WO2005085360A1 - Composition containing inorganic powder, transfer film, and method of forming inorganic sinter - Google Patents

Composition containing inorganic powder, transfer film, and method of forming inorganic sinter Download PDF

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Publication number
WO2005085360A1
WO2005085360A1 PCT/JP2005/003995 JP2005003995W WO2005085360A1 WO 2005085360 A1 WO2005085360 A1 WO 2005085360A1 JP 2005003995 W JP2005003995 W JP 2005003995W WO 2005085360 A1 WO2005085360 A1 WO 2005085360A1
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Prior art keywords
inorganic powder
inorganic
forming
containing composition
powder
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PCT/JP2005/003995
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French (fr)
Japanese (ja)
Inventor
Satoshi Iwamoto
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Jsr Corporation
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Publication date
Priority claimed from JP2004065662A external-priority patent/JP2005255716A/en
Priority claimed from JP2004067552A external-priority patent/JP2005257906A/en
Application filed by Jsr Corporation filed Critical Jsr Corporation
Publication of WO2005085360A1 publication Critical patent/WO2005085360A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds

Definitions

  • the present invention relates to an inorganic powder-containing composition, a transfer film, and a method for forming an inorganic sintered body.
  • the present invention relates to a novel inorganic powder-containing composition and a method for forming an inorganic sintered body using the composition.
  • the inorganic powder-containing composition of the present invention is excellent in the thermal decomposability of the organic component during firing, and the organic component hardly remains in the formed inorganic sintered body. Therefore, it is useful as a member for field emission display (FED), plasma display panel (PDP), and inorganic electorescence (inorganic EL), particularly as a material for forming a conductive member or a material for forming a partition wall.
  • FED field emission display
  • PDP plasma display panel
  • inorganic EL inorganic electorescence
  • a field emission display is a display that emits electrons from a cathode into a vacuum by applying an electric field and irradiates the electrons on a phosphor on an anode to emit light and display.
  • a method of forming a pattern of a member such as an electrode or a partition used in such a display there are (1) a screen printing method of forming a pattern by screen printing using a paste-like composition for forming a member, and (2) a photosensitive method.
  • a photolithography method for example, Patent Documents 1 and 2 in which a composition layer for forming a member is formed, and a pattern is formed by irradiating ultraviolet rays through a photomask and then developing.
  • baking is performed at a high temperature to remove organic components such as resin, thereby forming members such as electrodes and partition walls.
  • a member pattern is formed by using the photolithography method, starting with a member of a large substrate and a member of high definition.
  • the panel performance of the display is inferior.
  • the degree of vacuum decreases with time and the luminance of the panel decreases accordingly (Patent Document 3).
  • the composition for forming a photosensitive member used in a photolithography method contains an unsaturated compound that is crosslinked by a photopolymerization initiator, and therefore, it is required to improve the performance of removing organic components during firing. ing.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 9-142878
  • Patent Document 2 JP-A-10-64435
  • Patent Document 3 JP-A-8-171877
  • the present invention has an excellent thermal decomposition property of an organic component during firing of a member pattern such as an electrode pattern and a partition pattern, and an inorganic component in which an organic component hardly remains in an inorganic sintered body such as a formed electrode or a partition. It is an object of the present invention to provide a powder-containing composition and a method for forming an inorganic sintered body using the same.
  • the inorganic powder-containing composition according to the present invention comprises (A) an inorganic powder, (B) an alkali-soluble resin, (C) a compound represented by the following formula (1) (hereinafter, referred to as "compound (C1) And at least one compound selected from the group consisting of a compound represented by the following formula (2) (hereinafter also referred to as “compound (C2)”). And (D) a photopolymerization initiator.
  • R 1 is a hydrogen atom, a hydroxyl group, an alkyl group having 114 carbon atoms or a hydroxyalkyl group having 114 carbon atoms.
  • a and b are each independently
  • the inorganic powder (A) is preferably a conductive inorganic powder or a glass powder. It is preferable that the alkali-soluble resin (B) is a methacrylate copolymer.
  • the transfer film according to the present invention is characterized by comprising a support film and a layer formed on the support film using the inorganic powder-containing composition.
  • an electrode in the method of forming an inorganic sintered body, can be formed by forming a layer using the composition containing a conductive inorganic powder.
  • a partition can be formed by forming a layer using the glass powder-containing composition.
  • the inorganic powder-containing composition according to the present invention is excellent in the thermal decomposability of the organic component during firing of the member pattern, and the organic component hardly remains in the formed inorganic sintered body such as the electrodes and the partition walls. .
  • the transfer film according to the present invention has a layer obtained from the inorganic powder-containing composition formed on a support film, and has excellent handling properties. By using this transfer film, it is possible to obtain a member forming coating film having excellent film thickness uniformity.
  • the method for forming an inorganic sintered body according to the present invention includes a method for forming a field emission display (FED), a plasma display panel (PDP), and a member for inorganic electorescence (inorganic EL), in particular, electrodes and partition walls. It is suitably used for forming.
  • FED field emission display
  • PDP plasma display panel
  • inorganic EL member for inorganic electorescence
  • the inorganic powder-containing composition according to the present invention comprises (A) an inorganic powder, (B) an alkali-soluble resin, (C) a compound represented by the above formula (1) or (2), and (D) light Contains a polymerization initiator.
  • Examples of the inorganic powder used in the present invention include a conductive inorganic powder and a glass powder.
  • glass powder examples include (1) a mixture of zinc oxide, boron oxide, and silicon oxide (ZnO—B O —SiO system), and (2) a mixture of lead oxide, boron oxide, and silicon oxide (PbO— BO- (SiO-based), (3) a mixture of lead oxide, boron oxide, silicon oxide, and aluminum oxide (Pb
  • the softening point of the glass powder is preferably in the range of 400 to 600 ° C. from the viewpoint of the firing temperature in forming the inorganic sintered body. Further, the average particle size of the glass powder is preferably in the range of 0.5 to 2.5 zm.
  • the glass powder can be used in combination with an inorganic oxide such as aluminum oxide, chromium oxide, manganese oxide, titanium oxide, zirconium oxide, silicon oxide, cerium oxide, and cobalt oxide.
  • an inorganic oxide such as aluminum oxide, chromium oxide, manganese oxide, titanium oxide, zirconium oxide, silicon oxide, cerium oxide, and cobalt oxide.
  • the content of the inorganic oxide used in combination is preferably 30% by weight or less based on the total amount of the inorganic powder (A) (glass powder + inorganic oxide).
  • the conductive inorganic powder examples include particles of Ag, Au, Cu, Al, Ag_Pd alloy, Cr, Ni, and the like. These conductive inorganic powders can be used alone or in combination of two or more.
  • the particle diameter of the conductive inorganic powder is preferably 10 / m or less from the viewpoint of imparting sufficient conductivity to the obtained electrode.
  • the conductive inorganic powder can be used in combination with a glass frit.
  • a glass frit for example, in addition to the above glass powder (1)-(4), (5) a mixture of bismuth oxide, boron oxide, silicon oxide, and aluminum oxide (BiO-BO-SiO- Al O) and others.
  • the softening point of these glass frits is preferably in the range of 400 to 600 ° C.
  • the content of the glass frit used in combination is 50% by mass or less, preferably 30% by mass or less, based on the total amount of the inorganic powder (A) (conductive inorganic powder + glass frit).
  • the inorganic powder-containing composition according to the present invention includes a glass paste composition when the inorganic powder (A) is a glass powder, and a conductive composition when the inorganic powder (A) is a conductive inorganic powder. It becomes a thing.
  • alkali-soluble refers to a property of being dissolved by an alkaline developer and having such a solubility that the development using an alkaline developer is performed.
  • Such alkali-soluble resins include, for example, (meth) acrylic resins, hydroxys Examples include a tylene resin, a novolak resin, and a polyester resin.
  • alkali-soluble resins preferred are the following copolymers of monomer (a) and monomer (and copolymers of monomer (a), monomer (b) and monomer (c), and the like.
  • (Meth) acrylic resins are preferred, and more preferably a methacrylate copolymer obtained by copolymerizing a methacrylate monomer from the viewpoint of excellent thermal decomposability during firing.
  • Acrylic acid methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, mesaconic acid, cinnamic acid, succinic acid mono (2- (meth) atalyloic quichetyl), hexahydrophthalic acid mono (2- (Meta) ataryloy mouth quichetyl), monophthalic acid (2- (meta) ataliloyloxyshetyl), ⁇ - carboxy-polyproprotatonone mono (meta) acrylate.
  • Hydroxyl-containing monomers such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate; o-hydroxystyrene, m-hydroxystyrene, p-hydroxy A class of phenolic hydroxyl-containing monomers such as styrene.
  • copolymer of the monomer (a) and the monomer (c) and the copolymer of the monomer (a), the monomer (b) and the monomer (c) are composed of a monomer derived from the monomer (a).
  • the presence of the unit makes the compound soluble in alkali.
  • copolymers of monomer (a), monomer (b) and monomer (c) have excellent dispersion stability of inorganic powder (A) and dissolve in alkali developer described later. It is particularly preferable from the viewpoint of excellent properties.
  • the copolymer of the monomer (a) and the monomer (c) contains a structural unit derived from the monomer (a) in an amount of preferably 5 to 60% by mass, particularly preferably 10 to 40% by mass. I do. However, the total amount of the structural units derived from the monomer (a) and the monomer (c) shall be 100% by mass.
  • the copolymer of the monomer (a), the monomer (b) and the monomer (c) preferably contains 5 to 60% by mass, more preferably 10 40% by mass of the structural unit derived from the monomer (a). in containing the monomer (b) a constituent unit derived from preferably 1 one 50% by weight, particularly preferably in an amount of 5 30 wt 0/0.
  • the total amount of the structural units derived from the monomer (a), the monomer (b) and the monomer (c) is 100% by mass.
  • the constitutional unit derived from each of the above monomers is particularly preferably in the above range in terms of excellent dispersion stability of the inorganic particles and excellent solubility in an alkali developing solution described later.
  • the alkali-soluble resin (B) is obtained by copolymerizing the monomer (a) and the monomer (c) or the monomer (a), the monomer (b), and the monomer (c) by a conventionally known method. Can be manufactured.
  • the copolymer of the monomer (a) and the monomer (c) is preferably 5 to 60% by mass based on 100% by weight of the total amount of the monomer (a) and the monomer (c). %, particularly preferred properly is prepared using an amount of 10- 40 wt 0/0.
  • the copolymer of the monomer (a), the monomer (b) and the monomer (c) has a total amount of the monomer (a), the monomer (b) and the monomer (c) of 100% by mass.
  • the monomer (a) in an amount of preferably 5 to 60% by weight, particularly preferably 10 to 40% by weight, and the monomer (b) preferably in an amount of 1 to 50% by weight, particularly preferably 5 to 30% by weight. Is done.
  • the amount of each monomer is particularly preferably in the above range from the viewpoint that a copolymer having the above structural unit can be obtained.
  • alkali-soluble resin (B) glycidyl methacrylate or (meth) atalyliroxhetyl isocyanate is added to the alkali-soluble resin, and the alkali-soluble resin is polymerized by kneading. May be used.
  • the weight average molecular weight (Mw) of the alkali-soluble resin (B) is preferably 5,000 to 5,000,000, more preferably 10,000, and more preferably 10,000 to 300,000.
  • the Mw force S is preferably in the above range, since the solubility in an alkali developing solution is excellent and the film strength is sufficiently maintained when a transfer film is formed.
  • the content of the alkali-soluble resin (B) used in the present invention is usually 11 to 200 parts by mass, preferably 5 to 100 parts by mass with respect to 100 parts by mass of the inorganic powder (A). Particularly preferred is 10-80 parts by weight.
  • the compound (C) used in the present invention is at least one compound selected from the group consisting of the compound represented by the above formula (1) and the compound represented by the above formula (2). And has the effect of crosslinking the exposed portions of the coating film obtained from the composition containing an inorganic powder according to (1).
  • Examples of the compound (C1) represented by the formula (1) include trimetarylate such as trimethylolpropane triatalylate, pentaerythritol trimetatalate, and glycerin trimetatalate. These can be used alone or in combination of two or more. Among them, particularly preferred is trimethylolpropane trimethatalate.
  • Examples of the compound (C2) represented by the formula (2) include ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, polyethylene glycol dimethacrylate, and polypropylene glycol dimethacrylate. 1,3-butanediolesimethacrylate, 1,4-butanediol dimethacrylate, neopentylglycol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, 1,10- Examples include dimetharate such as decanediol dimetharate and glycerol dimetharate. These can be used alone or in combination of two or more. Of these, particularly preferred are ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, propylene glycol dimethacrylate, and glycerol dimethacrylate.
  • the compound (C) either the compound (C1) or the compound (C2) may be used, but it is preferable to use them in combination.
  • the sum of the compounds (C1) and (C2) shall be 1. It is preferable that the mass ratio is within the above range, since the pattern accuracy of the formed inorganic sintered body is excellent.
  • the content of the compound (C) is 100 parts by mass with respect to 100 parts by mass of the alkali-soluble resin (B). Parts by mass or less, and more preferably 20 to 80 parts by mass. If the amount is less than 20 parts by mass, it may be difficult to form a pattern of the inorganic sintered body due to poor curing of the exposed portion. On the other hand, if it exceeds 100 parts by mass, the deformation of the pattern of the inorganic sintered body during firing may be large.
  • Examples of the photopolymerization initiator (D) include benzyl, benzoin, benzophenone, camphorquinone, 2-hydroxy-2-methynole-1-phenyl-2-propane_1-one, 1-hydroxycyclohexylphenyl ketone, , 2-Dimethoxy_2_phenylacetophenone, 2_methyl_ [4 '-(methylthio) phenyl]-2-morpholino-1-propanone, 2-benzyl-2-dimethylamino_1_ (4-morpholino Carbonyl compounds such as phenyl) -butan-1-one; azo compounds or azide compounds such as azoisobutyronitrile and 4_azidobenzaldehyde; organic sulfur compounds such as mercaptan disulfide; benzoyl peroxide, dibenzoyl peroxide I-tert-butylperoxide, tert-butylhydride peroxide, cumenehydride per
  • the content of the photopolymerization initiator (D) is usually 1 to 100 parts by mass, preferably 5 to 50 parts by mass with respect to 100 parts by mass of the compound (C). It is preferable that the content is within the above range, since the accuracy of the pattern of the formed inorganic sintered body is excellent.
  • the inorganic powder-containing composition according to the present invention usually contains a solvent in order to impart appropriate fluidity or plasticity and good film-forming properties.
  • a solvent has good affinity for the inorganic powder (A) and good solubility of the alkali-soluble resin, and can impart appropriate viscosity to the inorganic powder-containing composition, and can be dried by drying. Preferably, it can be easily removed by evaporation.
  • Particularly preferred solvents include ketones, alcohols, and esters having a standard boiling point (boiling point at 1 atm) of 100 to 200 ° C.
  • ketones examples include getyl ketone, methyl butyl ketone, dipropyl ketone, and cyclohexanone.
  • alcohols examples include alcohols such as n-pentanol, 4-methinolene 2-pentanol, cyclohexanol, and diacetone alcohol; ethylene glycol monomethyl ether, ethylene glycol monomethyl ether ether, ethylene glycol monoethyl alcohol, and the like.
  • ether alcohols such as phenol glycolone monomethinoleate and propylene glycolone monoethylene phenol.
  • esters examples include alkyl esters of saturated aliphatic monocarbonates such as mono-n-butyl acetate and amyl acetate; lactate esters such as ethyl lactate and n-butyl lactate; Athenole esters such as tinoreserosonolebu acetate, propylene glycolone monomethinoleate enorea acetate, etinole 3-ethoxypropionate, and the like.
  • methyl butyl ketone, cyclohexanone, diacetone alcohol, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, ethyl lactate, propylene glycol monomethyl ether acetate, ethinoleate 3-ethoxypropionate and the like are preferred.
  • solvents other than the above-mentioned solvents include turpentine oil, ethyl ethyl solvate, methyl ethyl solvate, terpineol, butyl carbitol acetate, butynolecanolebitone, isopropyl alcohol, benzyl alcohol and the like.
  • the content of the solvent (E) in the composition containing an inorganic powder according to the present invention can be appropriately selected within a range where good film-forming properties (fluidity or plasticity) can be obtained.
  • the amount is usually from 90 to 90% by mass, and preferably from 5 to 70% by mass, based on the total amount of the composition containing the inorganic powder.
  • the inorganic powder-containing composition according to the present invention as an optional component, a plasticizer, a dispersant, Contains various additives such as development accelerator, adhesion aid, antihalation agent, leveling agent, storage stabilizer, defoamer, antioxidant, ultraviolet absorber, sensitizer, and chain transfer agent. Good.
  • the inorganic powder-containing composition according to the present invention comprises the inorganic powder (A), an alkali-soluble resin (B), a compound (C), a photopolymerization initiator (D), and, if necessary, a solvent (E).
  • the additive (F) can be prepared by kneading using a kneading machine such as a roll kneader, a mixer, a homomixer, a ball mill, a bead mill and the like.
  • composition containing inorganic powder prepared as described above is a paste-like composition having fluidity suitable for application, and its rice occupancy is usually 100-1,000,000. , 000cp, preferably 500 to 300, OOOcp.
  • the transfer film according to the present invention is composed of a support film and a layer obtained on the support film from the composition containing an inorganic powder.
  • a transfer film is obtained, for example, by applying the above-mentioned inorganic powder-containing composition on a support film and drying the coating film.
  • the support film constituting the transfer film is preferably a resin film having heat resistance and solvent resistance and having flexibility.
  • the paste-like composition can be applied by a roll coater, and the inorganic powder-containing composition can be stored and supplied in a rolled state.
  • the resin forming the support film examples include polyethylene terephthalate, polyester, polyethylene, polypropylene, polystyrene, polyimide, fluorine-containing resins such as polyvinyl alcohol, polyvinyl chloride, and polyfluoroethylene, nylon, and cellulose. That can be S.
  • the thickness of the supporting film is, for example, 20 lOOxm.
  • the surface of the support film to which the composition containing an inorganic powder is applied is preferably subjected to a release treatment. Thereby, in the transfer step described later, the operation of peeling the support film can be easily performed.
  • the composition can efficiently form a coating film having excellent uniformity in film thickness.
  • Preferred examples include a coating method using a roll coater, a coating method using a doctor blade, a coating method using a curtain coater, a coating method using a die coater, and a coating method using a wire coater.
  • the drying conditions of the coating film applied as described above are, for example, about 0.5 to 30 minutes at 50 150 ° C, and the residual ratio of the solvent after drying (the drying Content) is usually within 2% by mass.
  • the thickness of the coating film formed on the support film as described above varies depending on the content and size of the inorganic powder (A), the use of the inorganic sintered body, and the like. In the case of a coating film for forming a partition wall, for example, it is 5 to 50 zm.
  • a protective film layer which may be provided on the surface of the coating film for forming an inorganic sintered body a polyethylene film, a polyvinyl alcohol-based film, and the like can be given.
  • the inorganic sintered body when a glass paste composition is used as the inorganic powder-containing composition, a partition can be formed, and when a conductive composition is used, electrodes and the like can be formed. Can be formed.
  • a method for forming a layer (a coating film for forming an inorganic sintered body) using the composition containing an inorganic powder on a substrate a method for applying the composition containing an inorganic powder on a substrate, and a method according to the present invention.
  • a method of transferring a coating film for forming an inorganic sintered body onto a substrate by using a transfer film is exemplified.
  • a method using a transfer film is preferred, and a coating film for forming an inorganic sintered body having excellent film thickness uniformity can be easily formed. Can be achieved.
  • the radiation used is not particularly limited, but examples thereof include ultraviolet light such as a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, and a g-ray / gamma-ray stepper.
  • ultraviolet light such as a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, and a g-ray / gamma-ray stepper.
  • an electron beam, a laser beam and the like can also be used.
  • the radiation is ultraviolet light
  • the irradiation dose is usually 50-2000mjZcm.
  • Examples of the effective component of the alkaline developer include lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium hydrogen phosphate, diammonium hydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, and phosphoric acid.
  • Inorganic alkaline compounds such as lium and ammonia; tetramethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, monomethylamine, dimethylamine, trimethinoleamine, monoethylamine, getylamine, triethylamine, monoisopropylamine Reamin, diisopropyl ⁇ Min, organic alkaline compounds such as ethanol ⁇ Min, and the like.
  • the alkaline developer can be prepared by dissolving one or more of the alkaline compounds in water or the like.
  • concentration of the alkaline compound in the alkaline developer is usually from 0.001 to 10% by mass, preferably from 0.01 to 5% by mass.
  • the weight average molecular weight is the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) manufactured by Tosoh Corporation (device model name: HLC-802A). Amount.
  • the obtained copolymer (P1) had a polymerization conversion of 97% and a weight average molecular weight (Mw) in terms of polystyrene of 70,000.
  • a copolymer (P 2) was obtained in the same manner as in Synthesis Example 1 except that 35 parts of hexahydrophthalic acid mono (2-methacryloyl mouth xicetyl) was used in place of monosuccinic acid (2-methacryloy mouth mouth).
  • the obtained copolymer (P2) had a polymerization conversion of 97% and a weight average molecular weight (Mw) in terms of polystyrene of 66,000.
  • the obtained conductive composition (E1) was applied on a supporting film (200 mm in width, 30 m in length, 38 ⁇ m in thickness) using a die coater. 5 minutes to remove the solvent, and obtain a transfer film (F 1) having a 10 zm-thick electrode-forming coating film.
  • thermocompression bonding using a heating roller to form a coating film for electrode formation on a glass substrate.
  • the pressing conditions were as follows: the surface temperature of the heating roller was 90 ° C., the roll pressure was 2 kg / cm 2 , and the moving speed of the heating roller was 0.5 mZ.
  • i-line wavelength 365 nm
  • the glass substrate on which the electrode pattern was formed was fired in a firing furnace at a temperature of 590 ° C. for 15 minutes to remove organic components, thereby forming an electrode.
  • the conductive composition (E1) cured with ultraviolet light of 400 mj / cm 2 was placed on a thermobalance, When the temperature was raised at a rate of 20 ° C / min and the weight loss was measured, the weight loss was completed by 380 ° C, and the thermal decomposability of the organic components was good.
  • a conductive composition (E3) was produced in the same manner as in Example 1 except that 12.5 parts of glycerol dimethacrylate was used instead of propylene glycol dimethacrylate, and an electrode was formed thereafter. Was. As a result, an electrode could be formed in the same manner as in Example 1.
  • Example 1 Same as Example 1 except that 12.5 parts of trimethylolpropane triatalylate was used instead of trimethylolpropane trimetharate, and 12.5 parts of propylene glycol diatalylate was used instead of propylene glycol dimethacrylate. Then, a conductive composition (CE1) was manufactured, and then an electrode was formed. As a result, a target electrode could be formed as in Example 1.
  • the obtained glass paste composition (G1) was applied using a die coater on a support film (200 mm in width, 30 m in length, 38 ⁇ in thickness) composed of a PET film, and the coating was coated at 100 ° C. After drying at C for 5 minutes to remove the solvent, a transfer film (F1) having a glass sintered body forming coating film having a thickness of S10 / m was prepared.
  • the coating film for forming a glass sintered body of the obtained transfer film (F1) is applied to the surface of the glass substrate.
  • the sheets were overlapped so as to be in contact with each other, transferred by thermocompression bonding using a heating roller, and a coating film for forming a glass sintered body was formed on a glass substrate.
  • the crimping conditions are as follows: the surface temperature of the heating roller is 90 ° C, The moving speed of the heating roller was set to 0.5 mZ.
  • the support film was exposed to ultraviolet light (i-line: wavelength 365 nm) of 800 mJ / cm 2 from the support film side, and then the support film was peeled off.
  • i-line wavelength 365 nm
  • development processing is performed by a shower method using a 0.6% by mass aqueous solution of sodium carbonate (30 ° C.) as a developing solution, and then a shower of ultrapure water is applied for 1 minute to remove unexposed portions of ultraviolet rays. Removed. Further, a drying process was performed to form a partition pattern on the substrate.
  • the glass substrate on which the partition pattern was formed was baked in a firing furnace at a temperature of 590 ° C. for 15 minutes to remove organic components, thereby forming a partition made of a sintered glass body. .
  • the glass paste composition (G1) cured with 800 mj / cm 2 ultraviolet light was placed on a thermobalance. The sample was placed, the temperature was increased at a rate of 20 ° C / min, and the weight loss was measured. The weight reduction was completed by 380 ° C, and the thermal decomposability of the organic components was good.
  • the glass paste composition (P) was prepared in the same manner as in Example 4 except that 40 parts of the copolymer (P2) obtained in Synthesis Example 2 was used instead of the copolymer (P1) obtained in Synthesis Example 1. G2) was manufactured, and then a partition was formed. As a result, partition walls could be formed in the same manner as in Example 4.
  • the weight loss was measured in the same manner as in Example 4, the weight loss was completed up to 380 ° C. as in Example 4, and the thermal decomposability of the organic component was good.
  • a glass paste composition (G3) was produced in the same manner as in Example 4, except that 12.5 parts of glycerol dimetharate was used instead of propylene glycol dimetharate, and thereafter, partition walls were formed.
  • partition walls could be formed in the same manner as in Example G.
  • the weight loss was measured in the same manner as in Example 4, the weight loss was completed up to 380 ° C. as in Example 4, and the thermal decomposability of the organic component was good.
  • Example 4 Glass was prepared in the same manner as in Example 4 except that 10 parts of trimethylolpropane triatalylate was used instead of trimethylolpropane trimethacrylate, and 10 parts of propylene glycol diacrylate was used instead of propylene glycol dimethacrylate.
  • a paste composition (CG1) was manufactured, and then a partition was formed. As a result, a desired partition wall could be formed in the same manner as in Example 4.
  • the present invention relates to a novel composition containing an inorganic powder.
  • the inorganic powder-containing composition according to the present invention is excellent in the thermal decomposability of the organic component at the time of firing, and the organic component hardly remains in the formed inorganic sintered body such as the electrodes and the partition walls. Therefore, it is useful as a member forming material for field emission display (FED), plasma display panel (PDP), and inorganic electorescence (inorganic EL), particularly as an electrode forming material and a partition forming material.
  • FED field emission display
  • PDP plasma display panel
  • inorganic EL inorganic electorescence

Abstract

An inorganic-powder-containing composition comprising (A) an inorganic powder, (B) an alkali-soluble resin, (C) a specific methacrylate compound, and (D) a photopolymerization initiator. Also provided is a method of forming an inorganic sinter, characterized by using the inorganic-powder-containing composition.

Description

明 細 書  Specification
無機粉体含有組成物、転写フィルムおよび無機焼結体の形成方法 技術分野  TECHNICAL FIELD The present invention relates to an inorganic powder-containing composition, a transfer film, and a method for forming an inorganic sintered body.
[0001] 本発明は、新規な無機粉体含有組成物、およびこれを用いた無機焼結体の形成 方法に関する。本発明の無機粉体含有組成物は焼成時の有機成分の熱分解性に 優れ、形成された無機焼結体に有機成分が残留しにくい。そのため、フィールドエミ ッシヨンディスプレイ（FED)、プラズマディスプレイパネル（PDP)、無機エレクト口ルミ ネッセンス（無機 EL)用の部材、特に導電性部材形成用材料や隔壁形成用材料とし て有用である。  The present invention relates to a novel inorganic powder-containing composition and a method for forming an inorganic sintered body using the composition. The inorganic powder-containing composition of the present invention is excellent in the thermal decomposability of the organic component during firing, and the organic component hardly remains in the formed inorganic sintered body. Therefore, it is useful as a member for field emission display (FED), plasma display panel (PDP), and inorganic electorescence (inorganic EL), particularly as a material for forming a conductive member or a material for forming a partition wall.
背景技術  Background art
[0002] 近年、情報社会の発展により、通信、視野情報の受け渡し機能の役割を担うディス プレイの用途が拡大し、その重要性が高まっている。このような中、液晶ディスプレイ（  [0002] In recent years, with the development of the information society, the use of a display that plays a role of communication and transmission / reception of visual field information has been expanded and its importance has been increased. Under such circumstances, liquid crystal displays (
D)等の平面型ディスプレイが開発されている。この中でフィールドェミッションデイス プレイは、自発光型、広視野角、高応答速度、高精細、低消費電力という優れた性 能を有し注目されている。 Flat displays such as D) have been developed. Among them, field emission displays have attracted attention because of their excellent performance of self-luminous type, wide viewing angle, high response speed, high definition, and low power consumption.
[0003] フィールドェミッションディスプレイは電界印加によって陰極から真空中に電子を放 出させ、その電子を陽極上の蛍光体に照射することにより発光、表示を行うディスプ レイである。 [0003] A field emission display is a display that emits electrons from a cathode into a vacuum by applying an electric field and irradiates the electrons on a phosphor on an anode to emit light and display.
このようなディスプレイに用いられる電極や隔壁などの部材のパターンの形成方法 としては（1)ペースト状の部材形成用組成物を用いてスクリーン印刷によりパターンを 形成させるスクリーン印刷法、（2)感光性の部材形成用組成物層を形成し、フォトマ スクを介して紫外線を照射した上で現像することによりパターンを形成させるフォトリソ グラフィ一法 (たとえば、特許文献 1および 2)等が知られている。これらの方法では電 極や隔壁などの部材のパターンを形成した後、高温下で焼成を行い樹脂等の有機 成分を除去し、電極や隔壁などの部材を形成する。  As a method of forming a pattern of a member such as an electrode or a partition used in such a display, there are (1) a screen printing method of forming a pattern by screen printing using a paste-like composition for forming a member, and (2) a photosensitive method. There is known a photolithography method (for example, Patent Documents 1 and 2) in which a composition layer for forming a member is formed, and a pattern is formed by irradiating ultraviolet rays through a photomask and then developing. In these methods, after a pattern of members such as electrodes and partition walls is formed, baking is performed at a high temperature to remove organic components such as resin, thereby forming members such as electrodes and partition walls.
[0004] し力しながら、前記スクリーン印刷法では、部材パターンの位置精度が劣る、高精 細な部材パターンが形成できない、という問題がある。そのため、大型基板の部材、 高精細の部材を筆頭に、前記フォトリソグラフィ一法を用いて部材パターンの形成が 行われている。 However, in the screen printing method, the positional accuracy of the member pattern is poor, There is a problem that a fine member pattern cannot be formed. For this reason, a member pattern is formed by using the photolithography method, starting with a member of a large substrate and a member of high definition.
また、前記焼成過程において、有機成分の除去が不十分であると、ディスプレイの パネル性能が劣ることとなる。特にフィールドェミッションディスプレイでは陰極から電 子を放出するためにパネル内を真空にする必要があり、電極や隔壁などの部材中に 残留有機成分が多いと十分な真空度を得るのに時間を要する、或いは、時間ととも に真空度が低下し、それに伴いパネルの輝度が低下するという問題が発生する（特 許文献 3)。とりわけ、フォトリソグラフィ一法で用いられる感光性の部材形成用組成物 には、光重合開始剤によって架橋する不飽和化合物が含有されているため、焼成時 の有機成分の除去性能の向上が求められている。  In addition, if the removal of the organic components is insufficient in the firing step, the panel performance of the display is inferior. In particular, in a field emission display, it is necessary to evacuate the inside of the panel in order to emit electrons from the cathode, and if there is a large amount of residual organic components in the electrodes and partition walls, it takes time to obtain a sufficient degree of vacuum. Alternatively, there is a problem that the degree of vacuum decreases with time and the luminance of the panel decreases accordingly (Patent Document 3). In particular, the composition for forming a photosensitive member used in a photolithography method contains an unsaturated compound that is crosslinked by a photopolymerization initiator, and therefore, it is required to improve the performance of removing organic components during firing. ing.
[0005] この問題を解決するためには、有機成分を十分に除去するために、高温で長時間 焼成処理を行うことが必要になる。し力しながら、高温および長時間の焼成処理は、 ディスプレイ基板の変形や劣化という大きな問題につながるため、好ましくない。一方[0005] In order to solve this problem, it is necessary to perform a firing treatment at a high temperature for a long time in order to sufficiently remove the organic components. However, high-temperature and long-time baking treatment is not preferable because it leads to a serious problem of deformation and deterioration of the display substrate. on the other hand
、生産性向上の点からも、焼成時間の短縮化を目的として、焼成時の有機成分の除 去性能の向上が望まれている。 Also, from the viewpoint of improving productivity, it is desired to improve the performance of removing organic components during firing for the purpose of shortening the firing time.
特許文献 1：特開平 9 - 142878号公報  Patent Document 1: Japanese Patent Application Laid-Open No. 9-142878
特許文献 2：特開平 10 - 64435号公報  Patent Document 2: JP-A-10-64435
特許文献 3：特開平 8 - 171877号公報  Patent Document 3: JP-A-8-171877
発明の開示  Disclosure of the invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0006] 本発明は、電極パターンや隔壁パターン等の部材パターンの焼成時における有機 成分の熱分解性に優れ、形成された電極や隔壁等の無機焼結体に有機成分が残 留しにくい無機粉体含有組成物、およびこれを用いた無機焼結体の形成方法を提 供することを目的としている。 [0006] The present invention has an excellent thermal decomposition property of an organic component during firing of a member pattern such as an electrode pattern and a partition pattern, and an inorganic component in which an organic component hardly remains in an inorganic sintered body such as a formed electrode or a partition. It is an object of the present invention to provide a powder-containing composition and a method for forming an inorganic sintered body using the same.
また本発明は、前記無機粉体含有組成物から得られる塗膜を有し、ハンドリング性 、転写後の膜厚均一性に優れた転写フィルムを提供することを目的としている。 課題を解決するための手段 [0007] 本発明に係る無機粉体含有組成物は、（A)無機粉体、（B)アルカリ可溶性樹脂、 （ C)下記式（1)で表される化合物（以下、「化合物（C1)」ともレ、う）と下記式 (2)で表さ れる化合物（以下、「化合物（C2)」ともいう）とからなる群から選ばれる少なくとも 1種 の化合物（以下、これらをまとめて「ィ匕合物（C)」ともいう）、および (D)光重合開始剤 を含有することを特徴とする。 Another object of the present invention is to provide a transfer film having a coating film obtained from the inorganic powder-containing composition and having excellent handleability and uniformity of film thickness after transfer. Means for solving the problem [0007] The inorganic powder-containing composition according to the present invention comprises (A) an inorganic powder, (B) an alkali-soluble resin, (C) a compound represented by the following formula (1) (hereinafter, referred to as "compound (C1) And at least one compound selected from the group consisting of a compound represented by the following formula (2) (hereinafter also referred to as “compound (C2)”). And (D) a photopolymerization initiator.
[0008] [化 1]  [0008] [Formula 1]
( 1 )
Figure imgf000004_0001
(1)
Figure imgf000004_0001
[0009] [式（1)中、 R1は水素原子、水酸基、炭素数 1一 4のアルキル基または炭素数 1一 4の ヒドロキシアルキル基である。 ] [In the formula (1), R 1 is a hydrogen atom, a hydroxyl group, an alkyl group having 114 carbon atoms or a hydroxyalkyl group having 114 carbon atoms. ]
[0010] [化 2]
Figure imgf000004_0002
[0010] [Formula 2]
Figure imgf000004_0002
[0011] [式（2)中、 ITは（CH CH〇）、 (CH CH (CH )〇） 、 CH CH (OH) CH 0、 CH C [0011] [In equation (2), IT is (CH CH〇), (CH CH (CH) 〇), CH CH (OH) CH 0, CH C
2 2 a 2 3 b 2 2 2 2 2 a 2 3 b 2 2 2
H CH (CH ) 0または炭素数 2— 18のアルキレン基である。 aおよび bは各々独立にH CH (CH) 0 or an alkylene group having 2 to 18 carbon atoms. a and b are each independently
2 3 twenty three
1一 12の数である。 ]  It is a number of 1 to 12. ]
上記無機粉体 (A)は、導電性無機粉体またはガラス粉体であることが好ましい。 上記アルカリ可溶性樹脂（B)は、メタタリレート共重合体であることが好ましい。  The inorganic powder (A) is preferably a conductive inorganic powder or a glass powder. It is preferable that the alkali-soluble resin (B) is a methacrylate copolymer.
[0012] 本発明に係る転写フィルムは、支持フィルムと、この支持フィルム上に上記無機粉 体含有組成物を用いて形成された層とからなることを特徴とする。 [0012] The transfer film according to the present invention is characterized by comprising a support film and a layer formed on the support film using the inorganic powder-containing composition.
本発明に係る無機焼結体の形成方法は、  The method for forming an inorganic sintered body according to the present invention,
(i)基板上に上記無機粉体含有組成物を用いて層を形成し、 (ii)所望のパターンに放射線を照射して前記層を露光させ、露光部分を架橋させ てアルカリ性現像液に対して不溶化した後、 (i) forming a layer on the substrate using the inorganic powder-containing composition, (ii) irradiating a desired pattern with radiation to expose the layer, cross-linking the exposed portion to make it insoluble in an alkaline developer,
(iii)アルカリ性現像液を使用して未露光部分を溶解、除去してパターンを形成し、 (iii) using an alkaline developer to dissolve and remove unexposed portions to form a pattern,
(iv)前記パターンを焼成処理する (iv) baking the pattern
ことを特徴とする。  It is characterized by that.
[0013] 上記無機焼結体の形成方法において、導電性無機粉体含有組成物を用いて層を 形成することにより、電極を形成することができる。また、ガラス粉体含有組成物を用 いて層を形成することにより、隔壁を形成することができる。  [0013] In the method of forming an inorganic sintered body, an electrode can be formed by forming a layer using the composition containing a conductive inorganic powder. In addition, a partition can be formed by forming a layer using the glass powder-containing composition.
発明の効果  The invention's effect
[0014] 本発明に係る無機粉体含有組成物は、部材パターンの焼成時における有機成分 の熱分解性に優れ、形成された電極や隔壁等の無機焼結体には有機成分が残留し にくい。  [0014] The inorganic powder-containing composition according to the present invention is excellent in the thermal decomposability of the organic component during firing of the member pattern, and the organic component hardly remains in the formed inorganic sintered body such as the electrodes and the partition walls. .
本発明に係る転写フィルムは、前記無機粉体含有組成物から得られる層が支持フ イルム上に形成されたものであり、ハンドリング性に優れている。この転写フィルムを 用いることにより、膜厚均一性に優れた部材形成用塗膜を得ることができる。  The transfer film according to the present invention has a layer obtained from the inorganic powder-containing composition formed on a support film, and has excellent handling properties. By using this transfer film, it is possible to obtain a member forming coating film having excellent film thickness uniformity.
[0015] また、本発明に係る無機焼結体の形成方法は、フィールドェミッションディスプレイ（ FED) ,プラズマディスプレイパネル（PDP)、無機エレクト口ルミネッセンス（無機 EL) 用の部材、特に電極や隔壁の形成に好適に用いられる。 [0015] Further, the method for forming an inorganic sintered body according to the present invention includes a method for forming a field emission display (FED), a plasma display panel (PDP), and a member for inorganic electorescence (inorganic EL), in particular, electrodes and partition walls. It is suitably used for forming.
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0016] 以下、本発明を具体的に説明する。 Hereinafter, the present invention will be described specifically.
<無機粉体含有組成物 >  <Inorganic powder-containing composition>
本発明に係る無機粉体含有組成物は、（A)無機粉体、（B)アルカリ可溶性樹脂、 ( C)上記式（1)、式 (2)で表される化合物、ならびに (D)光重合開始剤を含有する。  The inorganic powder-containing composition according to the present invention comprises (A) an inorganic powder, (B) an alkali-soluble resin, (C) a compound represented by the above formula (1) or (2), and (D) light Contains a polymerization initiator.
[0017] (A)無機粉体 (A) Inorganic powder
本発明に用いられる無機粉体としては、導電性無機粉体やガラス粉体などが挙げ られる。  Examples of the inorganic powder used in the present invention include a conductive inorganic powder and a glass powder.
ガラス粉体としては、たとえば、 （1)酸化亜鉛、酸化ホウ素、酸化ケィ素の混合物 (Z nO-B O -SiO系）、（2)酸化鉛、酸化ホウ素、酸化ケィ素の混合物（PbO— B O - SiO系）、（3)酸化鉛、酸化ホウ素、酸化ケィ素、酸化アルミニウムの混合物（Pb〇一Examples of the glass powder include (1) a mixture of zinc oxide, boron oxide, and silicon oxide (ZnO—B O —SiO system), and (2) a mixture of lead oxide, boron oxide, and silicon oxide (PbO— BO- (SiO-based), (3) a mixture of lead oxide, boron oxide, silicon oxide, and aluminum oxide (Pb
B O -SiO -A1〇系）、 （4)酸化鉛、酸化亜鉛、酸化ホウ素、酸化ケィ素の混合物（(B O -SiO -A1〇), (4) A mixture of lead oxide, zinc oxide, boron oxide, and silicon oxide (
PbO-ZnO-B O -SiO系）等を挙げることができる。これらのガラス粉体は 1種単独 でまたは 2種以上を混合して用レ、てもよい。ガラス粉体の軟化点は、無機焼結体形成 における焼成温度の観点から、 400— 600°Cの範囲内にあることが好ましい。また、 ガラス粉体の平均粒子径は 0. 5-2. 5 z mの範囲内にあることが好ましい。 PbO-ZnO-B 2 O 3 -SiO system) and the like. These glass powders may be used alone or in combination of two or more. The softening point of the glass powder is preferably in the range of 400 to 600 ° C. from the viewpoint of the firing temperature in forming the inorganic sintered body. Further, the average particle size of the glass powder is preferably in the range of 0.5 to 2.5 zm.
[0018] 上記ガラス粉体は、たとえば、酸化アルミニウム、酸化クロム、酸化マンガン、酸化チ タン、酸化ジルコニウム、酸化ケィ素、酸化セリウム、酸化コバルトなどの無機酸化物 と併用することができる。併用する無機酸化物の含有量は、無機粉体 (A)全量 (ガラ ス粉体 +無機酸化物）に対して、好ましくは 30重量％以下である。  [0018] The glass powder can be used in combination with an inorganic oxide such as aluminum oxide, chromium oxide, manganese oxide, titanium oxide, zirconium oxide, silicon oxide, cerium oxide, and cobalt oxide. The content of the inorganic oxide used in combination is preferably 30% by weight or less based on the total amount of the inorganic powder (A) (glass powder + inorganic oxide).
導電性無機粉体としては、 Ag、 Au、 Cu、 Al、 Ag_Pd合金、 Cr、 Niなどの粒子を 挙げること力 Sできる。これらの導電性無機粉体は、単独でまたは 2種以上を組み合わ せて使用することができる。導電性無機粉体の粒径は、得られる電極に十分な導電 性を付与する点から 10 / m以下が好ましい。  Examples of the conductive inorganic powder include particles of Ag, Au, Cu, Al, Ag_Pd alloy, Cr, Ni, and the like. These conductive inorganic powders can be used alone or in combination of two or more. The particle diameter of the conductive inorganic powder is preferably 10 / m or less from the viewpoint of imparting sufficient conductivity to the obtained electrode.
[0019] 上記導電性無機粉体は、ガラスフリットと併用することができる。前記ガラスフリットの 組成としては、たとえば、上記ガラス粉体（1)一（4)の他、（5)酸化ビスマス、酸化ホウ 素、酸化ケィ素、酸化アルミニウムの混合物（Bi O -B O -SiO -Al O系）などを挙 げること力 Sできる。これらのガラスフリットの軟化点は、 400— 600°Cの範囲内にあるこ とが好ましい。併用するガラスフリットの含有量は、無機粉体 (A)全量 (導電性無機粉 体 +ガラスフリット）に対して、 50質量％以下、好ましくは 30質量％以下である。  [0019] The conductive inorganic powder can be used in combination with a glass frit. As the composition of the glass frit, for example, in addition to the above glass powder (1)-(4), (5) a mixture of bismuth oxide, boron oxide, silicon oxide, and aluminum oxide (BiO-BO-SiO- Al O) and others. The softening point of these glass frits is preferably in the range of 400 to 600 ° C. The content of the glass frit used in combination is 50% by mass or less, preferably 30% by mass or less, based on the total amount of the inorganic powder (A) (conductive inorganic powder + glass frit).
[0020] 本発明に係る無機粉体含有組成物は、上記無機粉体 (A)がガラス粉体からなる場 合にはガラスペースト組成物、導電性無機粉体からなる場合には導電性組成物とな る。 [0020] The inorganic powder-containing composition according to the present invention includes a glass paste composition when the inorganic powder (A) is a glass powder, and a conductive composition when the inorganic powder (A) is a conductive inorganic powder. It becomes a thing.
(B)アルカリ可溶性樹脂：  (B) Alkali-soluble resin:
本明細書における「アルカリ可溶性」とは、アルカリ性の現像液によって溶解し、ァ ルカリ性の現像液を使用した現像処理が遂行される程度に溶解性を有する性質をい う。  The term “alkali-soluble” as used herein refers to a property of being dissolved by an alkaline developer and having such a solubility that the development using an alkaline developer is performed.
[0021] このようなアルカリ可溶性樹脂としては、たとえば (メタ）アクリル系樹脂、ヒドロキシス チレン樹脂、ノボラック樹脂、ポリエステル樹脂などを挙げることができる。このようなァ ルカリ可溶性樹脂のうち、好ましいものとしては、下記のモノマー（a)とモノマー（ と の共重合体、モノマー（a)とモノマー（b)とモノマー（c)との共重合体などの（メタ）ァク リル系樹脂を挙げることができる。さらに好ましくは、焼成時の熱分解性に優れる点か ら、メタタリレートモノマーを共重合したメタタリレート共重合体であることが好ましい。 [0021] Such alkali-soluble resins include, for example, (meth) acrylic resins, hydroxys Examples include a tylene resin, a novolak resin, and a polyester resin. Among such alkali-soluble resins, preferred are the following copolymers of monomer (a) and monomer (and copolymers of monomer (a), monomer (b) and monomer (c), and the like. (Meth) acrylic resins are preferred, and more preferably a methacrylate copolymer obtained by copolymerizing a methacrylate monomer from the viewpoint of excellent thermal decomposability during firing.
[0022] モノマー（a)：カルボキシル基含有モノマー類  [0022] Monomer (a): Carboxyl group-containing monomers
アクリル酸、メタクリル酸、マレイン酸、フマル酸、クロトン酸、ィタコン酸、シトラコン酸 、メサコン酸、ケィ皮酸、コハク酸モノ（2— (メタ）アタリロイ口キシェチル）、 へキサヒドロ フタル酸モノ（2— (メタ）アタリロイ口キシェチル）、フタル酸モノ（2— (メタ）アタリロイロキ シェチル）、 ω—カルボキシーポリ力プロラタトンモノ（メタ）アタリレートなど。 Acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, mesaconic acid, cinnamic acid, succinic acid mono (2- (meth) atalyloic quichetyl), hexahydrophthalic acid mono (2- (Meta) ataryloy mouth quichetyl), monophthalic acid (2- (meta) ataliloyloxyshetyl), ω- carboxy-polyproprotatonone mono (meta) acrylate.
[0023] モノマー（b)：水酸基含有モノマー類  [0023] Monomer (b): hydroxyl group-containing monomers
(メタ）アクリル酸 2—ヒドロキシェチル、 （メタ）アクリル酸 2—ヒドロキシプロピル、（メタ） アクリル酸 3—ヒドロキシプロピルなどの水酸基含有モノマー類； o—ヒドロキシスチレン 、 m—ヒドロキシスチレン、 p—ヒドロキシスチレンなどのフエノール性水酸基含有モノマ 一類など。  Hydroxyl-containing monomers such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate; o-hydroxystyrene, m-hydroxystyrene, p-hydroxy A class of phenolic hydroxyl-containing monomers such as styrene.
[0024] モノマー（c)：その他の共重合可能なモノマー類  [0024] Monomer (c): Other copolymerizable monomers
(メタ）アクリル酸メチル、（メタ）アクリル酸ェチル、（メタ）アクリル酸 n-ブチル、（メタ） アクリル酸 2-ェチルへキシル、（メタ）アクリル酸 n-ラウリル、（メタ）アクリル酸ベンジ ノレ、（メタ）アクリル酸グリシジル、（メタ）アクリル酸ジシクロペンタニルなどのモノマー（ a)以外の（メタ）アクリル酸エステル類;スチレン、 α -メチルスチレンなどの芳香族ビ ニル系モノマー類；ブタジエン、イソプレンなどの共役ジェン類；ポリスチレン、ポリ（メ タ）アクリル酸メチル、ポリ（メタ）アクリル酸ェチル、ポリ（メタ）アクリル酸ベンジル等の ポリマー鎖の一方の末端に (メタ）アタリロイル基などの重合性不飽和基を有するマク 口モノマー類など。  Methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-lauryl (meth) acrylate, benzinole (meth) acrylate (Meth) acrylates other than monomer (a), such as glycidyl (meth) acrylate and dicyclopentanyl (meth) acrylate; aromatic vinyl monomers such as styrene and α-methylstyrene; butadiene And conjugated diene such as isoprene; poly (meth) acrylate, poly (meth) acrylate, poly (meth) acrylate, benzyl poly (meth) acrylate, etc. Macromolecules having polymerizable unsaturated groups.
[0025] 上記モノマー（a)とモノマー（c)との共重合体や、モノマー（a)とモノマー（b)とモノ マー（c)との共重合体は、モノマー（a)に由来する構成単位の存在により、アルカリ可 溶性を有するものとなる。中でもモノマー（a)とモノマー（b)とモノマー（c)との共重合 体は、無機粉体 (A)の分散安定性に優れる点や、後述するアルカリ現像液への溶解 性に優れる点から、特に好ましい。 [0025] The copolymer of the monomer (a) and the monomer (c) and the copolymer of the monomer (a), the monomer (b) and the monomer (c) are composed of a monomer derived from the monomer (a). The presence of the unit makes the compound soluble in alkali. Above all, copolymers of monomer (a), monomer (b) and monomer (c) have excellent dispersion stability of inorganic powder (A) and dissolve in alkali developer described later. It is particularly preferable from the viewpoint of excellent properties.
[0026] 上記モノマー（a)とモノマー（c)との共重合体は、モノマー（a)に由来する構成単位 を好ましくは 5— 60質量％、特に好ましくは 10— 40質量％の量で含有する。ただし、 モノマー（a)およびモノマー（c)に由来する構成単位の合計量を 100質量％とする。 また、モノマー（a)とモノマー（b)とモノマー（c)との共重合体は、モノマー（a)に由来 する構成単位を好ましくは 5— 60質量％、特に好ましくは 10 40質量％の量で含有 し、モノマー（b)に由来する構成単位を好ましくは 1一 50質量％、特に好ましくは 5— 30質量0 /0の量で含有する。ただし、モノマー（a)、モノマー（b)およびモノマー（c)に 由来する構成単位の合計量を 100質量％とする。上記各モノマーに由来の構成単 位は、無機粒子の分散安定性に優れる点や、後述するアルカリ現像液への溶解性 に優れる点から、上記範囲にあることが特に好ましい。 [0026] The copolymer of the monomer (a) and the monomer (c) contains a structural unit derived from the monomer (a) in an amount of preferably 5 to 60% by mass, particularly preferably 10 to 40% by mass. I do. However, the total amount of the structural units derived from the monomer (a) and the monomer (c) shall be 100% by mass. The copolymer of the monomer (a), the monomer (b) and the monomer (c) preferably contains 5 to 60% by mass, more preferably 10 40% by mass of the structural unit derived from the monomer (a). in containing the monomer (b) a constituent unit derived from preferably 1 one 50% by weight, particularly preferably in an amount of 5 30 wt 0/0. However, the total amount of the structural units derived from the monomer (a), the monomer (b) and the monomer (c) is 100% by mass. The constitutional unit derived from each of the above monomers is particularly preferably in the above range in terms of excellent dispersion stability of the inorganic particles and excellent solubility in an alkali developing solution described later.
[0027] アルカリ可溶性樹脂（B)は、上記モノマー（a)とモノマー（c)とを、または、モノマー（ a)とモノマー（b)とモノマー（c)とを、従来公知の方法で共重合することにより製造で きる。このとき、モノマー（a)とモノマー（c)との共重合体は、モノマー（a)とモノマー（c )との合計量 100重量％に対して、モノマー（a)を好ましくは 5— 60質量％、特に好ま しくは 10— 40質量0 /0の量使用して製造される。また、モノマー（a)とモノマー（b)とモ ノマー（c)との共重合体は、モノマー（a)とモノマー（b)とモノマー（c)との合計量を 10 0質量％に対して、モノマー（a)を好ましくは 5— 60質量％、特に好ましくは 10— 40 質量％の量、モノマー（b)を好ましくは 1一 50質量％、特に好ましくは 5— 30質量％ 使用して製造される。各モノマーの使用量は、上記構成単位を有する共重合を得る ことができる点から、上記範囲にあることが特に好ましい。 The alkali-soluble resin (B) is obtained by copolymerizing the monomer (a) and the monomer (c) or the monomer (a), the monomer (b), and the monomer (c) by a conventionally known method. Can be manufactured. At this time, the copolymer of the monomer (a) and the monomer (c) is preferably 5 to 60% by mass based on 100% by weight of the total amount of the monomer (a) and the monomer (c). %, particularly preferred properly is prepared using an amount of 10- 40 wt 0/0. Further, the copolymer of the monomer (a), the monomer (b) and the monomer (c) has a total amount of the monomer (a), the monomer (b) and the monomer (c) of 100% by mass. Prepared using the monomer (a) in an amount of preferably 5 to 60% by weight, particularly preferably 10 to 40% by weight, and the monomer (b) preferably in an amount of 1 to 50% by weight, particularly preferably 5 to 30% by weight. Is done. The amount of each monomer is particularly preferably in the above range from the viewpoint that a copolymer having the above structural unit can be obtained.
[0028] また、アルカリ可溶性樹脂（B)として、上記アルカリ可溶性樹脂にグリシジルメタタリ レート、または (メタ）アタリロイロキシェチルイソシァネートを付カ卩重合し、アルカリ可 溶性樹脂に不飽和基を導入した樹脂を用いることもできる。  [0028] Further, as the alkali-soluble resin (B), glycidyl methacrylate or (meth) atalyliroxhetyl isocyanate is added to the alkali-soluble resin, and the alkali-soluble resin is polymerized by kneading. May be used.
アルカリ可溶性樹脂（B)の重量平均分子量（Mw)は、 5, 000— 5, 000， 000であ ること力 S好ましく、さらに好ましくは 10, 000 300， 000とされる。 Mw力 S上記範囲に あると、アルカリ現像液への溶解性に優れ、転写フィルムを形成したときにフィルム強 度が十分保たれる点から、好ましい。 [0029] また、本発明に用いられるアルカリ可溶性樹脂（B)の含有量は、無機粉体 (A) 100 質量部に対して、通常 1一 200質量部であり、好ましくは 5— 100質量部、特に好まし くは 10— 80質量部である。 The weight average molecular weight (Mw) of the alkali-soluble resin (B) is preferably 5,000 to 5,000,000, more preferably 10,000, and more preferably 10,000 to 300,000. The Mw force S is preferably in the above range, since the solubility in an alkali developing solution is excellent and the film strength is sufficiently maintained when a transfer film is formed. [0029] The content of the alkali-soluble resin (B) used in the present invention is usually 11 to 200 parts by mass, preferably 5 to 100 parts by mass with respect to 100 parts by mass of the inorganic powder (A). Particularly preferred is 10-80 parts by weight.
(C)メタクリロイル基含有化合物  (C) Methacryloyl group-containing compound
本発明に用いられる化合物（C)は、上記式（1)で表される化合物と上記式 (2)で表 される化合物とからなる群からとから選ばれる少なくとも一種の化合物であり、本発明 に係る無機粉体含有組成物から得られた塗膜の露光部分を架橋させる効果を有す る。  The compound (C) used in the present invention is at least one compound selected from the group consisting of the compound represented by the above formula (1) and the compound represented by the above formula (2). And has the effect of crosslinking the exposed portions of the coating film obtained from the composition containing an inorganic powder according to (1).
[0030] 式（1)で表される化合物（C1)としては、トリメチロールプロパントリアタリレート、ペン タエリスリトールトリメタタリレート、グリセリントリメタタリレートなどのトリメタタリレートが挙 げられる。これらは単独で、または 2種以上を組み合わせて使用することができる。こ れらの中で、特に好ましいものはトリメチロールプロパントリメタタリレートである。  [0030] Examples of the compound (C1) represented by the formula (1) include trimetarylate such as trimethylolpropane triatalylate, pentaerythritol trimetatalate, and glycerin trimetatalate. These can be used alone or in combination of two or more. Among them, particularly preferred is trimethylolpropane trimethatalate.
[0031] 式（2)で表される化合物（C2)としては、エチレングリコールジメタタリレート、ジェチ レングリコールジメタタリレート、プロピレングリコールジメタタリレート、ポリエチレングリ コールジメタタリレート、ポリプロピレングリコールジメタタリレート、 1, 3—ブタンジォー ノレジメタクリレート、 1 , 4一ブタンジオールジメタタリレート、ネオペンチルグリコールジ メタタリレート、 1 , 6—へキサンジオールジメタタリレート、 1 , 9ーノナンジオールジメタク リレート、 1, 10—デカンジオールジメタタリレート、グリセロールジメタタリレートなどの ジメタタリレートが挙げられる。これらは単独で、または 2種以上を組み合わせて使用 すること力 Sできる。これらの中で、特に好ましいものは、エチレングリコールジメタクリレ ート、ジエチレングリコールジメタタリレート、プロピレングリコールジメタタリレート、グリ セロールジメタタリレートである。  [0031] Examples of the compound (C2) represented by the formula (2) include ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, polyethylene glycol dimethacrylate, and polypropylene glycol dimethacrylate. 1,3-butanediolesimethacrylate, 1,4-butanediol dimethacrylate, neopentylglycol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, 1,10- Examples include dimetharate such as decanediol dimetharate and glycerol dimetharate. These can be used alone or in combination of two or more. Of these, particularly preferred are ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, propylene glycol dimethacrylate, and glycerol dimethacrylate.
[0032] また、化合物（C)として、化合物（C1)と化合物（C2)のいずれか一方を用いてもよ いが、併用することが好ましい。併用の場合、好ましくは質量比で (C1)： (C2) =0. 2 一 0. 8 : 0. 8-0. 2、特に好ましくは 0. 4-0. 7 : 0. 6—0. 3の害 U合である。ただし、 化合物（C1)と（C2)との合計を 1とする。質量比が上記範囲であると形成される無機 焼結体のパターンの精度に優れる点から、好ましい。  [0032] As the compound (C), either the compound (C1) or the compound (C2) may be used, but it is preferable to use them in combination. In the case of combined use, preferably, the mass ratio is (C1) :( C2) = 0.2-0.8: 0.8-0.2, particularly preferably 0.4-0.7: 0.6-0. It is a harm U of 3. However, the sum of the compounds (C1) and (C2) shall be 1. It is preferable that the mass ratio is within the above range, since the pattern accuracy of the formed inorganic sintered body is excellent.
[0033] 化合物（C)の含有量は、アルカリ可溶性樹脂（B) 100質量部に対して、 100質量 部以下であり、さらに 20— 80質量部であることが好ましい。 20質量部未満では、露 光部の硬化不良により、無機焼結体のパターンの形成が困難となることがある。また 、 100質量部を超えると焼成時の無機焼結体のパターンの変形が大きくなることがあ る。 [0033] The content of the compound (C) is 100 parts by mass with respect to 100 parts by mass of the alkali-soluble resin (B). Parts by mass or less, and more preferably 20 to 80 parts by mass. If the amount is less than 20 parts by mass, it may be difficult to form a pattern of the inorganic sintered body due to poor curing of the exposed portion. On the other hand, if it exceeds 100 parts by mass, the deformation of the pattern of the inorganic sintered body during firing may be large.
(D)光重合開始剤  (D) Photopolymerization initiator
光重合開始剤（D)としては、ベンジル、ベンゾイン、ベンゾフヱノン、カンファーキノ ン、 2—ヒドロキシ _2—メチノレ一 1—フエ二ノレプロハ°ン_1—オン、 1—ヒドロキシシクロへキ シルフェニルケトン、 2, 2—ジメトキシ _2_フエニルァセトフエノン、 2_メチル _〔4'— (メ チルチオ）フエ二ル〕— 2—モルフォリノ— 1—プロパノン、 2—ベンジル— 2—ジメチルァミノ _1_ (4—モルフォリノフエ二ル)—ブタン一 1_オンなどのカルボニル化合物；ァゾイソブ チロニトリル、 4_アジドベンズアルデヒドなどのァゾ化合物あるいはアジド化合物；メ ルカブタンジスルフイドなどの有機硫黄化合物；ベンゾィルパーォキシド、ジ一 tert— ブチルパーォキシド、 tert—ブチルハイド口パーォキシド、クメンハイド口パーォキシド 、パラメタンハイド口パーォキシドなどの有機パーォキシド； 1, 3_ビス（トリクロロメチル )_5_(2，_クロロフェニル）_1 , 3, 5—トリアジン、 2_〔2_ (2_フラニル）ェチレニル〕_ 4, 6—ビス（トリクロロメチル)一1 , 3, 5—トリァジンなどのトリハロメタン類； 2, 2'—ビス（ 2_クロ口フエニル） 4, 5, 4' , 5 '—テトラフ工ニル 1, 2，—ビイミダゾールなどのイミダゾ 一ルニ量体などを挙げることができる。これらは単独でまたは 2種以上を組み合わせ て使用すること力できる。  Examples of the photopolymerization initiator (D) include benzyl, benzoin, benzophenone, camphorquinone, 2-hydroxy-2-methynole-1-phenyl-2-propane_1-one, 1-hydroxycyclohexylphenyl ketone, , 2-Dimethoxy_2_phenylacetophenone, 2_methyl_ [4 '-(methylthio) phenyl]-2-morpholino-1-propanone, 2-benzyl-2-dimethylamino_1_ (4-morpholino Carbonyl compounds such as phenyl) -butan-1-one; azo compounds or azide compounds such as azoisobutyronitrile and 4_azidobenzaldehyde; organic sulfur compounds such as mercaptan disulfide; benzoyl peroxide, dibenzoyl peroxide I-tert-butylperoxide, tert-butylhydride peroxide, cumenehydride peroxide, paramethanehydride Organic peroxides such as peroxide; 1,3_bis (trichloromethyl) _5_ (2, _chlorophenyl) _1,3,5-triazine, 2_ [2_ (2_furanyl) ethylenyl] _4,6-bis (trichloromethyl) Trihalomethanes such as 1,3,5-triazine; imidazo such as 2,2'-bis (2_chlorophenyl) 4,5,4 ', 5'-tetrafuconyl 1,2, -biimidazole Lunimer and the like can be mentioned. These can be used alone or in combination of two or more.
光重合開始剤（D)の含有量は、化合物（C) 100質量部に対して、通常、 1一 100 質量部であり、好ましくは、 5— 50質量部である。含有量が上記範囲であると形成さ れる無機焼結体のパターンの精度に優れる点から、好ましい。  The content of the photopolymerization initiator (D) is usually 1 to 100 parts by mass, preferably 5 to 50 parts by mass with respect to 100 parts by mass of the compound (C). It is preferable that the content is within the above range, since the accuracy of the pattern of the formed inorganic sintered body is excellent.
(E)溶剤  (E) Solvent
本発明に係る無機粉体含有組成物には、通常、適当な流動性または可塑性、良好 な膜形成性を付与するために、溶剤が含有される。このような溶剤としては、無機粉 体 (A)との親和性、アルカリ可溶性樹脂の溶解性が良好で、無機粉体含有組成物に 適度な粘性を付与することができると共に、乾燥することにより容易に蒸発除去できる ものであることが好ましい。 [0035] 特に好ましい溶剤として、標準沸点（1気圧における沸点）が 100— 200°Cであるケ トン類、アルコール類およびエステル類を挙げることができる。 The inorganic powder-containing composition according to the present invention usually contains a solvent in order to impart appropriate fluidity or plasticity and good film-forming properties. Such a solvent has good affinity for the inorganic powder (A) and good solubility of the alkali-soluble resin, and can impart appropriate viscosity to the inorganic powder-containing composition, and can be dried by drying. Preferably, it can be easily removed by evaporation. Particularly preferred solvents include ketones, alcohols, and esters having a standard boiling point (boiling point at 1 atm) of 100 to 200 ° C.
上記ケトン類としては、ジェチルケトン、メチルブチルケトン、ジプロピルケトン、シク 口へキサノンなどが挙げられる。  Examples of the ketones include getyl ketone, methyl butyl ketone, dipropyl ketone, and cyclohexanone.
上記アルコール類としては、 n—ペンタノール、 4ーメチノレー 2_ペンタノール、シクロへ キサノール、ジアセトンアルコールなどのアルコール類；エチレングリコールモノメチル エーテノレ、エチレングリコーノレモノェチノレエーテノレ、エチレングリコーノレモノブチノレエ ーテノレ、プロピレングリコーノレモノメチノレエーテノレ、プロピレングリコーノレモノェチノレエ 一テルなどのエーテル系アルコール類などが挙げられる。  Examples of the above-mentioned alcohols include alcohols such as n-pentanol, 4-methinolene 2-pentanol, cyclohexanol, and diacetone alcohol; ethylene glycol monomethyl ether, ethylene glycol monomethyl ether ether, ethylene glycol monoethyl alcohol, and the like. And ether alcohols such as phenol glycolone monomethinoleate and propylene glycolone monoethylene phenol.
[0036] 上記エステル類としては、酢酸一 n—ブチル、酢酸ァミルなどの飽和脂肪族モノカル ボン酸アルキルエステル類；乳酸ェチル、乳酸 _n_ブチルなどの乳酸エステル類；メ チノレセロソノレブアセテート、ェチノレセロソノレブアセテート、プロピレングリコーノレモノメ チノレエーテノレアセテート、ェチノレー 3—エトキシプロピオネートなどのエーテノレ系エス テル類などが挙げられる。  [0036] Examples of the esters include alkyl esters of saturated aliphatic monocarbonates such as mono-n-butyl acetate and amyl acetate; lactate esters such as ethyl lactate and n-butyl lactate; Athenole esters such as tinoreserosonolebu acetate, propylene glycolone monomethinoleate enorea acetate, etinole 3-ethoxypropionate, and the like.
[0037] これらの溶斉 IJは、単独でまたは 2種以上を組み合わせて使用することができる。  [0037] These soluble IJs can be used alone or in combination of two or more.
これらのうち、メチルブチルケトン、シクロへキサノン、ジアセトンアルコール、ェチレ ングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、乳酸ェ チル、プロピレングリコールモノメチルエーテルアセテート、ェチノレー 3—エトキシプロピ ォネートなどが好ましい。  Of these, methyl butyl ketone, cyclohexanone, diacetone alcohol, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, ethyl lactate, propylene glycol monomethyl ether acetate, ethinoleate 3-ethoxypropionate and the like are preferred.
[0038] 上記例示した溶剤以外の溶剤としては、テレビン油、ェチルセ口ソルブ、メチルセ口 ソルブ、テルピネオール、ブチルカルビトールアセテート、ブチノレカノレビトーノレ、イソ プロピルアルコール、ベンジルアルコールなどを挙げることができる。  [0038] Examples of the solvents other than the above-mentioned solvents include turpentine oil, ethyl ethyl solvate, methyl ethyl solvate, terpineol, butyl carbitol acetate, butynolecanolebitone, isopropyl alcohol, benzyl alcohol and the like.
本発明に係る無機粉体含有組成物における溶剤 (E)の含有量は、良好な膜形成 性 (流動性または可塑性）が得られる範囲内において適宜選択することができる。  The content of the solvent (E) in the composition containing an inorganic powder according to the present invention can be appropriately selected within a range where good film-forming properties (fluidity or plasticity) can be obtained.
[0039] たとえば、無機粉体含有組成物全量に対して、通常 1一 90質量％、好ましくは 5— 70質量％である。  [0039] For example, the amount is usually from 90 to 90% by mass, and preferably from 5 to 70% by mass, based on the total amount of the composition containing the inorganic powder.
(F)添加剤  (F) additive
また、本発明に係る無機粉体含有組成物には、任意成分として、可塑剤、分散剤、 現像促進剤、接着助剤、ハレーション防止剤、レべリング剤、保存安定剤、消泡剤、 酸化防止剤、紫外線吸収剤、増感剤、連鎖移動剤などの各種添加剤が含有されて あよい。 Further, the inorganic powder-containing composition according to the present invention, as an optional component, a plasticizer, a dispersant, Contains various additives such as development accelerator, adhesion aid, antihalation agent, leveling agent, storage stabilizer, defoamer, antioxidant, ultraviolet absorber, sensitizer, and chain transfer agent. Good.
(組成物の調製方法）  (Method of preparing composition)
本発明に係る無機粉体含有組成物は、上記無機粉体 (A)、アルカリ可溶性樹脂（ B)、化合物 (C)、光重合開始剤 (D)、および必要に応じて溶剤 (E)と添加剤 (F)とを 、ロール混練機、ミキサー、ホモミキサー、ボールミル、ビーズミルなどの混練機を用 レ、て混練することにより調製することができる。  The inorganic powder-containing composition according to the present invention comprises the inorganic powder (A), an alkali-soluble resin (B), a compound (C), a photopolymerization initiator (D), and, if necessary, a solvent (E). The additive (F) can be prepared by kneading using a kneading machine such as a roll kneader, a mixer, a homomixer, a ball mill, a bead mill and the like.
[0040] 上記のようにして調製される無機粉体含有組成物は、塗布に適した流動性を有す るペースト状の組成物であり、その米占度 ίま、通常 100— 1 , 000， 000cp、好ましく fま 5 00— 300, OOOcpである。 [0040] The composition containing inorganic powder prepared as described above is a paste-like composition having fluidity suitable for application, and its rice occupancy is usually 100-1,000,000. , 000cp, preferably 500 to 300, OOOcp.
<転写フィルム >  <Transfer film>
本発明に係る転写フィルムは、支持フィルムと、この支持フィルム上に上記無機粉 体含有組成物から得られる層とから構成される。このような転写フィルムは、たとえば 支持フィルム上に上記無機粉体含有組成物を塗布し、この塗膜を乾燥することにより 得られる。転写フィルムを構成する支持フィルムは、耐熱性および耐溶剤性を有する と共に可撓性を有する樹脂フィルムであることが好ましレ、。支持フィルムが可撓性を 有することにより、ロールコータによってペースト状組成物を塗布することができ、無 機粉体含有組成物をロール状に卷回した状態で保存し、供給することができる。支 持フィルムを形成する樹脂としては、例えばポリエチレンテレフタレート、ポリエステノレ 、ポリエチレン、ポリプロピレン、ポリスチレン、ポリイミド、ポリビュルアルコール、ポリ 塩化ビュル、ポリフロロエチレンなどの含フッ素樹脂、ナイロン、セルロースなどを挙 げること力 Sできる。支持フィルムの厚さは、例えば 20 lOO x mである。  The transfer film according to the present invention is composed of a support film and a layer obtained on the support film from the composition containing an inorganic powder. Such a transfer film is obtained, for example, by applying the above-mentioned inorganic powder-containing composition on a support film and drying the coating film. The support film constituting the transfer film is preferably a resin film having heat resistance and solvent resistance and having flexibility. When the support film has flexibility, the paste-like composition can be applied by a roll coater, and the inorganic powder-containing composition can be stored and supplied in a rolled state. Examples of the resin forming the support film include polyethylene terephthalate, polyester, polyethylene, polypropylene, polystyrene, polyimide, fluorine-containing resins such as polyvinyl alcohol, polyvinyl chloride, and polyfluoroethylene, nylon, and cellulose. That can be S. The thickness of the supporting film is, for example, 20 lOOxm.
[0041] 無機粉体含有組成物が塗布される支持フィルムの表面には、離型処理が施されて レ、ることが好ましい。これにより、後述する転写工程において、支持フィルムの剥離操 作を容易に行うことができる。 [0041] The surface of the support film to which the composition containing an inorganic powder is applied is preferably subjected to a release treatment. Thereby, in the transfer step described later, the operation of peeling the support film can be easily performed.
無機粉体含有組成物を支持フィルム上に塗布する方法としては、膜厚の均一性に 優れた塗膜を効率よく形成することができるものであることが必要とされる。具体的に は、ロールコータによる塗布方法、ドクターブレードによる塗布方法、カーテンコータ による塗布方法、ダイコータによる塗布方法、ワイヤーコータによる塗布方法などを好 ましいものとして挙げることができる。 As a method of applying the inorganic powder-containing composition on the support film, it is necessary that the composition can efficiently form a coating film having excellent uniformity in film thickness. Specifically Preferred examples include a coating method using a roll coater, a coating method using a doctor blade, a coating method using a curtain coater, a coating method using a die coater, and a coating method using a wire coater.
[0042] 上記のようにして塗布された塗膜の乾燥条件は、例えば、 50 150°Cで 0. 5— 30 分間程度であり、乾燥後における溶剤の残存割合 (乾燥後の塗膜中の含有率）は、 通常 2質量％以内である。 [0042] The drying conditions of the coating film applied as described above are, for example, about 0.5 to 30 minutes at 50 150 ° C, and the residual ratio of the solvent after drying (the drying Content) is usually within 2% by mass.
上記のようにして支持フィルム上に形成された塗膜の厚さは、無機粉体 (A)の含有 率やサイズ、無機焼結体の用途などによっても異なるが、電極形成用の塗膜や隔壁 形成用の塗膜であれば、例えば 5— 50 z mである。なお、無機焼結体形成用塗膜の 表面に設けられることのある保護フィルム層としては、ポリエチレンフィルム、ポリビニ ルアルコール系フィルムなどを挙げることができる。  The thickness of the coating film formed on the support film as described above varies depending on the content and size of the inorganic powder (A), the use of the inorganic sintered body, and the like. In the case of a coating film for forming a partition wall, for example, it is 5 to 50 zm. In addition, as a protective film layer which may be provided on the surface of the coating film for forming an inorganic sintered body, a polyethylene film, a polyvinyl alcohol-based film, and the like can be given.
[0043] ぐ無機焼結体の形成方法 >  [0043] Method for Forming Inorganic Sintered Body>
本発明に係る無機焼結体の形成方法は、  The method for forming an inorganic sintered body according to the present invention,
(i)基板上に前記無機粉体含有組成物を用いて層を形成し、  (i) forming a layer on the substrate using the inorganic powder-containing composition,
(ii)所望のパターンに放射線を照射して前記層を露光させ、露光部分を架橋させ てアルカリ性現像液に対して不溶化させた後、  (ii) irradiating a desired pattern with radiation to expose the layer, cross-linking the exposed portion to make it insoluble in an alkaline developer,
(iii)アルカリ性現像液を使用して未露光部分を溶解、除去してパターンを形成し、 (iii) using an alkaline developer to dissolve and remove unexposed portions to form a pattern,
(iv)前記パターンを焼成処理する (iv) baking the pattern
ことを特徴とする。  It is characterized by that.
[0044] この無機焼結体の形成方法にぉレ、て上記無機粉体含有組成物としてガラスペース ト組成物を使用すると、隔壁を形成することができ、導電性組成物を使用すると電極 などの導電性部材を形成することができる。  According to the method of forming the inorganic sintered body, when a glass paste composition is used as the inorganic powder-containing composition, a partition can be formed, and when a conductive composition is used, electrodes and the like can be formed. Can be formed.
基板上に無機粉体含有組成物を用いて層（無機焼結体形成用塗膜)を形成する 方法としては、基板上に無機粉体含有組成物を塗布する方法や、本発明に係る転 写フィルムを用い、基板上に無機焼結体形成用塗膜を転写する方法が挙げられる。 これらの内、転写フィルムを用いる方法が好ましぐ膜厚均一性に優れた無機焼結体 形成用塗膜を容易に形成することができ、形成される無機焼結体パターンの膜厚均 一化を図ることができる。 [0045] 用いられる放射線としては、特に限定されるものではなレ、が、低圧水銀灯、高圧水 銀灯、メタルハライドランプ、 g線 ·ί線ステッパー等の紫外線が挙げられる。また、電子 線、レーザー光線等も挙げられる。 As a method for forming a layer (a coating film for forming an inorganic sintered body) using the composition containing an inorganic powder on a substrate, a method for applying the composition containing an inorganic powder on a substrate, and a method according to the present invention. A method of transferring a coating film for forming an inorganic sintered body onto a substrate by using a transfer film is exemplified. Of these, a method using a transfer film is preferred, and a coating film for forming an inorganic sintered body having excellent film thickness uniformity can be easily formed. Can be achieved. [0045] The radiation used is not particularly limited, but examples thereof include ultraviolet light such as a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, and a g-ray / gamma-ray stepper. In addition, an electron beam, a laser beam and the like can also be used.
放射線の照射は、放射線が紫外線の場合は、通常、所望のパターンを有するフォト マスクを介して照射することが好ましい。この場合、照射量は通常 50— 2000mjZc mである。  When the radiation is ultraviolet light, it is usually preferable to irradiate the radiation through a photomask having a desired pattern. In this case, the irradiation dose is usually 50-2000mjZcm.
[0046] 電子線あるいはレーザー光線等の場合は、直接所望のパターンに照射するのが好 ましい。  In the case of an electron beam or a laser beam, it is preferable to directly irradiate a desired pattern.
また、上記アルカリ性現像液の有効成分としては、例えば水酸化リチウム、水酸化 ナトリウム、水酸化カリウム、リン酸水素ナトリウム、リン酸水素二アンモニゥム、リン酸 水素二カリウム、リン酸水素ニナトリウム、リン酸二水素アンモニゥム、リン酸二水素力 リウム、リン酸二水素ナトリウム、ケィ酸リチウム、ケィ酸ナトリウム、ケィ酸カリウム、炭 酸リチウム、炭酸ナトリウム、炭酸カリウム、ホウ酸リチウム、ホウ酸ナトリウム、ホウ酸力 リウム、アンモニアなどの無機アルカリ性化合物；テトラメチルアンモニゥムヒドロキシド 、トリメチルヒドロキシェチルアンモニゥムヒドロキシド、モノメチルァミン、ジメチルアミ ン、トリメチノレアミン、モノェチルァミン、ジェチルァミン、トリェチルァミン、モノイソプロ ピノレアミン、ジイソプロピルァミン、エタノールァミンなどの有機アルカリ性化合物など を挙げることができる。  Examples of the effective component of the alkaline developer include lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium hydrogen phosphate, diammonium hydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, and phosphoric acid. Ammonium dihydrogen, potassium dihydrogen phosphate, sodium dihydrogen phosphate, lithium silicate, sodium silicate, potassium silicate, lithium carbonate, sodium carbonate, potassium carbonate, lithium borate, sodium borate, sodium borate Inorganic alkaline compounds such as lium and ammonia; tetramethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, monomethylamine, dimethylamine, trimethinoleamine, monoethylamine, getylamine, triethylamine, monoisopropylamine Reamin, diisopropyl § Min, organic alkaline compounds such as ethanol § Min, and the like.
[0047] アルカリ現像液は、前記アルカリ性化合物の 1種または 2種以上を水などに溶解さ せることにより調製すること力 Sできる。アルカリ性現像液におけるアルカリ性化合物の 濃度は、通常 0. 001— 10質量％とされ、好ましくは 0. 01— 5質量％とされる。  [0047] The alkaline developer can be prepared by dissolving one or more of the alkaline compounds in water or the like. The concentration of the alkaline compound in the alkaline developer is usually from 0.001 to 10% by mass, preferably from 0.01 to 5% by mass.
なお、アルカリ性現像液による現像処理がなされた後は、通常、水洗処理が施され る。 [実施例]  It should be noted that, after the development processing with the alkaline developer is performed, a water washing processing is usually performed. [Example]
以下、本発明の実施例について説明するが、本発明はこれらの実施例に限定され るものではない。なお、以下において「部」は「質量部」を示す。  Hereinafter, examples of the present invention will be described, but the present invention is not limited to these examples. In the following, “parts” indicates “parts by mass”.
[0048] ぐ重量平均分子量の測定方法 > [0048] Measuring method of weight average molecular weight>
重量平均分子量は、東ソー株式会社製ゲルパーミエーシヨンクロマトグラフィー（G PC) (装置機種名： HLC-802A)により測定したポリスチレン換算の重量平均分子 量である。 The weight average molecular weight is the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) manufactured by Tosoh Corporation (device model name: HLC-802A). Amount.
[合成例 1]  [Synthesis example 1]
くアルカリ可溶性樹脂の合成 >  Synthesis of alkali-soluble resin>
表 1に示した化合物を混合し、この混合物を攪拌器付きオートクレープに仕込み、 窒素雰囲気下で室温で均一になるまで攪拌した後、 80°Cで 3時間重合し、さらに 10 0°Cで 1時間反応を続けた後、室温まで冷却し、共重合体 (P1)の溶液を得た。  The compounds shown in Table 1 were mixed, and the mixture was charged into an autoclave equipped with a stirrer, stirred under a nitrogen atmosphere at room temperature until uniform, then polymerized at 80 ° C for 3 hours, and further polymerized at 100 ° C. After continuing the reaction for 1 hour, the solution was cooled to room temperature to obtain a solution of the copolymer (P1).
[表 1] 表 1  [Table 1] Table 1
Figure imgf000015_0001
Figure imgf000015_0001
[0050] 得られた共重合体 (P1)は、重合転化率が 97%であり、ポリスチレン換算重量平均 分子量（Mw)が 70, 000であった。 The obtained copolymer (P1) had a polymerization conversion of 97% and a weight average molecular weight (Mw) in terms of polystyrene of 70,000.
[合成例 2]  [Synthesis example 2]
くアルカリ可溶性樹脂の合成 >  Synthesis of alkali-soluble resin>
コハク酸モノ（2—メタクリロイ口キシェチル）の代わりに、へキサヒドロフタル酸モノ（2 ーメタクリロイ口キシェチル） 35部を用いた以外は合成例 1と同様にして、共重合体 (P 2)を得た。得られた共重合体 (P2)は、重合転化率が 97%であり、ポリスチレン換算 重量平均分子量（Mw)が 66, 000であった。  A copolymer (P 2) was obtained in the same manner as in Synthesis Example 1 except that 35 parts of hexahydrophthalic acid mono (2-methacryloyl mouth xicetyl) was used in place of monosuccinic acid (2-methacryloy mouth mouth). Was. The obtained copolymer (P2) had a polymerization conversion of 97% and a weight average molecular weight (Mw) in terms of polystyrene of 66,000.
[0051] ぐ導電性組成物および電極の作製 > Preparation of Conductive Composition and Electrode>
実施例 1  Example 1
[0052] 表 2に示す化合物を混合し、この混合物を分散機で混練することにより導電性組成 物（S1)を製造した。  [0052] The compounds shown in Table 2 were mixed, and the mixture was kneaded with a disperser to produce a conductive composition (S1).
[0053] [表 2] 表 2 [0053] [Table 2] Table 2
Figure imgf000016_0001
Figure imgf000016_0001
[0054] 得られた導電性組成物（E1 )を PETフィルムよりなる支持フィルム（幅 200mm、長 さ 30m、厚さ 38 μ ΐη)上にダイコーターを用いて塗布し、塗膜を 100°Cで 5分間乾燥 して溶剤を除去し、厚さが 10 z mの電極形成用塗膜を有する転写フィルム (F 1 )を [0054] The obtained conductive composition (E1) was applied on a supporting film (200 mm in width, 30 m in length, 38 μm in thickness) using a die coater. 5 minutes to remove the solvent, and obtain a transfer film (F 1) having a 10 zm-thick electrode-forming coating film.
E  E
作製した。  Produced.
得られた転写フィルム（F 1 )の電極形成用塗膜がガラス基板の表面に当接するよう  Make sure that the coating film for electrode formation of the obtained transfer film (F 1) is in contact with the surface of the glass substrate.
E  E
に重ね合わせ、加熱ローラにて熱圧着し転写を行い、ガラス基板上に電極形成用塗 膜を形成した。ここで圧着条件は、加熱ローラの表面温度を 90°C、ロール圧を 2kg/ cm2、加熱ローラの移動速度を 0. 5mZ分とした。 Then, transfer was performed by thermocompression bonding using a heating roller to form a coating film for electrode formation on a glass substrate. Here, the pressing conditions were as follows: the surface temperature of the heating roller was 90 ° C., the roll pressure was 2 kg / cm 2 , and the moving speed of the heating roller was 0.5 mZ.
[0055] 続いて、ガラス基板上に形成された電極形成用塗膜に対して、フォトマスク (L/S = 100/400 μ mのストライプパターン）を介して、支持フィルム側力、ら 400mj/cm2 の紫外線 (i線:波長 365nm)を露光させた後、支持フィルムを剥離した。 Then, the support film side force was applied to the electrode forming coating film formed on the glass substrate through a photomask (a stripe pattern of L / S = 100/400 μm). After exposure to ultraviolet light (i-line: wavelength 365 nm) of cm 2 , the support film was peeled off.
その後、 0· 6質量％の炭酸ナトリウム水溶液（30°C)を現像液とするシャワー法によ る現像処理を行い、次いで、 1分間超純水のシャワーを浴びせることにより、紫外線 未露光部を除去した。さらに乾燥処理を行ない、電極パターンを基板上に形成した。  Thereafter, development processing by a shower method using a 0.6% by mass aqueous solution of sodium carbonate (30 ° C.) as a developing solution is performed, and then a shower of ultrapure water is applied for 1 minute to remove unexposed portions of ultraviolet rays. Removed. Further, a drying process was performed to form an electrode pattern on the substrate.
[0056] その後、この電極パターンが形成されたガラス基板を焼成炉内で 590°Cの温度雰 囲気下で 15分間焼成を行い、有機成分を除去し、電極を形成した。  Thereafter, the glass substrate on which the electrode pattern was formed was fired in a firing furnace at a temperature of 590 ° C. for 15 minutes to remove organic components, thereby forming an electrode.
一方、 400mj/cm2の紫外線で硬化させた導電性組成物 (E1 )を熱天秤に載せ、 20°C/分の速度で昇温を行い、重量減少を測定したところ、 380°Cまでに重量減少 は完了し、有機成分の熱分解性が良好であつた。 On the other hand, the conductive composition (E1) cured with ultraviolet light of 400 mj / cm 2 was placed on a thermobalance, When the temperature was raised at a rate of 20 ° C / min and the weight loss was measured, the weight loss was completed by 380 ° C, and the thermal decomposability of the organic components was good.
実施例 2  Example 2
[0057] 合成例 1で得た共重合体 (P1)の代わりに合成例 2で得た共重合体 (P2) 50部を用 いた以外は、実施例 1と同様にして導電性組成物（E2)を製造し、その後、電極の形 成を行った。その結果、実施例 1と同様に電極を形成することができた。  [0057] Except that 50 parts of the copolymer (P2) obtained in Synthesis Example 2 was used instead of the copolymer (P1) obtained in Synthesis Example 1, the conductive composition ( E2) was manufactured, and then electrodes were formed. As a result, an electrode could be formed in the same manner as in Example 1.
また、実施例 1と同様にして重量減少を測定したところ、実施例 1と同様に 380°Cま でに重量減少は完了し、有機成分の熱分解性が良好であった。  When the weight loss was measured in the same manner as in Example 1, the weight loss was completed up to 380 ° C. as in Example 1, and the thermal decomposability of the organic component was good.
実施例 3  Example 3
[0058] プロピレングリコールジメタタリレートの代わりにグリセロールジメタタリレート 12. 5部 を用いた以外は、実施例 1と同様にして導電性組成物 (E3)を製造し、その後、電極 の形成を行った。その結果、実施例 1と同様に電極を形成することができた。  [0058] A conductive composition (E3) was produced in the same manner as in Example 1 except that 12.5 parts of glycerol dimethacrylate was used instead of propylene glycol dimethacrylate, and an electrode was formed thereafter. Was. As a result, an electrode could be formed in the same manner as in Example 1.
また、実施例 1と同様にして重量減少を測定したところ、実施例 1と同様に 380°Cま でに重量減少は完了し、有機成分の熱分解性が良好であった。  When the weight loss was measured in the same manner as in Example 1, the weight loss was completed up to 380 ° C. as in Example 1, and the thermal decomposability of the organic component was good.
[0059] [比較例 1]  [Comparative Example 1]
トリメチロールプロパントリメタタリレートの代わりにトリメチロールプロパントリアタリレー ト 12. 5部を、プロピレングリコールジメタタリレートの代わりにプロピレングリコールジ アタリレート 12. 5部を用いた以外は、実施例 1と同様にして導電性組成物（CE1)を 製造し、その後、電極の形成を行った。その結果、実施例 1と同様に目的とする電極 を形成することができた。  Same as Example 1 except that 12.5 parts of trimethylolpropane triatalylate was used instead of trimethylolpropane trimetharate, and 12.5 parts of propylene glycol diatalylate was used instead of propylene glycol dimethacrylate. Then, a conductive composition (CE1) was manufactured, and then an electrode was formed. As a result, a target electrode could be formed as in Example 1.
[0060] しかし、実施例 1と同様にして重量減少を測定したところ、重量減少が完了したのは 460°Cと高ぐ有機成分の熱分解性が劣った。 However, when the weight loss was measured in the same manner as in Example 1, the completion of the weight reduction was as high as 460 ° C., and the thermal decomposability of the organic component was poor.
<ガラスペースト組成物および隔壁の作製 >  <Preparation of glass paste composition and partition>
実施例 4  Example 4
[0061] 表 3に示した化合物を混合し、この混合物を分散機で混練することによりガラスペ一 スト組成物（G1)を製造した。  [0061] The compounds shown in Table 3 were mixed, and the mixture was kneaded with a disperser to produce a glass paste composition (G1).
[0062] [表 3] 表 3 [Table 3] Table 3
Figure imgf000018_0002
Figure imgf000018_0002
[0063] 得られたガラスペースト組成物（G1)を PETフィルムよりなる支持フィルム（幅 200m m、長さ 30m、厚さ 38 μ ΐη)上にダイコーターを用いて塗布し、塗膜を 100°Cで 5分 間乾燥して溶剤を除去し、厚さ力 S10 / mのガラス焼結体形成用塗膜を有する転写フ イルム（F 1)を作製した。 [0063] The obtained glass paste composition (G1) was applied using a die coater on a support film (200 mm in width, 30 m in length, 38 μΐη in thickness) composed of a PET film, and the coating was coated at 100 ° C. After drying at C for 5 minutes to remove the solvent, a transfer film (F1) having a glass sintered body forming coating film having a thickness of S10 / m was prepared.
G  G
得られた転写フィルム（F 1)のガラス焼結体形成用塗膜がガラス基板の表面に当  The coating film for forming a glass sintered body of the obtained transfer film (F1) is applied to the surface of the glass substrate.
G  G
接するように重ね合わせ、加熱ローラにて熱圧着し転写を行い、ガラス基板上にガラ ス焼結体形成用塗膜を形成した。ここで圧着条件は、加熱ローラの表面温度を 90°C 、
Figure imgf000018_0001
加熱ローラの移動速度を 0. 5mZ分とした。 The sheets were overlapped so as to be in contact with each other, transferred by thermocompression bonding using a heating roller, and a coating film for forming a glass sintered body was formed on a glass substrate. Here, the crimping conditions are as follows: the surface temperature of the heating roller is 90 ° C,
Figure imgf000018_0001
The moving speed of the heating roller was set to 0.5 mZ.
[0064] 続いて、ガラス基板上に形成されたガラス焼結体形成用塗膜に対して、フォトマスク  Subsequently, a photomask was applied to the glass sintered body forming coating film formed on the glass substrate.
(L/S = 200/200 μ mのストライプパターン）を介して、支持フィルム側から 800mJ /cm2の紫外線 (i線:波長 365nm)を露光させた後、支持フィルムを剥離した。 (L / S = 200/200 μm stripe pattern), the support film was exposed to ultraviolet light (i-line: wavelength 365 nm) of 800 mJ / cm 2 from the support film side, and then the support film was peeled off.
その後、 0. 6質量％の炭酸ナトリウム水溶液（30°C)を現像液とするシャワー法によ る現像処理を行い、次いで、 1分間超純水のシャワーを浴びせることにより、紫外線 未露光部を除去した。さらに乾燥処理を行ない、隔壁パターンを基板上に形成した。  Thereafter, development processing is performed by a shower method using a 0.6% by mass aqueous solution of sodium carbonate (30 ° C.) as a developing solution, and then a shower of ultrapure water is applied for 1 minute to remove unexposed portions of ultraviolet rays. Removed. Further, a drying process was performed to form a partition pattern on the substrate.
[0065] その後、この隔壁パターンが形成されたガラス基板を焼成炉内で 590°Cの温度雰 囲気下で 15分間焼成を行い、有機成分を除去し、ガラス焼結体からなる隔壁を形成 した。  Thereafter, the glass substrate on which the partition pattern was formed was baked in a firing furnace at a temperature of 590 ° C. for 15 minutes to remove organic components, thereby forming a partition made of a sintered glass body. .
一方、 800mj/cm2の紫外線で硬化させたガラスペースト組成物（G1)を熱天秤に 載せ、 20°C/分の速度で昇温を行い、重量減少を測定したところ、 380°Cまでに重 量減少は完了し、有機成分の熱分解性が良好であつた。 On the other hand, the glass paste composition (G1) cured with 800 mj / cm 2 ultraviolet light was placed on a thermobalance. The sample was placed, the temperature was increased at a rate of 20 ° C / min, and the weight loss was measured. The weight reduction was completed by 380 ° C, and the thermal decomposability of the organic components was good.
実施例 5  Example 5
[0066] 合成例 1で得た共重合体 (P1)の代わりに合成例 2で得た共重合体 (P2) 40部を用 いた以外は、実施例 4と同様にしてガラスペースト組成物（G2)を製造し、その後、隔 壁の形成を行った。その結果、実施例 4と同様に隔壁を形成することができた。 また、実施例 4と同様にして重量減少を測定したところ、実施例 4と同様に 380°Cま でに重量減少は完了し、有機成分の熱分解性が良好であった。  The glass paste composition (P) was prepared in the same manner as in Example 4 except that 40 parts of the copolymer (P2) obtained in Synthesis Example 2 was used instead of the copolymer (P1) obtained in Synthesis Example 1. G2) was manufactured, and then a partition was formed. As a result, partition walls could be formed in the same manner as in Example 4. When the weight loss was measured in the same manner as in Example 4, the weight loss was completed up to 380 ° C. as in Example 4, and the thermal decomposability of the organic component was good.
実施例 6  Example 6
[0067] プロピレングリコールジメタタリレートの代わりにグリセロールジメタタリレート 12. 5部 を用いた以外は、実施例 4と同様にしてガラスペースト組成物（G3)を製造し、その後 、隔壁の形成を行った。その結果、実施例 Gと同様に隔壁を形成することができた。 また、実施例 4と同様にして重量減少を測定したところ、実施例 4と同様に 380°Cま でに重量減少は完了し、有機成分の熱分解性が良好であった。  [0067] A glass paste composition (G3) was produced in the same manner as in Example 4, except that 12.5 parts of glycerol dimetharate was used instead of propylene glycol dimetharate, and thereafter, partition walls were formed. Was. As a result, partition walls could be formed in the same manner as in Example G. When the weight loss was measured in the same manner as in Example 4, the weight loss was completed up to 380 ° C. as in Example 4, and the thermal decomposability of the organic component was good.
[0068] [比較例 2]  [0068] [Comparative Example 2]
トリメチロールプロパントリメタタリレートの代わりにトリメチロールプロパントリアタリレー ト 10部を、プロピレングリコールジメタタリレートの代わりにプロピレングリコールジァク リレート 10部を用いた以外は、実施例 4と同様にしてガラスペースト組成物（CG1)を 製造し、その後、隔壁の形成を行った。その結果、実施例 4と同様に目的とする隔壁 を形成することができた。  Glass was prepared in the same manner as in Example 4 except that 10 parts of trimethylolpropane triatalylate was used instead of trimethylolpropane trimethacrylate, and 10 parts of propylene glycol diacrylate was used instead of propylene glycol dimethacrylate. A paste composition (CG1) was manufactured, and then a partition was formed. As a result, a desired partition wall could be formed in the same manner as in Example 4.
[0069] しかし、実施例 4と同様にして重量減少を測定したところ、重量減少が完了したのは [0069] However, when the weight loss was measured in the same manner as in Example 4, the weight reduction was completed.
460°Cと高ぐ有機成分の熱分解性が劣った。  Thermal decomposition of organic components as high as 460 ° C was poor.
産業上の利用可能性  Industrial applicability
[0070] 本発明は、新規な無機粉体含有組成物に関する。本発明に係る無機粉体含有組 成物は焼成時の有機成分の熱分解性に優れ、形成された電極や隔壁等の無機焼 結体に有機成分が残留しにくい。そのため、フィールドェミッションディスプレイ (FED )、プラズマディスプレイパネル (PDP)、無機エレクト口ルミネッセンス（無機 EL)用の 部材形成材料、特に電極形成材料や隔壁形成材料として有用である。 [0070] The present invention relates to a novel composition containing an inorganic powder. The inorganic powder-containing composition according to the present invention is excellent in the thermal decomposability of the organic component at the time of firing, and the organic component hardly remains in the formed inorganic sintered body such as the electrodes and the partition walls. Therefore, it is useful as a member forming material for field emission display (FED), plasma display panel (PDP), and inorganic electorescence (inorganic EL), particularly as an electrode forming material and a partition forming material.

Claims

請求の範囲 (A)無機粉体、（B)アルカリ可溶性樹脂、（C)下記式（1)で表される化合物と下記 式（2)で表される化合物とからなる群から選ばれる少なくとも 1種の化合物、および（ D)光重合開始剤を含有することを特徴とする無機粉体含有組成物。 [化 3] Claims At least one member selected from the group consisting of (A) an inorganic powder, (B) an alkali-soluble resin, (C) a compound represented by the following formula (1) and a compound represented by the following formula (2): An inorganic powder-containing composition comprising: a kind of compound; and (D) a photopolymerization initiator. [Formula 3]
[式（1)中、 R1は水素原子、水酸基、炭素数 1一 4のアルキル基または炭素数 1一 4の ヒドロキシアルキル基である。 ] [In the formula (1), R 1 is a hydrogen atom, a hydroxyl group, a C14 alkyl group or a C14 hydroxyalkyl group. ]
[化 4]  [Formula 4]
0 H 3 OH 3 0 H 3 OH 3
H2C = C - C一〇一 R 2— C— C =CH 2 H 2 C = C-C 1〇1 R 2 — C— C = CH 2
I I I I  I I I I
0 O  0 O
[式（2)中、 R2は（CH CH O)、 (CH CH (CH )〇）、 CH CH (OH) CH 0、 CH C[In the formula (2), R 2 is (CH CH O), (CH CH (CH) OH), CH CH (OH) CH 0, CH C
H CH (CH ) 0または炭素数 2 18のアルキレン基である。 aおよび bは各々独立にH CH (CH) 0 or an alkylene group having 218 carbon atoms. a and b are each independently
1一 12の数である。 ] It is a number of 1 to 12. ]
[2] 無機粉体 (A)が導電性無機粉体であることを特徴とする請求項 1に記載の無機粉 体含有組成物。  [2] The composition containing an inorganic powder according to claim 1, wherein the inorganic powder (A) is a conductive inorganic powder.
[3] 無機粉体 (A)がガラス粉体であることを特徴とする請求項 1に記載の無機粉体含有 組成物。  [3] The inorganic powder-containing composition according to claim 1, wherein the inorganic powder (A) is a glass powder.
[4] アルカリ可溶性樹脂（B)がメタタリレート共重合体である請求項 1に記載の無機粉 体含有組成物。  [4] The inorganic powder-containing composition according to claim 1, wherein the alkali-soluble resin (B) is a metathallate copolymer.
[5] 支持フィルムと、この支持フィルム上に請求項 1一 4のいずれかに記載の無機粉体 含有組成物を用いて形成された層とからなることを特徴とする転写フィルム。 [5] A transfer film comprising a support film and a layer formed on the support film using the inorganic powder-containing composition according to any one of claims 14 to 14.
[6] (i)基板上に請求項 1一 4のいずれかに記載の無機粉体含有組成物を用いて層を 形成し、 [6] (i) forming a layer on the substrate by using the inorganic powder-containing composition according to any one of claims 14 to 14,
(ii)所望のパターンに放射線を照射して前記層を露光させ、露光部分を架橋させ てアルカリ性現像液に対して不溶化させた後、  (ii) irradiating a desired pattern with radiation to expose the layer, cross-linking the exposed portion to make it insoluble in an alkaline developer,
(iii)アルカリ性現像液を使用して未露光部分を溶解、除去してパターンを形成し、 (iii) using an alkaline developer to dissolve and remove unexposed portions to form a pattern,
(iv)前記パターンを焼成処理する (iv) baking the pattern
ことを特徴とする無機焼結体の形成方法。  A method for forming an inorganic sintered body, comprising:
[7] 請求項 2に記載の無機粉体含有組成物を用いて層を形成し、得られる無機焼結体 が電極であることを特徴とする請求項 6記載の無機焼結体の形成方法。 [7] The method for forming an inorganic sintered body according to claim 6, wherein a layer is formed using the inorganic powder-containing composition according to claim 2, and the obtained inorganic sintered body is an electrode. .
[8] 請求項 3に記載の無機粉体含有組成物を用いて層を形成し、得られる無機焼結体 が隔壁であることを特徴とする請求項 6記載の無機焼結体の形成方法。 [8] The method for forming an inorganic sintered body according to claim 6, wherein a layer is formed using the inorganic powder-containing composition according to claim 3, and the obtained inorganic sintered body is a partition. .
PCT/JP2005/003995 2004-03-09 2005-03-08 Composition containing inorganic powder, transfer film, and method of forming inorganic sinter WO2005085360A1 (en)

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