystyrene.

  A preferable binder polymer when the component a) is used as the photosensitive organic component is a reactive functional group of the binder polymer obtained by copolymerization of the ethylenically unsaturated double bond-containing compound as described above or by copolymerization. It can be obtained by adding an ethylenically unsaturated group-containing compound having a reactive functional group to a part of the group. Specifically, a carboxyl group and an ethylenically unsaturated double bond are obtained by adding an epoxy group-containing acrylate compound such as glycidyl methacrylate to a part of the carboxyl group of a binder polymer having an unsaturated carboxylic acid as a copolymer component. A binder polymer having is obtained. The acid value of such a binder polymer is preferably 50 to 140 (mgKOH / g). By setting the acid value to 140 or less, the allowable development width can be widened, and by setting the acid value to 50 or more, the solubility in the alkali developer in the unexposed area is maintained, and a high-definition pattern is obtained. be able to. The acid value is measured by dissolving 1 g of the binder polymer in 100 mL of ethanol and then titrating with a 0.1N aqueous potassium hydroxide solution. Further, the double bond density of the binder polymer is preferably 0.1 to 2.5 mmol / g, and more preferably 0.2 to 1.6 mmol / g. When the double bond density is less than 0.1 mmol / g, pattern formation by exposure is not sufficient, film loss is large, and developability is remarkably deteriorated. On the other hand, in the range exceeding 2.5 mmol / g, cracks, peeling, warping, etc. occur in the firing step.

  The content of the binder polymer in the photosensitive organic component is preferably 1 to 50% by weight with respect to the photosensitive organic component. More preferably, it is 5 to 40% by weight. By setting the content in the range of 1 to 50% by weight, it is possible to achieve both pattern processability and characteristics such as shrinkage during firing.

  The inorganic component (B) used in the present invention contains bismuth glass powder. Since the atomization of the inorganic particles constituting the inorganic component is required, the glass powder contained in the inorganic component needs to be a bismuth-based material that can be atomized. The glass includes amorphous glass and crystallized glass, but the present invention can be used for both amorphous glass and crystallized glass. In general, amorphous glass has a property of crystallizing when heated to a crystallization temperature. In the crystallized glass, glass crystals are formed from several tens to about 90% by volume, so that the strength and the coefficient of thermal expansion can be improved. It is also possible to use already crystallized glass. In this case, since the glass crystallizes as it approaches the crystallization peak temperature, it has the property of consolidating the glass. In the case of crystallized glass, it is desirable to use glass having a crystallization temperature of 550 ° C. or lower. In addition to cost reduction and productivity improvement by low-temperature firing, if the firing temperature is 500 ° C. or lower, there is an advantage that an inexpensive glass substrate can be used.

  The low softening point in the present invention means that the thermal softening point temperature of the glass is 350 ° C. to 600 ° C., more preferably 400 ° C. to 580 ° C., further preferably 450 ° C. to 500 ° C. The glass used is preferably alkali-free glass. When an alkali metal or alkaline earth metal, such as Na (sodium), Li (lithium), K (potassium), Ba (barium), Ca (calcium), or the like is included, a glass substrate or electrode after firing or after firing This is not preferable because ion exchange with the glass component therein is likely to occur, electrical characteristics are deteriorated, and thermal expansion coefficients are mismatched, resulting in defects. As mentioned above, when using the low softening point glass by this invention, although Zn-Bi type | system | group and Bi-Zr type | system | group glass are preferable, it is not limited to this.

As a component of the bismuth glass, Bi ₂ O ₃ is desirably contained in the range of 70 to 95% by weight, more preferably 73 to 85% by weight, and further preferably 76 to 80% by weight. If it is less than 70% by weight, the etching resistance to acid is weak, and it dissolves. If it exceeds 95% by weight, the heat resistant temperature of the glass is lowered, which is not preferable in terms of baking onto a glass substrate.

SiO2 is preferably ₃ to 15% by weight. When it is less than 3% by weight, vitrification becomes difficult. On the other hand, if it exceeds 15% by weight, the heat softening point becomes high, and baking on the glass substrate becomes difficult.

B ₂ O ₃ is preferably 5 to 20 wt%. More preferably, it is 7 to 15% by weight. By including B ₂ O ₃ , electrical, mechanical and thermal characteristics such as electrical insulation, strength, thermal expansion coefficient, and denseness can be adjusted. If it exceeds 20% by weight, the stability of the glass with respect to acid and water decreases.

ZrO ₂ is preferably contained in the range of 0 to 3% by weight, more preferably 0.01 to 2.5% by weight, and still more preferably 0.01 to 1% by weight. ZrO ₂ improves the acid resistance of the glass material, but if it exceeds 3% by weight, the glass becomes non-uniform and a residue is generated by etching with acid.

  ZnO is preferably 1 to 10% by weight, more preferably 2 to 5% by weight. If it is less than 1% by weight, the effect of improving the density is small, and if it exceeds 20% by weight, the baking temperature becomes low and it becomes difficult to control, and the insulation resistance also becomes low.

In addition to the above oxides, Al ₂ O ₃ , PbO and the like may be contained. By containing Al ₂ O ₃ , the strength can be sufficiently maintained. By containing PbO, the softening point can be kept low.

  The amount of the bismuth-based glass powder contained in the inorganic component is preferably 50 to 100% by volume with respect to the entire inorganic component. More preferably, it is 80-100 volume%. If it is in this range, the inorganic substance obtained by baking maintains the glass state.

  Moreover, the photosensitive composition for firing of the present invention may undergo a step of etching a metal such as chromium after firing, and even in the step of etching the metal, a glass that is difficult to dissolve, that is, an inorganic substance obtained after firing is an acid. It is preferable to become a glass having high etching resistance to the above.

  The average particle size of the glass powder is preferably 0.1 to 5 μm, more preferably 0.1 to 2 μm, and even more preferably 0.1 to 1 μm. By using a glass powder having an average particle size of 0.1 μm or more, a photosensitive composition for firing having good dispersion stability can be obtained, and by using a glass powder having an average particle size of 5 μm or less, fine photo on a thin film can be obtained. Lithography processing is possible. When the laser diffraction scattering method is used, the average particle size of the glass powder indicates the particle size when the cumulative frequency of the obtained particle size distribution is 50%. When using the BET method conversion value, after adsorbing an inert gas such as nitrogen gas and measuring the specific surface area, the particle diameter is obtained from the specific surface area assuming that the particles are spheres, and the number average is obtained. Obtain the average particle size. When the particles are nano-sized or smaller, it is difficult to measure accurately due to aggregation or the like, and therefore it is preferable to use a BET method conversion value.

Moreover, you may put a filler other than the said glass powder. Specific fillers include ceramic powders such as SiO ₂ , Al ₂ O ₃ , ZrO ₂ , mullite, spinel, magnesia, ZnO, titanium oxide, zircon, etc. These may be used alone or in combination. It may be used. The addition amount of the filler is preferably less than 20% by volume with respect to the inorganic component of the photosensitive composition for baking. If it is more than that, cracking may occur during sintering or sintering may be insufficient. The filler is preferably one that does not melt during sintering. The average particle size of the filler is preferably 0.01 μm to 0.5 μm, and more preferably 0.01 to 0.05 μm. The strength of the fired member can be improved by adding a filler of 0.01 μm or more, and good photosensitive characteristics can be obtained by using a filler of 0.5 μm or less. The average particle diameter of the filler is determined by measuring the specific surface area by the BET method using nitrogen gas, then determining the particle diameter from the specific surface area assuming that the particles are spheres, and determining the average particle diameter as a number average.

  As content of the inorganic component in the photosensitive composition for baking, 50 to 95 weight% is preferable, 70 to 95 weight% is more preferable, 80 to 90 weight% is further more preferable. By setting it to 50% by weight or more, the pattern shape at the time of firing can be made preferable, while by setting it to 95% by weight or less, good photosensitive characteristics can be obtained. When it is 95% by weight or more, it becomes difficult to make a paste itself.

  The average refractive index of the glass powder used is preferably 1.8 or more. More preferably, it is larger than 2 and smaller than 2.7. More preferably, it is 2.0 or more and 2.2 or less. When the glass composition is satisfied, the above range of average refractive index may be satisfied.

  The refractive index of the glass powder is measured using a Becke method, a V block method, an ellipsometer, or the like. Measuring the refractive index at the exposure wavelength is accurate in confirming the effect. In particular, it is preferable to measure with light in the wavelength range of 350 to 650 nm. Furthermore, refractive index measurement with i-line (365 nm) or g-line (436 nm) is preferable.

  Further, within the range of the content of the inorganic component, the specific gravity of the glass is preferably 4 or more and 7 or less, more preferably 4.5 or more and 6.5 or less, and further preferably 5.5 or more and 6.3 or less. Within this range, shrinkage during firing can be reduced, and the pattern shape after firing can be made preferable. The specific gravity of the glass powder is measured using the Archimedes method, the specific gravity bottle method, the floating method, or the like.

Thermal expansion coefficient of the glass powder is preferably 70~100 × ^{10 -7} / K value of the thermal expansion coefficient alpha _{50 to 350} in the range of 50 to 350 ° C., more preferably 72~90 × ^{10 -7} / K. Within this range, it is preferable because it matches the thermal expansion coefficient of the substrate glass and can reduce the stress applied to the glass substrate during firing.

  The metal chelate compound in the present invention consists of a ligand that is a central metal and an organic substituent, and is a complex compound in which an organic ligand is coordinated to the metal or a covalent bond with an organic functional group. It is an organometallic compound. The ligand which is an organic substituent is classified into a monodentate ligand and a polydentate ligand, and preferably has a polydentate ligand, particularly a bidentate ligand. Also, inorganic compounds such as metal oxides are not applicable. These metal chelate compounds undergo a substitution reaction with a compound containing an active hydrogen group. Examples of the active hydrogen group-containing compound include a hydroxyl group-containing compound, an amino group-containing compound, a carboxyl group-containing compound, a thiol group-containing compound, and the like, but a hydroxyl group-containing compound is preferable. In the present invention, the hydroxyl group formed on the substrate surface and the glass powder surface reacts with the metal chelate compound, so that the shrinkage suppressing effect is exhibited not only before firing but also after firing.

  Examples of the central metal of at least one metal chelate compound selected from (C) metal diketenate, metal alkoxide, alkyl metal, and metal carboxylate used in the present invention include metals in the second to sixth periods of the periodic table. Among them, metals of the third period to the fifth period are preferable, and Al of the third period metal, Ti, Mn, Fe, Co, Ni, Cu, Zn, Ge of the fourth period metal, Zr of the fifth period metal , In and Sn are particularly preferable. A metal chelate compound is formed between the above-described metals and an organic compound. Specific examples thereof include the following compounds (1) to (5), but are not limited thereto.

  (1) Metal diketenate: A diketone in which a hydroxyl group of an enol hydroxyl group and a metal atom are substituted, and a central metal is bonded via an oxygen atom. Since the diketone carbonyl can be further coordinated to the metal, it is a relatively stable compound. Specifically, the chelate moiety is 2,4-pentanedionate (acetylacetonate), fluoropentanedionate, 2,2,6,6-tetramethyl-3,5-heptanedionate, benzoylacetonate, Metal pentanedionates (metal acetylacetonates) such as thenoyl trifluoroacetonate and 1,3-diphenyl-1,3-propanedionate, methyl acetoacetate, ethyl acetoacetate, methacryloxyethyl acetoacetate and allyl Examples thereof include metal acetoacetates such as acetoacetate and salicylaldehyde complex salts.

  (2) Metal alkoxide: a compound in which an alkyl group is bonded to a metal alkoxide central metal via an oxygen atom. Examples thereof include metal alkoxides in which the chelate portion is methoxide, ethoxide, propoxide, butoxide, phenoxide, allyl oxide, methoxyethoxide, aminoethoxide and the like.

  (3) Alkyl metal: The alkyl metal central metal has an alkyl group as it is, and in this case, the metal is bonded to a carbon atom. Even if the chelate moiety compound is a diketone, it is classified here if the metal is bonded by a carbon atom. Of these, acetylacetone metal is preferably used.

  (4) Metal carboxylates: metal carboxylates such as acetic acid metal salts, lactic acid metal salts, acrylic acid metal salts, methacrylic acid metal salts, and stearic acid metal salts.

  (5) Other metal chelate compounds with amines such as ethylenediamine, metal oxide chelate compounds such as titanium oxide acetonate, metal complexes such as titanocene phenoxide, and hetero molecules having two or more metal atoms in one molecule A metal chelate compound is mentioned.

  Among the metal chelate compounds as described above, specific examples of metal chelate compounds that are preferably used include the following compounds.

  Specific examples of the aluminum chelate compound include aluminum isopropylate, monosec-butoxyaluminum diisopropylate, aluminum sec-butyrate, ethyl acetate aluminum diisopropylate, propyl acetate aluminum diisopropylate, butyl acetate aluminum diisopropylate, heptyl acetate. Aluminum diisopropylate, hexyl acetate aluminum diisopropylate, octyl acetate aluminum diisopropylate, nonyl acetate aluminum diisopropylate, ethyl acetate aluminum diethylate, ethyl acetate aluminum dibutyrate, ethyl acetate aluminum diheptylate, ethyl acetate aluminum dino Elm , Diethyl acetate aluminum isopropylate, aluminum tris (ethyl acetoacetate), aluminum tris (propyl acetoacetate), aluminum tris (butyl acetoacetate), aluminum tris (hexyl acetoacetate), aluminum tris (nonyl acetoacetate), aluminum tris Acetylacetonate, aluminum bisethylacetoacetate monoacetylacetonate, aluminum diacetylacetonate ethylacetoacetate, aluminum monoacetylacetonate bispropylacetoacetate, aluminum monoacetylacetonate bisbutylacetoacetate, aluminum monoacetylacetonate bishexylacetate Acetate, aluminum monoethylene Acetoacetate bispropyl acetoacetonate, aluminum monoethyl acetoacetate bisbutyl acetoacetonate, aluminum monoethyl acetoacetate bishexyl acetoacetonate, aluminum monoethyl acetoacetate bisnonyl acetoacetonate, aluminum dibutoxide monoacetoacetate, aluminum di Propoxide monoacetoacetate, aluminum dibutoxide monoethylacetoacetate, aluminum oxide acrylate, aluminum oxide octate, aluminum oxide stearate, trisalizarin aluminum, aluminum-s-butoxide bis (ethylacetoacetate), aluminum di-s-butoxide Ethyl acetoacetate, aluminum-9-oct Examples include tadecenyl acetoacetate diisopropoxide, aluminum phenoxide, aluminum acrylate, and aluminum methacrylate.

  Specific examples of the titanium chelate compound include isopropyl triisostearoyl titanate, isopropyl tri-n-stearoyl titanate, isopropyl trioctanoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphite) titanate, tetraisopropyl bis (dioctyl) Phosphite) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (di-tridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, Bis (dioctyl pyrophosphate) ethylene titanate, Tris (dioctyl pyrophosphate) ethylene titanate Isopropyl dimethacrylisostearoyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumyl phenyl titanate, isopropyl tri (N-aminoethylaminoethyl) titanate, dicumyl phenyloxyacetate titanate, Diisostearoyl ethylene titanate, isopropyl diisostearoyl cumylphenyl titanate, isopropyl distearoyl methacryl titanate, isopropyl diisostearoyl acryl titanate, isopropyl 4-aminobenzenesulfonyldi (dodecylbenzenesulfonyl) titanate, isopropyltrimethacryl titanate, isopropyldi ( 4-aminobenzoyl) iso Thearoyl titanate, isopropyl tri (dioctyl pyrophosphate) titanate, isopropyl triacryl titanate, isopropyl tri (N, N-dimethylethylamino) titanate, isopropyl trianthranyl titanate, isopropyl octyl (butyl pyrophosphate) titanate, isopropyl dibutyl (methyl pyro) Phosphate) titanate, tetraisopropyl di (dilauroyl phosphite) titanate, diisopropyloxyacetate titanate, isostearoyl methacryloxyacetate titanate, isostearoyl acryloxyacetate titanate, di (dioctyl phosphate) oxyacetate titanate, 4-aminobenzenesulfonyldodecylbenzene Sulfonyloxyace Tate titanate, dimethacryloxyacetate titanate, dicumyl phenolate oxyacetate titanate, 4-aminobenzoylisostearoyloxyacetate titanate, diacryloxyacetate titanate, di (octyl, butylpyrophosphate) oxyacetate titanate, isostearoyl methacrylethylene titanate , Di (dioctyl phosphate) ethylene titanate, 4-aminobenzenesulfonyldodecylbenzenesulfonylethylene titanate, dimethacrylethylene titanate, 4-aminobenzoylisostearoylethylene titanate, diacrylethylene titanate, dianthranylethylene titanate, di (butyl, methylpyro Phosphate) ethylene titanate, titanium allyl Cetoacetate triisopropoxide, titanium bis (triethanolamine) diisopropoxide, titanium di-n-butoxide (bis-2,4-pentanedionate), titanium diisopropoxide bis (tetramethylheptanedionate), titanium Examples include diisopropoxide bis (ethyl acetoacetate), titanium methacryloxyethyl acetoacetate triisopropoxide, titanium methylphenoxide, titanium oxide bis (pentanedionate), and the like.

  Other metal chelate compounds include zirconium peroxoethylenediaminetetraacetate pyridinium, zirconium glutamate diacetate bis (3,5-dimethylpyridinium), zirconium benzoylacetonate bis (1,3-butanediol), zirconium allyl acetoacetate triisopropoxy. Side, zirconium di-n-butoxide (bis-2,4-pentanedionate), zirconium diisopropoxide (bis-2,4-pentanedionate), zirconium diisopropoxide bis (tetramethylheptanedionate) , Zirconium diisopropoxide bis (ethyl acetoacetate), zirconium methacryloxyethyl acetoacetate triisopropoxide, zirconium butoxide (acetate) Ruacetate) (bisethyl acetoacetate), iron (III) acetylacetonate, dibenzoylmethane iron (II), tropolone iron, tristropolono iron (III), hinokitiol iron, tris hinokitioro iron (III), acetoacetate Iron (III), iron (III) benzoylacetonate, iron (III) trifluoropentanedionate, salicylaldehyde copper (II), copper (II) acetylacetonate, salicylaldehyde imine copper, kojic acid copper, biscojato copper (II), tropolone copper, bistropolono copper (II), bis (5-oxynaphthoquinone-1,4) copper, bis (1-oxyanthraquinone) nickel, acetoacetate copper, salicylamine copper, o-oxyazobenzene copper, Copper (II) benzoyl acetate, copper (II) ethyl acetoacetate, copper (II Methacryloxyethyl acetoacetate, copper (II) methoxyethoxy ethoxide, copper (II) 2,4-pentanedionate, copper (II) 2,2,6,6-tetramethyl-3,5-heptanedionate, Zinc N, N-dimethylaminoethoxide, zinc 2,4-pentanedionate, zinc 2,2,6,6-tetramethyl-3,5-heptanedionate, salicylaldehyde cobalt, o-oxyacetophenone nickel, bis (1-oxyxanthone) nickel, nickel pyromeconate, salicylaldehyde nickel, allyltriethylgermane, allyltrimethylgermane, ammoniumtris (oxalate) germanate, bis [bis (trimethylsilyl) amino] germanium (II), carboxyethylgermanium sesquioxide , Clopentadienyltrimethylgermane, di-n-butyldiacetoxygermane, di-n-butyldichlorogermane, dimethylaminotrimethylgermane, diphenylgermane, hexaallyldigermanoxane, hexaethyldigermanoxane, hexamethyldigermane , Hydroxygermatrane monohydrate, methacryloxymethyltrimethylgermane, methacryloxytriethylgermane, tetraallylgermane, tetra-n-butylgermane, tetraisopropoxygermane, tri-n-butylgermane, trimethylchlorogermane, triphenylgermane , Vinyltriethylgermane, bis (2,4-pentanedionate) dichlorotin, di-n-butylbis (2,4-pentanedionate) tin, calcium 2,4-pentanedi Cerium (III) 2,4-pentanedionate, cobalt (II) 2,4-pentanedionate, cobalt (III) 2,4-pentanedionate, europium 2,4-pentanedionate, europium (III ) Thenoyl trifluoroacetonate, indium 2,4-pentanedionate, manganese (II) 2,4-pentanedionate, manganese (III) 2,4-pentanedionate and the like, and are preferably used in the present invention. .

  Among these specific examples, particularly preferably used metal chelate compounds are those having a bidentate ligand, particularly acetylacetonate (pentanedionate), ethylacetoacetonate (hexanedionate), propylacetate. Those having acetonate (heptanedionate), tetramethylheptanedionate or benzoylacetonate as a ligand are preferred.

  Further, aluminum, zirconia, titanium acetylacetonate (pentanedionate), ethylacetoacetonate (hexanedionate), propylacetoacetonate (heptanedionate), tetramethylheptanedionate, benzoylacetonates and the like are preferable. As a compound. More preferred is titanium acetylacetonate (pentandionate).

  These metal chelate compounds can be used alone or in combination of two or more. The method of inclusion in the composition may be added to the photosensitive organic component first, or may be added to the inorganic powder first, and the order of addition is not particularly limited. The content is preferably from 0.01 to less than 5% by weight, more preferably from 0.1 to 3% by weight, even more preferably from 0.2 to 1.5% by weight, based on the entire solid content contained in the composition. When the content is more than 5% by weight, gelation tends to occur. When the content is less than 0.01% by weight, the effect of reducing shrinkage cannot be obtained.

  Moreover, you may add a ultraviolet absorber to the photosensitive composition for baking of this invention other than each component of (A), (B), (C) mentioned above. By adding an absorbent having a high ultraviolet absorption effect, a high aspect ratio, high definition, and high resolution can be obtained. As the ultraviolet absorber, an organic dye, particularly an organic dye having a high UV absorption coefficient in a wavelength range of 350 to 450 nm is preferably used. Even when an organic dye is added as an ultraviolet absorber, it is preferable because it does not remain in the glass film after firing and the deterioration of the insulating film characteristics due to the ultraviolet absorber can be reduced. As such a compound, an azo dye or a benzophenone dye is preferable because the absorption wavelength can be easily controlled in a desired wavelength region. The addition amount of the organic dye in the photosensitive organic component is preferably 0.05 to 5% by weight with respect to the photosensitive organic component. More preferably, it is 0.1 to 1 weight%. If it is less than 0.05% by weight, the effect of adding an ultraviolet absorber is reduced, and if it exceeds 5% by weight, the properties of the insulating film after firing are deteriorated.

  A sensitizer is added in order to improve sensitivity. In the present invention, one or more of these can be used. Some sensitizers can also be used as photopolymerization initiators. When adding a sensitizer, the addition amount is preferably 0.05 to 30% by weight, more preferably 0.1 to 20% by weight, based on the photosensitive component. If the amount of the sensitizer is too small, the effect of improving the photosensitivity is not exhibited, and if the amount of the sensitizer is too large, the residual ratio of the exposed portion may be too small.

  Furthermore, it is preferable to add a polymerization inhibitor. When a polymerization inhibitor is added, the addition amount is preferably 0.001 to 1% by weight with respect to the composition.

  Moreover, you may add a plasticizer and antioxidant. When adding a plasticizer, the addition amount is preferably 0.5 to 10% by weight based on the composition. When adding antioxidant, the addition amount is 0.001-1 weight% with respect to a composition.

  The refractive index of the photosensitive organic component contained in the photosensitive composition for firing of the present invention is generally in the range of 1.4 to 1.7, but the refractive index of the inorganic component is 1.4 to 2.3 and the width thereof. Widely, in some cases, the refractive index difference between the organic component and the inorganic component is very large, 0.1 to 1.3. In such a case, a compound that emits light having a wavelength longer than the wavelength absorbed and absorbed by the photosensitive organic component, and the emitted light cures or solubilizes the photosensitive organic component (hereinafter referred to as Compound (X)). If this is included, the same effect as that when the difference in refractive index is small is exhibited. Originally, it is desirable that the difference in refractive index is small, but even if the difference in refractive index is inevitably large, the compound (X) is contained and the compound (X) absorbs ultraviolet rays to suppress scattering. In addition, it is possible to cure a portion far from the exposure surface by emitting from the compound (X) fluorescence having a high transmittance and longer wavelength than the absorbed ultraviolet rays.

  The average refractive index of the photosensitive organic component is determined by the following method. First, the refractive index at a desired wavelength is measured for each component by the V-block method. Next, it is obtained by adding the respective refractive indexes according to the weight% of the photosensitive organic component. For example, a certain photosensitive organic component is composed of A (50% by weight) and B (50% by weight), A has a refractive index at a certain wavelength of 1.46, and B has a refractive index at the same wavelength as A. In the case of 1.58, the average refractive index of the photosensitive organic component is (1.46 × 0.5) + (1.58 × 0.5) = 0.73 + 0.79 = 1.52. Alternatively, the photosensitive organic component is applied and dried on glass, and then directly measured using an ellipsometer. Measuring the refractive index at the exposure wavelength is accurate in confirming the effect. In particular, it is preferable to measure with light in the wavelength range of 350 to 650 nm. Furthermore, refractive index measurement with i-line (365 nm) or g-line (436 nm) is preferable.

  The compound (X) used in the present invention refers to a compound that absorbs ultraviolet rays and emits blue fluorescence. Examples of the compound (X) used in the present invention include fluorescent whitening agents such as coumarin fluorescent whitening agents, oxazole fluorescent whitening agents, stilbene fluorescent whitening agents, imidazole fluorescent whitening agents, and triazole fluorescent whitening agents. Agents, imidazolone-based, oxacyanine-based, methine-based, pyridine-based, anthrapyridazine-based, and carbostyryl-based fluorescent whitening agents are used.

  In the present invention, the coumarin fluorescent whitening agent has a coumarin structure represented by the following formula in the molecule. Specific examples of the coumarin fluorescent brightener include 7-diethyldiamino-4-methylcoumarin, 7-hydroxy-4-methylcoumarin, 7-ethylamino-4-methylcoumarin, 7-dimethylamino-4- Examples thereof include methylcoumarin and 7-amino-4-methylcoumarin.

  In the present invention, the oxazole fluorescent whitening agent has an oxazole ring represented by the following formula in the molecule.

  In the present invention, the stilbene fluorescent whitening agent has a stilbene structure represented by the following formula in the molecule. Specific examples of the stilbene fluorescent brightener include s-triazine ring substitution of 4,4'-diaminostilbene-2,2'-disulfonic acid, stilbene triazole, imidazole, and oxazole substitution.

  In the present invention, the imidazole fluorescent brightener has an imidazole structure represented by the following formula in the molecule.

  In the present invention, the triazole fluorescent whitening agent has a hetero 5-membered ring composed of 3 nitrogen atoms and 2 carbon atoms in the molecule. Examples of such a hetero 5-membered ring include the following rings.

  Preferably, a coumarin-based fluorescent brightener or an oxazole-based fluorescent brightener is used because of its good compatibility with the compounds selected from a) to c) contained in the photosensitive organic component and a binder polymer. If these compounds are used, they function effectively. In particular, a coumarin-based optical brightener is preferable because of its high solubility in polar solvents. The solubility of the compound (X) in the polar solvent is preferably 2 g / 100 g solvent or more, more preferably 50 g / 100 g solvent or more. From the viewpoint of solubility, a coumarin derivative is particularly preferable. These may be used alone or in combination.

  The content of the compound (X) in the present invention is preferably 0.1 to 30% by weight with respect to the photosensitive organic component, and in particular, field emission in which a glass powder having a low softening point and a high refraction must be used. In the member and the fluorescent light emitting device application, 2 to 20% by weight is preferable, and 5 to 15% by weight is more preferable. Within this range, fine pattern processing is possible.

  Field emission refers to field emission. Field emission refers to a cathode made of a conductor such as a semiconductor or metal in a vacuum, and when an anode is placed near the surface, electrons move from the cathode surface toward the anode in vacuum. A physical phenomenon that is released into In the present invention, the field emission member refers to a member using such field emission. Specific examples include, but are not limited to, field emission displays, backlights for liquid crystal displays, field emission lamps, electron beam sources for scanning electron microscopes, and micro vacuum tubes.

  The absorption wavelength range in which the compound (X) used in the present invention absorbs ultraviolet rays is a wavelength range of 320 to 410 nm, more preferably a wavelength range of 350 nm to 380 nm, and still more preferably 360 nm to 375 nm. Moreover, the fluorescence emission wavelength region of the compound (X) is a wavelength region of 400 to 500 nm, more preferably a wavelength region of 400 nm to 450 nm, and further preferably 430 nm to 445 nm. Within this range, it effectively absorbs ultraviolet rays at the time of exposure, suppresses scattering, and emits fluorescence in the above wavelength range, which is more transmissive than the absorbed ultraviolet rays, to the deep part, that is, the part far from the exposure surface. The photosensitive organic component can be cured.

  Moreover, it is preferable that the molar extinction coefficient of compound (X) is 20000 or more in the range of content of the said compound (X). Moreover, it is preferable that it is 60000 or less. In this range, ultraviolet rays can be effectively absorbed, and scattering of ultraviolet rays during exposure can be suppressed, and the photosensitive organic component can be cured to a deeper portion.

  Absorption wavelength of ultraviolet rays, emission wavelength of fluorescence and molar extinction coefficient were measured with a spectrofluorometer (F-2500, manufactured by Hitachi, Ltd.) and an ultraviolet-visible spectrophotometer (MultiSpec 1500, manufactured by Shimadzu Corporation). It can be measured.

  The inorganic shaped article of the present invention is obtained by applying the photosensitive composition for firing to a substrate or a base material, shaping the obtained coating film into a desired shape, and firing it after shaping.

  In producing the above-described inorganic shaped article, the substrate and base material used may be either an organic material or an inorganic material, and each material is not particularly limited. As the organic material, polyethylene terephthalate is generally used. As the inorganic material, for example, soda lime glass can be used. When an organic material is used as the substrate or the base material, the substrate or the base material is separated from the shaped object formed from the photosensitive composition for firing, and then the shaped object is baked to obtain an inorganic shaped object. In addition, when an inorganic material is used as the substrate or the base material, the substrate or the base material is separated, and then the molded article formed from the photosensitive composition for firing is fired or the substrate or the base material is not separated. The modeled object may be fired. In the latter case, an inorganic modeled object in which the modeled object made of the substrate and the base material and the inorganic powder is integrated is obtained.

  The photosensitive composition for baking of the present invention can be prepared as follows. After mixing a compound selected from components a) to c) as photosensitive organic components, and if necessary, a binder polymer, compound (X), various additives, etc., and (C) after adding and mixing a metal chelate compound Filter and prepare the organic vehicle. To this, pretreated (B) glass powder is added if necessary, and homogeneously mixed and dispersed in a kneader such as a ball mill to prepare a photosensitive composition for firing.

  The viscosity of the photosensitive composition for baking is appropriately adjusted depending on the addition ratio of inorganic components, thickeners, organic solvents, plasticizers, precipitation inhibitors, etc., but the range is 2 to 200 Pa · s (Pascal · seconds). is there. For example, when applying to a glass substrate by a spin coat method, 2-5 Pa.s is preferable. In order to obtain a film thickness of 10 to 20 μm by applying it once by the screen printing method, 50 to 200 Pa · s is preferable. In the case of using a blade coater method or a die coater method, 2 to 20 Pa · s is preferable.

  Examples of the organic solvent used to adjust the viscosity of the solution include methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl ethyl ketone, dioxane, acetone, cyclohexanone, cyclopentanone, isobutyl alcohol, isopropyl alcohol, and 3-methoxy-3-methyl-1. -Butanol, tetrahydrofuran, dimethyl sulfoxide, γ-butyrolactone, bromobenzene, chlorobenzene, dibromobenzene, dichlorobenzene, bromobenzoic acid, chlorobenzoic acid, etc., and organic solvent mixtures containing one or more of these are used .

  The photosensitive composition for baking of the present invention includes various members (partitions, spacers, dielectrics, etc.) of flat panel displays, fluorescent light emitting tube (cold cathode tube) members, insulating layers (field emission members) of field emission displays, etc. The display member is preferably used.

  When manufacturing a field emission member from the photosensitive composition for baking of the present invention, it is preferable to use a glass substrate as the substrate. As the glass substrate, soda lime glass or heat resistant glass (PD200 manufactured by Asahi Glass Co., Ltd., PP8 manufactured by Nippon Electric Glass Co., Ltd., CS25 manufactured by Saint-Gobain Co., Ltd., CP600V manufactured by Central Glass Co., Ltd.) can be preferably used. In addition, ceramic substrates, metal substrates, semiconductor substrates (AlN, CuW, CuMo, SiC substrates, etc.) and various plastic films can be used, but substrates with particularly smooth surfaces such as glass substrates, metal substrates, semiconductor substrates, etc. In the case of a substrate, the present invention is particularly effective.

  On these substrates, if necessary, one or more insulators, semiconductors, and conductors, or a combination thereof may be formed.

  Next, as an example, a method for manufacturing a display member will be described with reference to a method for manufacturing an insulating layer of a field emission display.

  As a substrate, a photosensitive composition for baking is applied over the whole or a part of a glass substrate on which an ITO electrode is formed. As a coating method, general methods such as screen printing, bar coater, roll coater, and slit die coater can be used. The coating thickness can be adjusted by selecting the number of coatings, the screen mesh, and the viscosity of the photosensitive composition for baking. However, the thickness after drying is 5 to 100 μm, preferably 5 to 5 μm, considering shrinkage due to drying and baking. It is preferable to apply so as to be 60 μm, more preferably 5 to 40 μm.

  When the photosensitive composition for baking is applied a plurality of times, the photosensitive composition for baking to be applied for the first time and the second and subsequent times may be the same photosensitive composition for baking or for different baking. It may be a photosensitive composition. Moreover, when apply | coating the photosensitive composition for baking in multiple times, it is preferable to bake after the photosensitive composition for baking of the 1st time and before the photosensitive composition for baking of the 2nd time or later. If it does so, the photosensitive composition for baking apply | coated 1st time can dry, and the reduction | decrease of the thickness of the coating film at the time of the photosensitive composition for baking of 2nd time can be prevented. Although the baking temperature and time vary depending on the composition of the photosensitive composition for baking, it is preferably applied at 50 to 100 ° C. for about 5 to 30 minutes. Further, it is desirable to perform the baking in a convection baking furnace or an IR baking furnace.

A pattern can be formed by applying the photosensitive composition for baking on the substrate entirely or partially, and then exposing and developing. The shape of the pattern varies depending on the field emission member. In the case of the insulating layer of the field emission display, a pattern including a circular hole having a diameter of 3 to 100 μm or a square having a side of 3 to 100 μm is formed. More preferably, it is 3-50 micrometers, More preferably, it is 3-20 micrometers. If it exists in this range, the effect of the photosensitive composition for baking can fully be exhibited. For exposure, a mask exposure method using a photomask and a direct drawing exposure method using a laser beam or the like can be used. However, exposure using a photomask can shorten the exposure time. As an exposure apparatus in this case, a stepper exposure machine, a proximity exposure machine, or the like can be used. Examples of the active light source used include visible light, near ultraviolet light, ultraviolet light, near infrared light, electron beam, X-ray, and laser light. Among these, ultraviolet light is preferable, and as the light source, for example, Low pressure mercury lamp, high pressure mercury lamp, super high pressure mercury lamp, halogen lamp, germicidal lamp, etc. can be used. Among these, an ultrahigh pressure mercury lamp is suitable. Although exposure conditions vary depending on the coating thickness, exposure is performed for 0.5 to 30 minutes using an ultrahigh pressure mercury lamp having an output of 5 to 1000 W / m ² . In particular, it is preferable to perform exposure with an exposure amount of about 0.05 to 1 J / cm ² .

  Thereafter, development is performed using a developing solution. In this case, the immersion method, the spray method, the shower method, and the brush method are used. Among these, the shower method is preferable in that uniform development can be realized. The flow rate and pressure of the developing solution when developing by the shower method vary depending on the type and concentration of the developing solution, but the flow rate is preferably 50 ml / min to 200 ml / min, more preferably 100 ml / min to 170 ml / min. The pressure is preferably 0.05 MPa to 0.2 MPa, more preferably 1 kg / min to 1.6 kg / min. As the developer, an organic solvent or an aqueous solution in which an organic component in the baking photosensitive composition can be dissolved or dispersed is used. Further, an aqueous solution containing an organic solvent may be used. When a compound having a functional group such as a carboxyl group, a phenolic hydroxyl group, or a silanol group is present in the photosensitive composition for baking, development can be performed with an alkaline aqueous solution. A metal alkali aqueous solution such as sodium hydroxide, calcium hydroxide, sodium carbonate aqueous solution or the like can be used as the alkaline aqueous solution. However, it is preferable to use an organic alkaline aqueous solution because an alkaline component can be easily removed during firing. As the organic alkali, a general amine compound can be used. When a metal alkali aqueous solution is used, the alkali component is removed by washing with an acid after development. Specific examples include tetramethylammonium hydroxide, trimethylbenzylammonium hydroxide, monoethanolamine, and diethanolamine. The concentration of the alkali component in the aqueous alkali solution is preferably 0.01 to 10% by weight, more preferably 0.1 to 5% by weight. If the alkali concentration is too low, the unexposed portion is not removed, and if the alkali concentration is too high, the pattern portion may be peeled off and the exposed portion may be corroded. The temperature of the developer during development is preferably 20 to 50 ° C. for process control.

  In addition, it is preferable to add a surfactant to the developer for the purpose of improving the wettability of the photosensitive composition for baking to the coating film, the uniformity of development and the reduction of residues. As the surfactant, nonionic, anionic, cationic, and amphoteric surfactants can be used. The addition amount of the surfactant is preferably in the range of 0.01 to 20% by weight, more preferably 0.05 to 10% by weight, and still more preferably 0.1 to 5% by weight. If the addition amount exceeds 20% by weight, the developability may be insufficient. If the addition amount is less than 0.01% by weight, the effect of adding a surfactant may be difficult to be exhibited.

  Moreover, it is preferable to perform ultrasonic treatment in a developing solution at the time of development, and further, frequency modulation ultrasonic treatment in which frequency modulation ultrasonic treatment is modulated in a wavelength range of 20 to 50 KHz is particularly preferable. By such ultrasonic treatment, a great effect can be obtained in forming a fine and uniform pattern and reducing the residue.

  By the method as described above, a pattern containing a circular hole having a thickness of 5 to 100 μm and a diameter of 3 to 100 μm or a side of 3 to 100 μm can be formed on the substrate from the photosensitive composition for baking of the present invention. it can.

  Thereafter, directly or as necessary, after forming a gate electrode, an emitter, or the like, baking is performed in a baking furnace. The firing atmosphere, temperature, and time can be appropriately selected depending on the photosensitive composition for firing and the type of the substrate, and firing is performed in an atmosphere of air, nitrogen, hydrogen, or the like. Baking is performed by holding at a temperature of 400 to 600 ° C. for 10 to 60 minutes. As the firing furnace, a batch-type firing furnace or a belt-type continuous firing furnace can be used. Moreover, you may heat at 50-300 degreeC in the above each process for the purpose of drying and a preliminary reaction.

  Through the above steps, an insulating layer for a field emission display having a pattern including a circular hole having a thickness of 5 to 100 μm and a diameter of 3 to 100 μm or a square of 3 to 100 μm on one side formed on the substrate is obtained. In order to drive the field emission display at a low voltage, it is necessary to make the distance between the gate electrode portion and the electron-emitting device closer. Therefore, the thickness of the insulating layer is preferably 30 μm or less. The aspect ratio of the holes formed in the insulating layer (the thickness of the insulating layer / the holes formed in the insulating layer) is preferably 0.5 or more. Further, in order to achieve high resolution and uniform luminance, the holes formed in the insulating layer are preferably 30 μm or less.

  The gate electrode is formed by the following method. After obtaining an insulating layer on which a desired pattern is formed, a chromium film is formed by uniformly forming a chromium-based thin film by sputtering or vapor deposition. Alternatively, pattern formation may be performed using a photosensitive conductor paste or the like. Next, a positive resist is applied to the entire surface of the chromium film by a known coating method such as spin coating or screen printing, and prebaked with a hot plate or the like. Next, a photomask with a desired pattern is placed on the chromium film provided with the above resist layer, and an etching mask is formed from the positive resist remaining on the chromium film through the steps of ultraviolet irradiation, exposure and development. To do. Next, the chromium film that is not covered with the etching mask is etched for several minutes with an acidic etching solution (cerium nitrate cerium nitrate: 9 wt% + perchloric acid: 6 wt%, etc.). Remove the part. Thereafter, the etching mask is peeled off using a stripping solution and washed with water to leave a chromium layer in which only unnecessary portions are etched, and a gate electrode is formed. At this time, it is necessary that the insulating layer on which a desired pattern is formed is difficult to dissolve in the etching solution.

The electron-emitting device is formed by the following method. The formation method differs depending on the electron emission source. In the case of a Spindt type metal chip (or microchip) mainly made of molybdenum, the vapor deposition method is used. In the case of using CNT, a photosensitive CNT paste is used inside the pattern. A step of irradiating light from the rear surface of the substrate after being applied by a screen printing method or the like, and selectively exposing only a portion inside the pattern of the CNT paste, and a portion of the CNT paste that is not exposed. Is formed by a method of leaving the exposed CNTs.
In addition to such an insulating layer and gate electrode, the substrate on which the electron-emitting device is formed is used as a back plate, and after sealing with a separately manufactured front plate, wiring is performed and high brightness and contrast are achieved. A high field emission display can be obtained.

  Below, it demonstrates concretely using an Example. However, the present invention is not limited to this.

<Metal chelate compound I>
"Narsem Ti" (titanium diisopropoxide (bis-2,4-pentandionate), manufactured by Nippon Chemical Industry Co., Ltd.)
<Metal chelate compound II>
"Orgatics TC-401" (titanium tetraacetylacetonate, manufactured by Matsumoto Pharmaceutical Co., Ltd.)
<Metal chelate compound III>
"ALCH-TR" (aluminum (III) trisethyl acetoacetate, manufactured by Kawaken Fine Chemical Co., Ltd.)
<Metal chelate compound IV>
“Orgachix ZC-150” (zirconium tetraacetylacetonate, manufactured by Matsumoto Pharmaceutical Co., Ltd.)
<Metal chelate compound V>
Iron (III) acetylacetonate (manufactured by Hanai Chemicals Co., Ltd.)
<Metal chelate compound VI>
"Orgatics TA-10" (tetraisopropyl titanate, manufactured by Matsumoto Pharmaceutical Co., Ltd.).

<Binder polymer I>
Weight average obtained by addition reaction of 0.4 equivalent of glycidyl methacrylate (GMA) to a carboxyl group of a copolymer composed of 30 parts by weight of methyl acrylate, 40 parts by weight of ethyl acrylate, and 30 parts by weight of methacrylic acid It is a polymer having a molecular weight of 17000, an acid value of 100 mgKOH / g, a double bond density of 1.5 mmol / g, and a viscosity of 8.2 Pa · s. The thermal decomposition temperature was 390 ° C. and Tg was 25 ° C.

  The weight average molecular weight of the binder polymer was measured by size exclusion chromatography using tetrahydrofuran as a mobile phase. The column was Shodex KF-803, and the weight average molecular weight was calculated in terms of polystyrene.

  The acid value was measured by dissolving 1 g of the binder polymer in 100 mL of ethanol and then titrating with a 0.1N potassium hydroxide aqueous solution.

  The viscosity was measured with a rotational viscometer (RVDVII +, manufactured by Brookfield) at a temperature of 25 ± 0.1 ° C., a rotational speed of 10 rpm, and a viscosity 5 minutes after the start of measurement.

  The thermal decomposition temperature is set with a sample of about 20 mg using a TG measuring device (TGA-50, manufactured by Shimadzu Corporation), the flow rate is 20 ml / min in an air atmosphere, and the heating rate is 20 to 0.6 ° C./min. The temperature is raised to 700 ° C. As a result, a chart in which the relationship between temperature (vertical axis) and weight change (horizontal axis) is plotted is printed, the tangent line between the part before decomposition and the part during decomposition is drawn, and the temperature at the intersection is defined as the thermal decomposition temperature. . The glass transition point is determined by using a DSC-50 type measuring device manufactured by Shimadzu Corporation, raising the temperature at a rate of temperature increase of 20 ° C./min under a sample weight of 10 mg under a nitrogen stream, and starting the deviation of the baseline. Tg.

<Glass powder I>
As glass powder, Bi ₂ O ₃ (74 wt%), SiO ₂ (7.2 wt%), B ₂ O ₃ (10 wt%), ZnO (2.3 wt%), ZrO ₂ (2.2 wt%) %) And Al ₂ O ₃ (2.5% by weight) glass powder. This glass powder had a glass softening point of 509 ° C., an average particle size of 0.5 μm, a specific gravity of 5.86 _g / cm ³ , and a refractive index ( _ng ) of 2.15.

  The glass softening point is obtained by putting glass powder in a platinum cell, and using a differential thermal analyzer (TG8120, manufactured by Rigaku Denki Co., Ltd.), performing a differential thermal analysis at a temperature increase rate of 20 ° C./minute from room temperature to 700 ° C., The temperature at which the endotherm ends through the minimum point of the endothermic portion that appears first was defined as the softening point (Ts). The average particle diameter was measured using a laser diffraction / scattering measuring device (Microtrac particle size distribution meter HRA, manufactured by Nikkiso Co., Ltd.). The specific gravity was measured by processing the glass into a size of about 5 × 5 × 5 mm and using the Archimedes method.

  The refractive index was measured for light having a wavelength of 436 nm at 25 ° C. by ellipsometry using an ellipsometer after a glass film was formed on quartz glass.

<Glass powder II>
The glass powder consists of Bi ₂ O ₃ (77 wt%), SiO ₂ (6.7 wt%), B ₂ O ₃ (10 wt%), ZrO ₂ (0.58 wt%), ZnO (2.3 wt%). %) And Al ₂ O ₃ (2.5% by weight) glass powder. This glass powder had a glass softening point of 493 ° C., an average particle diameter of 0.5 μm, a specific gravity of 6 g / cm ³ , and a refractive index ( _ng ) of 2.2.

<Glass powder III>
The glass powder consists of Bi ₂ O ₃ (77.2 wt%), SiO ₂ (6.9 wt%), B ₂ O ₃ (10.2 wt%), ZrO ₂ (0 wt%), ZnO (2. Glass powder having a composition of 5 wt%) and Al ₂ O ₃ (2.7 wt%) was used. This glass powder had a glass softening point of 493 ° C., an average particle diameter of 0.5 μm, a specific gravity of 6.1 g / cm ³ , and a refractive index ( _ng ) of 2.21.

<Glass powder IV>
The glass powder consists of Bi ₂ O ₃ (67 wt%), SiO ₂ (7.6 wt%), B ₂ O ₃ (13.7 wt%), ZrO ₂ (0 wt%), ZnO (8.0 wt%). %), Glass powder having a composition of Al ₂ O ₃ (3.2 wt%) was used. This glass powder had a glass softening point of 534 ° C., an average particle size of 1.4 μm, a specific gravity of 5.4 g / cm ³ , and a refractive index ( _ng ) of 1.98.

<Glass powder V>
The glass powder consists of Bi ₂ O ₃ (67% by weight), SiO ₂ (9.7% by weight), B ₂ O ₃ (11.5% by weight), ZrO ₂ (3.3% by weight), ZnO (3. 8% by weight) and glass powder having a composition of Al ₂ O ₃ (4% by weight) were used. This glass powder had a glass softening point of 529 ° C., an average particle diameter of 0.5 μm, a specific gravity of 5.33 _g / cm ³ , and a refractive index ( _ng ) of 1.95.

<Glass powder VI>
As glass powder, Bi ₂ O ₃ (70 wt%), SiO ₂ (16 wt%), B ₂ O ₃ (9.2 wt%), ZrO ₂ (0 wt%), ZnO (2.3 wt%) A glass powder having a composition of Al ₂ O ₃ (2.5 wt%) was used. This glass powder had a glass softening point of 590 ° C., an average particle diameter of 1.6 μm, a specific gravity of 5.0 g / cm ³ , and a refractive index ( _ng ) of 1.95.

<Glass powder VII>
The inorganic powder is a glass powder having a composition of PbO (70 wt%), SiO ₂ (13 wt%), Al ₂ O ₃ (3% wt), B ₂ O ₃ (10 wt%), ZnO (4 wt%). Was used. This glass powder had a glass softening point of 590 ° C., an average particle size of 1.2 μm, and a refractive index ( _ng ) of 2.1.

<Glass powder VIII>
The glass powder is Bi ₂ O ₃ (76 wt%), SiO ₂ (6.4 wt%), B ₂ O ₃ (9 wt%), ZrO ₂ (0 wt%), ZnO (2.3 wt%). A glass powder having a composition of Al ₂ O ₃ (2.4 wt%) and MgO (3.4 wt%) was used. This glass powder had a glass softening point of 456 ° C., an average particle diameter of 0.5 μm, a specific gravity of 5.9 g / cm ³ , and a refractive index ( _ng ) of 2.1.

<Glass powder IX>
Glass powder is Bi ₂ O ₃ (74 wt%), SiO ₂ (6 wt%), B ₂ O ₃ (7 wt%), ZrO ₂ (0 wt%), ZnO (2 wt%), Al ₂ O ₃ (2 wt%), Li ₂ O (8.7 wt%) composition was used. This glass powder had a glass softening point of 436 ° C., an average particle diameter of 0.5 μm, a specific gravity of 5.2 g / cm ³ , and a refractive index ( _ng ) of 1.98.

<Filler I>
Ceramics: Alumina particles having an average particle size of 37 nm (trade name Nanotech, manufactured by C.I. Kasei Co., Ltd.) The average particle size is determined by measuring the specific surface area by the BET method using nitrogen gas, and then assuming that the particles are spheres. From this, the particle diameter was determined, and the average particle diameter was determined as the number average.
<Filler II>
Silica: Silica particles having an average particle diameter of 12 nm (Nippon Aerosil Co., Ltd., trade name: Aerosil 200), the average particle diameter is determined by measuring the specific surface area by the BET method using nitrogen gas, and assuming that the particles are spheres. The particle diameter was determined from the surface area, and the average particle diameter was determined as the number average.

<Compound (X)>
The maximum absorption wavelength of ultraviolet light in a coumarin derivative (Nippon Kayaku Co., Ltd., trade name Kalight B), 3-methoxy-3-methyl-1-butanol solution was 370 nm, and the maximum emission wavelength of fluorescence was 441 nm. It was.

<Substrate I>
Soda lime glass (glass thickness 1.8mm)
<Substrate II>
High strain point glass “PD200” (Asahi Glass Co., Ltd., glass thickness 2.8 mm)
<Substrate III>
Silicon wafer (manufactured by Shin-Etsu Chemical Co., Ltd., P type, thickness 0.525 mm)
<Substrate IV>
Alumina substrate (Nikko Corporation, thickness 0.635 mm)
<Substrate V>
Soda lime glass (with a glass thickness of 1.8 mm) treated with a silane coupling agent. In the silane coupling agent treatment method, a 0.1 wt% ethanol solution of silane coupling agent “KBE903” (manufactured by Shin-Etsu Silicone Co., Ltd.) was applied to the substrate I with a spinner and then dried at 150 ° C. for 1 minute.

Example 1
As a photosensitive organic component, 7 parts by weight of an acrylic monomer (Nara Kayaku Co., Ltd. Karayad TPA-330), which is an ethylenically unsaturated group-containing compound, and 7 parts by weight of the above binder polymer I (solvent (3-methyl- 10 parts by weight of 3-methoxybutanol), photopolymerization initiator (manufactured by Nippon Kayaku Co., Ltd., 2,4-dimethyloxanthone and Ciba Specialty Chemicals, Inc., trade name Irgacure 369 in a weight ratio of 1: 2. 2 parts by weight, 3 parts by weight of compound (X), 0.2 parts by weight of ultraviolet light absorber (organic dye, Kayase SF-G: manufactured by Nippon Kayaku Co., Ltd.), dispersant (San Nopco Co., Ltd.) Product name Nop Cosperth 092) 0.3 parts by weight, polymerization inhibitor (p-methoxyphenol) 0.5 parts by weight, the metal chelate compound I is 0 2 parts by weight, as an inorganic component, and the above glass powder I were mixed 79.8 parts by weight. This was passed 5 times with 3 rolls to prepare a photosensitive composition for firing. This baking photosensitive composition was further filtered using a 400 mesh filter.

The above baking photosensitive composition is uniformly applied on a soda lime glass substrate using screen printing, dried at 80 ° C. for 15 minutes to form a layer of baking photosensitive composition having a thickness of 20 μm. did. Then, using a negative chrome mask having a 20 μm via pattern / 60 μm pitch and a 30 μm via pattern / 90 μm pitch, UV exposure was performed with an ultrahigh pressure mercury lamp having an output of 0.5 kW from the upper surface. As a result of adjusting the exposure to an optimum amount, the exposure was performed at an exposure amount of 400 mJ / cm ² .

  Next, a 0.1% by weight aqueous solution of sodium carbonate maintained at 25 ° C. is developed for 30 seconds in a shower, and then washed with water using a shower spray to remove the non-light-cured portion and about 20 μm on the glass substrate. A via pattern having a hole diameter of about 30 μm was formed.

The refractive index of the photosensitive organic component was measured with respect to light having a wavelength of 436 nm at 25 ° C. by ellipsometry using an ellipsometer after the coating and drying steps after producing only the photosensitive organic component. The refractive index ( _ng ) was 1.52.

  The board | substrate after pattern formation was observed with the optical microscope, and the ratio in which the pattern was formed among 100 via patterns of a mask was evaluated as a via | veer processing rate (%). Moreover, the diameter of 10 via patterns was measured, and the average value was obtained to obtain the average via processing diameter before firing the substrate. As a result, 100 via patterns were formed in both 20 μm and 30 μm, and the via processing rate was 100%.

  The substrate after pattern formation was heated to a temperature near the softening point of the glass powder at a temperature rising rate of 4 ° C./min, and held for 20 minutes for firing.

  The substrate pattern after firing was observed with an optical microscope in the same manner as before firing, the diameter of 10 via patterns was measured in the same manner, and the average value of 10 was obtained, whereby the average via processing diameter after firing the substrate It was. The average via machining diameter was calculated. When the via enlargement ratio was defined and evaluated as follows, it was as good as 1.3.

Via enlargement ratio = (average via processing diameter after firing) / (average via processing diameter before firing).
Next, a chromium film having a film thickness of 150 nm was formed on the patterned substrate after firing by sputtering. A positive photoresist (trade name AZ1500, manufactured by AZ Electronic Materials Co., Ltd.) was applied to the obtained patterned substrate with a chromium film by a spin coater method, and then baked at 100 ° C. for 1 minute. The film thickness of the photoresist was 1.5 μm. After that, using a negative chrome mask having a 25 μm via pattern / 60 μm pitch, a 37.5 μm via pattern / 90 μm pitch, UV exposure was performed from the top surface with an ultra-high pressure mercury lamp with an output of 0.5 kW. The exposure amount was 100 mJ / cm ² .

  Next, after dipping and shaking for 60 seconds in a resist developer maintained at 25 ° C. (trade name AZ400K manufactured by AZ Electronic Materials Co., Ltd. diluted 5 times), washed with pure water for 30 seconds, 120 ° C. for 2 minutes A resist pattern was obtained by performing post-baking. A chromium etching solution prepared with a composition of 9 wt% cerium nitrate cerium nitrate, 6 wt% perchloric acid, and 85 wt% pure water was kept at 25 ° C., immersed for 180 seconds, and then washed pure. After the chrome etching, the resist was removed by washing with acetone.

  Surface observation was performed using a scanning electron microscope (SEM) of the obtained patterned substrate after chromium etching, and the number of lumps having a size of 0.3 μm or more was visually observed in an area of 3 μm square at a magnification of 15,000. When the average value repeated 10 times by changing the observation place was evaluated, it was 2 and there were few residues.

Examples 2 to 21 and Comparative Examples 1 to 5
Based on the compositions described in Tables 1 to 3, a baking photosensitive composition was prepared in the same manner as in Example 1, and the via enlargement ratio, pattern processability, and etching solution resistance were evaluated. In each example and comparative example, the exposure amount at the time of forming the via pattern of the photosensitive composition for baking was adjusted to an optimal amount, and the exposure was performed with each amount shown in Tables 1 to 3.

  In Examples 8 and 10, although the residue after etching was measured, the pattern was greatly dissolved, and the film thickness of 20 μm decreased to 5 μm in Example 8 and to 8 μm in Example 10. Was.

Claims (5)

(A) a photosensitive organic component, (B) an inorganic component having a bismuth-based glass powder, and (C) at least one metal chelate compound selected from a metal diketenate, a metal alkoxide, an alkyl metal, and a metal carboxylate A photosensitive composition for firing, which is a photosensitive composition for firing, and the metal chelate compound (C) is contained in an amount of 0.01% by weight or more and less than 5% by weight based on the total solid content contained in the composition. The metal chelate compound (C) is a chelate compound of at least one metal selected from the group consisting of Al, Ti, Mn, Fe, Co, Ni, Cu, Zn, Ge, In, Zr, and Sn. A photosensitive composition for baking. The photosensitive composition for firing according to claim 1, wherein the glass powder is bismuth glass. An inorganic shaped article obtained by firing the photosensitive composition for firing according to claim 1. A display member comprising the photosensitive composition for firing according to claim 1.