TW201727364A - Photosensitive electroconductive paste and process of producing electroconductive pattern - Google Patents

Abstract

A photosensitive electroconductive paste capable of forming an electroconductive pattern of a thick film, and a process of producing an electroconductive pattern using the paste are disclosed. The photosensitive electroconductive paste contains an electroconductive powder (A), an alkaline-soluble resin (B) having at least one carboxyl group, and a reactive compound (C) having at least one carbon-carbon double bond, and the reactive compound (C) contains a dendritically branched molecule compound (C1). The process of producing an electroconductive pattern includes a coating step of coating a film with the photosensitive electroconductive composition to obtain a coating film, a drying step of drying the coating film to obtain a dry film, an exposing and developing step of exposing and developing the dry film to form a pattern, and a transferring step of transferring the pattern to form a pattern on a ceramic green sheet.

Description

Photosensitive conductive paste and method of manufacturing conductive pattern using same

The present invention relates to a photosensitive conductive paste and a method of producing a conductive pattern using the same.

In recent years, with the development of high-speed, high-frequency, and miniaturization of electronic components, it is required to form a fine and high-density conductive pattern for mounting such ceramic substrates. A conventional method of forming a conductive pattern on a ceramic green sheet of one of the ceramic substrates may be, for example, a screen printing method or an evaporation method, but there is a limit to the miniaturization of the line and line pitch of the conductive pattern by the screen printing method. Further, although the vapor deposition method can form a fine conductive pattern of 20 μm or less, there is a problem that the cost is increased due to equipment investment and complicated manufacturing steps.

In order to solve such problems, there has been proposed a technique of forming a fine conductive pattern by an optical lithography method (Patent Documents 1 and 2).

[Previous Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent No. 3218767

Patent Document 2: Japanese Patent Laid-Open No. 2004-271788

However, the photosensitive conductive paste is affected by the conductive powder contained therein, and it is pointed out that the transmittance of the exposure light is low, and it is impossible to form a thick film pattern of 10 μm or more with high precision.

It is an object of the present invention to provide a photosensitive conductive paste capable of forming a conductive film of a thick film.

The inventors of the present invention have intensively studied and found that by using a dendritic compound having a carbon-carbon double bond as a cross-linking component, even if the exposure light does not penetrate deep into the coating film due to the influence of the conductive powder, the promotion can be promoted. In the deep hardening, a thick film pattern can be formed, and the present invention is completed.

In other words, the photosensitive conductive paste provided by the present invention contains conductive powder (A), alkali-soluble resin (B), and one or more reactive compounds having one or more carbon-carbon double bonds. (C); at least one of the above-mentioned one or more reactive compounds (C) is a dendritic compound (C1).

Furthermore, the method for producing a conductive pattern on a ceramic green sheet provided by the present invention includes a coating step of applying the photosensitive conductive paste of the present invention to a ceramic green sheet to obtain a coating film; drying The step of drying the coating film to obtain a dried film, and exposing and developing the film to form a pattern by exposing and developing the dried film.

Furthermore, the method for manufacturing the conductive pattern on the ceramic green sheet provided by the present invention includes: a coating step of applying the photosensitive conductive paste of the present invention to a temporary support to obtain a coating film; and a drying step of drying the coating film to obtain a dried film; exposure and development a step of forming a pattern by exposing and developing the dried film, and a transfer step of transferring the pattern to form a pattern on the ceramic green sheet.

Furthermore, the method for producing a ceramic member according to the present invention includes a step of laminating a ceramic green sheet having a conductive pattern formed by the above-described manufacturing method of the present invention, performing lamination and pressure bonding to obtain a laminated body; And a calcination step of calcining the laminate to obtain a ceramic member.

According to the present invention, the conductive paste can form a thick film pattern of up to 10 μm or more.

The reactive compound (C) contained in the photosensitive conductive paste of the present invention has one or more carbon-carbon double bonds and has a function of a so-called "crosslinking component".

At least one of the one or more reactive compounds (C) used in the present invention is required to be a dendritic compound (C1), and a dendritic compound (C1) is used, even if it contains a conductive powder. The effect is that the exposure light does not penetrate deep into the coating film, and the deep hardening can be promoted to form a thick film pattern.

The dendritic compound (C1) of the present invention refers to a dendrimer or a superbranched polymer (manufactured by reacting a component monomer in one step) Any one of a branched polymer) and a regular dendron, a polyfunctional (meth) acrylate compound represented by the general formula (1) and a polyvalent fluorene represented by the general formula (2) The compound is preferably one which is polymerized by Michael addition (the relevant carbonyl group is at the β position).

In the general formula (1), R ¹ represents hydrogen or an alkyl group having 1 to 4 carbon atoms; and R ² represents a remainder of the compound R ³ (OH) _m after supplying n hydroxyl groups to the ester bond; R ³ The (OH) _m system represents a polyol based on a non-aromatic linear or branched hydrocarbon skeleton having 2 to 8 carbon atoms, or a dehydration condensation of an alcohol from a plurality of molecules of the polyol, and is linked via an ether bond The polyol ether, or the ester of the polyol or polyol ether and the hydroxy acid, wherein m represents an integer of 2 to 50, m≧n, and n represents an integer of 2-20.

In the general formula (2), R ⁴ is a single bond, or a hydrocarbon group having a carbon number of 1 or a carbon number of 2 to 5 and further containing an oxygen atom, or a linear or branched hydrocarbon group, or Further, the hydrocarbon group is further bonded to a group of at least a part of the methylthio group of the formula 2 and having a carbonyloxy group; and the p system represents an integer of 2 to 6, but if R ⁴ represents a single bond, the p system represents 2, When the carbon number of R ⁴ is 1, p is an integer of 2 to 4.

The polyfunctional (meth) acrylate compound represented by the above formula (1) and the polyvalent fluorene compound represented by the general formula (2) are reacted as follows to form a dendritic compound.

For the polyfunctional (meth) acrylate compound represented by the general formula (1), the general addition of the polyvalent fluorene compound represented by the formula (2) is such that the dendrimer obtained can be carbon-carbon subsequently The radiation polymerization is carried out on the basis of a double bond, and it is preferred to carry out the method in which the compound represented by the general formula (1) has a carbon-carbon double bond and remains in the range of 0.1% to 50% as a whole.

For example, the fluorenyl group of the polyvalent fluorene compound represented by the general formula (2) is added to the carbon-carbon double bond of the polyfunctional (meth) acrylate compound represented by the general formula (1), depending on the group and the double bond. The molar ratio is preferably from 1/200 to 1/2, more preferably from 1/100 to 1/3, particularly preferably from 1/50 to 1/5, and most preferably from 1/20 to 1/8.

The reaction solvent is removed before it adversely affects the reaction, and various solvents which are conventionally used in organic synthesis can be used. Specific examples include aprotic polar organic solvents (for example, N,N-dimethylformamide, dimethyl hydrazine, N,N-dimethylacetamide, tetramethylurea, and a ring). Butane, N-methyl-2-pyrrolidone, 1,3-dimethylimidazolidinone, etc., ethers (eg diisopropyl ether, propylene glycol-1-monomethyl ether-2-acetate) , third butyl methyl ether, tetrahydrofuran, two Alkane, etc.), aliphatic hydrocarbons (eg hexane, cyclohexane, n-octane, n-decane, decalin, petroleum ether, etc.), aromatic hydrocarbons (eg benzene, chlorobenzene, o-dichloro Benzene, nitrated benzene, toluene, xylene, mesitylene, tetrahydronaphthalene, etc.), esters (eg ethyl acetate, etc.), halogenated hydrocarbons (eg chloroform, dichloromethane, 1,2-dichloroethane) Alkanes, carbon tetrachloride, etc.), ketones (eg acetone, methyl ethyl ketone, methyl butanone, methyl isobutyl ketone, cyclohexanone, etc.), alkoxyalkanes (eg 1,2-dimethoxy) These may be used singly or in combination of two or more kinds thereof, such as ethane, 1,2-diethoxyethane or diglyme.

In the dendrimer used in the present embodiment, the polyvalent fluorene compound represented by the general formula (2) is a (meth) acrylate group of the polyfunctional (meth) acrylate compound represented by the general formula (1). The addition reaction is carried out by mixing a polyfunctional (meth) acrylate compound (monomer) with a polyvalent ruthenium compound, and adding an alkaline catalyst at room temperature to 100 ° C. The reaction time is usually from about 30 minutes to about 6 hours.

In the dendritic compound (C1) of the present invention, preferred examples of the polyfunctional (meth) acrylate compound represented by the general formula (1) include, for example, ethylene glycol di(meth)acrylate. , diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, three Hydroxymethylpropane tri(meth)acrylate, ethylene oxide modified trimethylolpropane tri(meth)acrylate, propylene oxide modified trimethylolpropane tri(meth)acrylate, three Hydroxymethylethane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, Dipentaerythritol hexa(meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, caprolactone modified pentaerythritol tri(meth) acrylate, caprolactone modified pentaerythritol Tetrakis (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, epichlorohydrin modified six Phthalocyanine Acid di(meth)acrylate, hydroxytrimethylacetic acid neopentyl glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide modified neopentyl glycol di Methyl) acrylate, propylene oxide modified neopentyl glycol di(meth) acrylate, caprolactone modified hydroxy trimethyl acetate neopentyl glycol di(meth) acrylate, stearic acid Modified pentaerythritol di(meth)acrylate, epichlorohydrin modified di(meth)acrylate, poly(ethylene glycol butanediol) di(meth)acrylate, poly(propylene glycol extension) Alcohol) Di(meth)acrylate, polyester (meth)acrylate, polyethylene glycol di(meth)acrylate, polyethylene glycol-polypropylene glycol-polyethylene glycol di(meth)acrylate , polypropylene glycol di(meth)acrylate, epichlorohydrin modified propylene glycol di(meth)acrylate, propylene oxide modified bisphenol A diglycidyl ether di(meth)acrylate, polyoxyn 2 (Meth) acrylate, triethylene glycol di(meth) acrylate, tetraethylene glycol di(meth) acrylate, tricyclodecane dimethanol di(meth) acrylate, neopentyl glycol Trimethylolpropane (Meth) acrylate, tripropylene glycol di(meth) acrylate, ethylene oxide modified tripropylene glycol di(meth) acrylate, triglycerin di(meth) acrylate, dipropylene glycol di (a) Acrylate, epichlorohydrin modified glycerol tri(meth)acrylate, ethylene oxide modified glycerol tri(meth)acrylate, propylene oxide modified glycerol tris(methyl) ) acrylate, ethylene oxide modified tris (meth) acrylate, caprolactone modified trimethylolpropane tri (meth) acrylate, HPA modified trimethylolpropane tri (methyl) Acrylate, ethylene oxide modified trimethylolpropane tri(meth)acrylate, propylene oxide modified trimethylolpropane tri(meth)acrylate, trimethylolpropane benzoate ( Methyl) acrylate, tris((meth) propylene oxiranyl) isocyanurate, alkoxy modified trimethylolpropane tri(meth) acrylate, dipentaerythritol poly(methyl) A (meth) acrylate such as an acrylate or an alkyl modified dipentaerythritol tri(meth)acrylate or bis(trimethylolpropane)tetra(meth)acrylate. These compounds may be used alone or in combination of two or more.

In the dendritic compound (C1) of the present embodiment, the polyvalent fluorene compound represented by the general formula (2) may, for example, be 1,2-dimercaptoethane, 1,3-dimercaptopropane or 1,4-di Mercaptan, bis-decylethanethiol (HS-CH ₂ CH ₂ -S-CH ₂ CH ₂ -SH), trimethylolpropane tris(mercaptoacetate), trimethylolpropane tris(mercaptopropionic acid) Ester), pentaerythritol tetrakis(mercaptoacetate), pentaerythritol tris(mercaptoacetate), pentaerythritol tetrakis(mercaptopropionate), dipentaerythritol hexa(mercaptoacetate), dipentaerythritol hexa(mercaptopropionate), and the like. These compounds may be used alone or in combination of two or more.

The double bond equivalent of the dendritic compound (C1) (average weight average molecular weight of one double bond) is preferably from 110 to 150. When the double bond equivalent of the dendritic compound (C1) is 110 or more, the amount of carbon-carbon double bonds present in the photosensitive conductive paste can be suppressed, and cracking due to excessive hardening of the pattern can be suppressed. Moreover, defects due to organic components remaining during firing can be alleviated. When it is 150 or less, the amount of carbon-carbon double bonds present in the photosensitive conductive paste can be made sufficient, so that the sensitivity at the time of exposure can be improved.

The weight average molecular weight of the dendritic compound (C1) is preferably from 15,000 to 25,000. When the weight average molecular weight is 15,000 or more, the length promoted by the radical reaction becomes long, so that it can be easily hardened to a deep portion, and if it is 25,000 or less, defects due to organic components remaining during firing can be alleviated.

The dendritic compound (C1) of the present invention can be used to confirm the molecular weight, the amount of double bonds, and the like by using a gel permeation chromatography analyzer, a liquid chromatography layer analyzer, or another general analysis device. For the gel permeation chromatography, for example, Tosoh Co., HLC-8220GPC, column: Shodex KF-804L+KF-803L can be used.

The reactive compound (C) may be only a dendritic compound (C1), or may contain other reactive compounds (C) in addition to the dendritic compound (C1). The reactive compound (C) other than the dendritic compound (C1) may, for example, be methyl acrylate or C. Ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, dibutyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-amyl acrylate, allyl acrylate, benzyl acrylate , butoxyethyl acrylate, butoxy triethylene glycol acrylate, cyclohexyl acrylate, dicyclopentyl acrylate, dicyclopentenyl acrylate, 2-ethylhexyl acrylate, glycerol acrylate , glycidyl acrylate, heptafluorodecyl acrylate, 2-hydroxyethyl acrylate, isodecyl acrylate, 2-hydroxypropyl acrylate, isodecyl acrylate, isooctyl acrylate, lauryl acrylate, acrylic acid 2-methoxyethyl ester, methoxyethylene glycol acrylate, methoxy diethylene glycol acrylate, octachloropentyl acrylate, phenoxyethyl acrylate, stearyl acrylate, trifluoroethyl acrylate Ester, allylated cyclohexyl diacrylate, 1,4-butanediol diacrylate, 1,3-butanediol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, three Ethylene glycol diacrylate, polyethylene glycol diacrylate, second season Tetraol hexaacrylate, dipentaerythritol monohydroxypentaacrylate, bis(trimethylolpropane) tetraacrylate, glycerol diacrylate, methoxycyclohexyl diacrylate, neopentyl glycol diacrylate , propylene glycol diacrylate, polypropylene glycol diacrylate, triglycerol diacrylate, trimethylolpropane triacrylate, acrylamide, amine acrylate, phenyl acrylate, phenoxyethyl acrylate, acrylic acid Benzyl ester, 1-naphthyl acrylate, 2-naphthyl acrylate, bisphenol A diacrylate, diacrylate of bisphenol A-ethylene oxide adduct, bisphenol A-propylene oxide adduct Acrylates such as diacrylate, epoxy acrylate or urethane acrylate; thiophenol acrylate or benzyl thiol acrylate, or 1 to 5 of the aromatic ring hydrogen atoms of the monomers are substituted with chlorine Or a monomer of a bromine atom or a substitute of the acrylate to a methacrylate. Further, for example, styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, chlorinated styrene, brominated styrene, α-methylstyrene, and α-methyl chloride may also be mentioned. Methylstyrene, brominated α-methylstyrene, chloroform Styrene, hydroxymethylstyrene, carboxymethylstyrene, vinylnaphthalene, vinylhydrazine or vinylcarbazole. Further, a acryl group, a methacryl group, a vinyl group or an allyl group may be mixed in the polyfunctional reactive compound (C). These reactive compounds (C) may be used alone or in combination of two or more.

The proportion of the reactive compound (C) which is contained in the total solid content in the photosensitive conductive paste is preferably 5 to 30% by volume. When the proportion in the total solid content is 5% by volume or more, the carbon-carbon double bond existing in the photosensitive conductive paste is sufficient, and the sensitivity at the time of exposure can be improved. More preferably, it is 10% by volume or more. On the other hand, when the occupation in the total solid content is 30% by volume or less, the viscosity of the photosensitive conductive paste can be appropriately maintained, which is preferable. More preferably, it is 20% by volume or less. Further, when the reactive compound (C) contains a dendritic compound (C1) and a dendritic compound (C1), the proportion of the dendritic compound (C1) in the reactive compound (C) is higher. More than 50% by volume.

The conductive powder (A) contained in the photosensitive conductive paste of the present invention may, for example, be silver, gold, copper, platinum, palladium, tin, nickel, aluminum, tungsten, molybdenum, cerium oxide, chromium, titanium or indium, and The metal particles or carbon particles selected from the group consisting of the alloys of the metals, or a mixture of the particles, are preferably silver, copper or gold from the viewpoint of conductivity, from the viewpoint of cost and stability. Good silver.

The median diameter (D50) of the conductive powder (A) is preferably 0.1 to 10 μm. When D50 is 0.1 μm or more, when the photosensitive conductive paste is fired, the contact probability of the conductive powders (A) is increased, and the specific resistance and the probability of disconnection of the formed conductive pattern are lowered. Further, in the exposure and development step, the exposure light can be smoothly penetrated into the coating film obtained by coating the photosensitive conductive paste, and the crucible can be easily finely patterned. More preferably, the system is more than 0.5 μm. On the other hand, if D50 is 10 μm or less, the surface smoothness, pattern accuracy, and dimensional accuracy of the produced conductive pattern can be improved. Better system at 6μm the following. Further, D50 can be measured by a laser light scattering method using Microtrac HRA (Model No. 9320-X100; manufactured by Nikkiso Co., Ltd.).

The proportion of the conductive powder (A) in the total solid content in the photosensitive conductive paste is preferably 25 to 45% by volume. When the proportion of the total solid content is 25% by volume or more, the contact probability between the conductive powders (A) is increased during calcination, and the specific resistance and the probability of disconnection of the produced conductive pattern are lowered. On the other hand, if the proportion in the total solid content is 45% by volume or less, in the exposure and development step, the exposure light can be smoothly penetrated into the coating film obtained by coating the photosensitive conductive paste.俾 can easily become thick film and finely patterned. Here, the "total solid content" is a total constituent component of a photosensitive conductive paste other than a solvent. In the ratio of the conductive powder (A), the vertical cross section is observed by a transmission electron microscope (for example, "JEM-4000EX" manufactured by JEOL Ltd.), and the inorganic component is distinguished by the density of the image. Image analysis can be performed with organic components. The evaluation area of the transmission electron microscope is, for example, an area of about 20 μm × 100 μm, and can be observed at about 1000 to 3000 times.

The "alkali-soluble resin (B)" contained in the photosensitive conductive paste of the present invention means a resin having one or more carboxyl groups.

The alkali-soluble resin (B) can be, for example, an acrylic copolymer. Here, the "acrylic copolymer" means a copolymerized component containing a unit derived from an acrylic monomer having a carbon-carbon double bond. Examples of the acrylic single system having a carbon-carbon double bond include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, second butyl acrylate, and isobutyl acrylate. Tert-butyl acrylate, n-amyl acrylate, allyl acrylate, benzyl acrylate, butoxyethyl acrylate, butoxy triethylene glycol acrylate, cyclohexyl acrylate, dicyclopentyl acrylate, acrylic double ring Pentenyl ester, 2-ethylhexyl acrylate, glycerol acrylate, glycidyl acrylate, heptafluorodecyl acrylate, 2-hydroxyethyl acrylate, acrylic acid Ester, 2-hydroxypropyl acrylate, isodecyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxy ethylene glycol acrylate, methoxy diethylene glycol Acrylate, octaamyl acrylate, phenoxyethyl acrylate, stearyl acrylate, trifluoroethyl acrylate, acrylamide, amine acrylate, phenyl acrylate, 1-naphthyl acrylate, 2-naphthalene Base acrylate, thiophenol acrylate or benzyl thiol acrylate, or those acrylates substituted with methacrylate. The copolymerization component other than the acrylic monomer may, for example, be a compound having a carbon-carbon double bond, and for example, styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, α-A Styrene such as styrene, chloromethylstyrene or hydroxymethylstyrene, or 1-vinyl-2-pyrrolidone.

When the acryl-based copolymer is used as the alkali-soluble resin (B), an unnecessary portion can be dissolved and removed by using an alkaline developing solution after the exposure. Therefore, the amount of the carboxyl group of the acryl-based copolymer (for example, acrylic copolymerization) can be appropriately adjusted. The acid value of the complex can be used, and the acid value is preferably in the range of 50 to 150. The carboxyl group can be introduced into the acrylic copolymer by using an unsaturated acid such as an unsaturated carboxylic acid as a copolymerization component. The unsaturated acid system may, for example, be acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid or vinyl acetate, or an acid anhydride thereof. The acid value of the obtained acrylic copolymer can be adjusted by the amount of the unsaturated acid used.

In order to increase the curing reaction rate of the acrylic copolymer at the time of exposure, the acrylic copolymer preferably has a carbon-carbon double bond at a side chain or a molecular end. The structure having a carbon-carbon double bond may, for example, be a vinyl group, an allyl group, a propenyl group or a methacryl group. Acrylic copolymer having such a functional group at a side chain or a molecular end For the acrylic copolymer, the carboxyl group (when the acrylic copolymer system has a mercapto group, an amine group or a hydroxyl group, it may be a mercapto group, an amine group or a hydroxyl group), and has a glycidyl group or an isocyanate group and a carbon-carbon. The double bond compound, chlorinated acrylic acid, methacrylonitrile chloride or allyl chloride can be synthesized by reaction.

Examples of the compound having a glycidyl group and a carbon-carbon double bond include glycidyl methacrylate, glycidyl acrylate, allyl epoxidized ether, glycidyl acrylate, and croton. Glycidyl ether, butyl crotonate, glycidyl isocrotate, or "Cyclomer" (registered trademark) M100 or A200 (all of which are manufactured by Daicel Chemical Industries, Ltd.). The compound having an isocyanate group and a carbon-carbon double bond may, for example, be acrylonitrile isocyanate, methacryl oxime isocyanate, propylene decyl ethyl isocyanate or methacryl methacrylate.

The glass transition point of the alkali-soluble resin (B) is preferably 80 to 160 °C. When the glass transition point is 80 ° C or higher, for example, when a pattern is formed on a ceramic green sheet (hereinafter referred to as "embroid"), the alkali-soluble resin (B) does not soften even if the photosensitive conductive paste is dried at about 70 ° C. The ruthenium can be prevented from being absorbed into the plaque together with other components, whereby it can be easily finely patterned. More preferably, it is 100 ° C or more. On the other hand, when the glass transition point is 160 ° C or less, the thermal decomposition property is improved, and the defects due to the organic components remaining during firing can be alleviated. More preferably, it is below 140 °C. Further, the glass transition point of the alkali-soluble resin (B) can be measured by differential scanning calorimetry (DSC).

The alkali-soluble resin (B) may also be a mixture of two or more kinds. When the alkali-soluble resin (B) is a mixture of two or more kinds (that is, when the photosensitive conductive paste contains two or more kinds of alkali-soluble resins (B)), the glass transition point of all the alkali-soluble resins (B) contained is higher. Jiajun is within the above range.

The glass transition point of the alkali-soluble resin (B) is, for example, utilized to constitute propylene The glass transition point of the monomer component of the acid-based copolymer can be controlled. The monomer component having a higher glass transition point may, for example, be methyl methacrylate, butyl methacrylate, (meth)acrylic acid, acrylonitrile, acrylamide, styrene, methacrylic acid-4- Third butylcyclohexyl ester, dicyclopentyl (meth) acrylate, biscyclopentadienyl (meth) acrylate, iso (meth) acrylate, methacrylic acid-3,3,5-trimethyl A (meth) acrylate having a cyclic aliphatic hydrocarbon group having 6 to 15 carbon atoms, such as cyclohexyl ester.

The proportion of the alkali-soluble resin (B) in the total solid content in the photosensitive conductive paste is preferably 20 to 55 vol%. When the proportion of the total solid content is 20% by volume or more, for example, when a pattern is formed on the green sheet, the alkali-soluble resin (B) which is absorbed into the green sheet together with other components can be reduced during drying, and can be easily finely Patterned. More preferably, it is 30% by volume or more. On the other hand, when the proportion in the total solid content is 55% by volume or less, the viscosity of the photosensitive conductive paste can be appropriately maintained, and defects due to residual organic components during firing can be reduced. More preferably, it is 45% by volume or less.

The weight average molecular weight of the alkali-soluble resin (B) is preferably 7,000 to 35,000. When the weight average molecular weight is 7,000 or more, the viscosity of the photosensitive conductive paste is moderate, and the coating film adhesion after drying can be suppressed. More preferably 24,000 or more. On the other hand, when the weight average molecular weight is 35,000 or less, the solubility of the non-exposed portion to the developer can be improved, and the development time can be shortened. More preferably, it is 30,000 or less.

The conductive paste of the present invention may also contain a photopolymerization initiator. The photopolymerization initiator is a compound which generates a radical by decomposing or dehydrogenating a short-wavelength light such as ultraviolet rays. The photopolymerization initiator may, for example, be 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzamide)], 2,4,6-trimethyl. Benzhydryl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzylidene) phenylphosphine oxide, ethyl ketone, 1-[9-ethyl-6-2(2-methyl Benzobenzyl)-9H-indazol-3-yl]-1-(O-acetamidine), diphenyl ketone, o-benzimidylbenzoic acid methyl, 4,4'-bis (two Methylamino)diphenyl ketone, 4,4'-bis(diethylamino)diphenyl ketone, 4,4'-dichlorodiphenyl ketone, 4-benzylidene-4'-methyl Benzophenone, dibenzyl ketone, fluorenone, 2,2'-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylbenzene Acetone, p-tert-butyldichloroacetophenone, oxysulfide 2-methyloxosulfur 2-chlorooxosulfur 2-isopropyloxysulfur Diethyl oxysulfide , benzyl, benzyl dimethyl ketal, benzyl-β-methoxyethyl acetal, benzoin, benzoin methyl ether, benzoin butyl ether, hydrazine, 2-tert-butyl Bismuth, 2-pentyl hydrazine, β-barium chloride, fluorenone, benzofluorenone, dibenzocycloheptanone, methylene fluorenone, 4-azidobenzylidene acetophenone, 2 ,6-bis(p-azidobenzylidene)cyclohexanone, 6-bis(p-azidobenzylidene)-4-methylcyclohexanone, 1-phenyl-1,2-butanedione -2-(o-methoxycarbonyl)anthracene, 1-phenyl-propanedione-2-(o-ethoxycarbonyl)anthracene, 1-phenyl-propanedione-2-(o-benzylidene) fluorene, 1,3-diphenyl-propanetrione-2-(o-ethoxycarbonyl)anthracene, 1-phenyl-3-ethoxy-propanetrione-2-(o-benzylidene) hydrazine, rice bran Ketone (Michler's ketone), 2-methyl-[4-(methylthio)phenyl]-2- Naphthyl-1-propanone, naphthalene sulfonyl chloride, quinoline sulfonium chloride, N-phenylthioacridone, 4,4'-azobisisobutyronitrile, diphenyl diphenyl Disulfide), benzothiazole disulfide, triphenylphosphine, hydrazine, 2,4-diethyl oxysulfide Isopropyl oxysulfide A combination of a photoreductive dye such as carbon tetrabromide, tribromophenylhydrazine, benzoin, and a red or methylene blue with a reducing agent such as ascorbic acid or triethanolamine.

The amount of the photopolymerization initiator to be added is preferably 0.05 to 40 parts by mass based on 100 parts by mass of the total of the alkali-soluble resin (B) and the reactive compound (C). When the amount of the photopolymerization initiator added is 0.05 parts by mass or more, the hardening density of the exposed portion of the photosensitive conductive paste is increased, and the residual film ratio after development is improved. More preferably, it is 0.5 mass part or more. On the other hand, when the amount of the photopolymerization initiator added is 40 parts by mass or less, excessive light absorption from the upper portion of the coating film obtained by applying the photosensitive conductive paste can be suppressed. Result, can It is suppressed that the conductive pattern produced has a reverse push-pull shape, and the adhesion to the green sheet is lowered. More preferably, it is 30 mass parts or less. Further, the photopolymerization initiator may be used alone or in combination of two or more.

The conductive paste of the present invention may contain a sensitizer together with the photopolymerization initiator. The sensitizer may, for example, be 2,4-diethyloxysulfide Isopropyl oxysulfide , 2,3-bis(4-diethylaminobenzylidene)cyclopentanone, 2,6-bis(4-dimethylaminobenzylidene)cyclohexanone, 2,6-bis(4-di Methylaminobenzylidene)-4-methylcyclohexanone, Michler's ketone, 4,4-bis(diethylamino)diphenyl ketone, 4,4-bis(dimethylamino)chalcone , 4,4-bis(diethylamino)chalcone, p-dimethylamino cinnamyl ketone, p-dimethylaminobenzylidene ketone, 2-(p-dimethylaminophenyl phenyl) Vinyl)isonaphthylthiazole, 1,3-bis(4-dimethylaminophenylvinylidene)isonaphthylthiazole, 1,3-bis(4-dimethylaminobenzylidene)acetone, 1 , 3-carbonyl bis(4-diethylaminobenzylidene)acetone, 3,3-carbonylbis(7-diethylaminocoumarin), N-phenyl-N-ethylethanolamine, N-benzene Ethylethanolamine, N-tolyldiethanolamine, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 3-phenyl-5-benzimidyltetrazole or 1-phenyl-5 - Ethoxycarbonylthiotetrazole. In addition, one type of the sensitizer may be used, or two or more types may be used in combination.

The amount of the sensitizer added is preferably 0.05 to 30 parts by mass based on the total amount of the alkali-soluble resin (B) and the reactive compound (C). When the amount of the sensitizer added is 0.05 parts by mass or more, the exposure sensitivity is sufficient. It is preferably 0.1 part by mass or more. On the other hand, when the amount of the sensitizer added is 30 parts by mass or less, excessive light absorption in the upper portion of the coating film obtained by coating the conductive paste can be suppressed. More preferably, it is 10 parts by mass or less. As a result, it is possible to suppress the adhesion of the conductive pattern to the reverse push-pull shape, resulting in a decrease in the adhesion to the green sheet.

The photosensitive conductive paste of the present invention can control pattern shrinkage during firing, and can also contain a filler. The filler of the ceramic powder may, for example, be alumina (Al ₂ O ₃ ), zirconium dioxide (ZrO ₂ ), magnesium oxide (MgO), cerium oxide (BeO), mullite (3Al ₂ O ₃ ‧ ₂ SiO ₂ ), cordierite (5SiO ₂ ‧2Al ₂ O ₃ ‧2MgO), spinel (MgO-Al ₂ O ₃ ), forsterite (2MgO‧SiO ₂ ), anorthite (CaO-Al ₂ O ₃ ‧2SiO _{2 )} ), Hexacelsian (BaO-Al ₂ O ₃ ‧2SiO ₂ ), cerium oxide (SiO ₂ ), aluminum nitride (AlN) or ferrite iron (garnet type: Y ₃ Fe ₅ O ₁₂ series, spinel type: MeFe ₂ O ₄ system).

The glass-ceramic composite filler may, for example, be a glass composition powder containing, for example, SiO ₂ , Al ₂ O ₃ , CaO, B ₂ O ₃ , MgO or TiO ₂ , and from alumina, zirconia, magnesia, A mixture of inorganic filler powders selected from the group consisting of cerium oxide, mullite, cordierite, spinel, forsterite, anorthite, hexagonal yttrium aluminum lanthanum, cerium oxide and aluminum nitride.

The photosensitive conductive paste of the present invention may contain one or two or more kinds of plasticizers, leveling agents, and the like, in a range that does not impair the desired properties (usually 5% by mass or less based on the total amount of the paste). Additives such as dispersants and decane coupling agents.

The plasticizer may, for example, be dibutyl phthalate, dioctyl phthalate, polyethylene glycol or glycerin.

Examples of the leveling agent include a high-boiling aromatic group, a ketone, an ester, and a polyphthalocyanine resin or an acrylic resin dissolved in a solvent such as a ketone, an ester, a xylene or an alcohol, such as "Byketol"-OK or Special or BYK-300, 302, 306, 307, 335, 310, 320, 322, 323, 324, 325, 330, 331, 344, 370, 371, 354, 358 or 361 (all of which are BYK-Chemie) ). Further, for example, an acrylic polymer having a molecular weight of 300 to 3,000 or a modified vinyl polymer may be dissolved in a solvent such as naphtha, xylene, toluene, ethyl acetate, 1-butanol or turpentine. For example: "DISPARON" (registered trademark) L-1980-50, L-1982-50, L-1983-50, L-1984-50, L-1985-50, #1970, #230, LC-900, LC-951, #1920N, #1925N or P-410 (all of which are Nanben Chemical Co., Ltd. Or COLORSPERSE 188-A, HIPHOENIX PE series, MODECOR L or DAPRO S-65, U-99 or W-77 (all of which are manufactured by Sannocop Co., Ltd.).

The decane coupling agent may, for example, be methyltrimethoxydecane, dimethyldiethoxysilane, phenyltriethoxysilane, hexamethyldiazepine or 3-methylpropenyloxypropyl group. Trimethoxydecane, 3-glycidoxypropyltrimethoxydecane or ethylenetrimethoxydecane.

The photosensitive conductive paste of the present invention may also contain a solvent. The solvent may, for example, be N,N-dimethylacetamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, dimethylimidazolidinone, dimethylene碸, diethylene glycol monoethyl ether, dipropylene glycol methyl ether, dipropylene glycol n-propyl ether, dipropylene glycol n-butyl ether, tripropylene glycol methyl ether, tripropylene glycol n-butyl ether, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether Acetate, propylene glycol phenyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, γ-butyrolactone, ethyl lactate, 1-methoxy 2-propanol, 1-ethoxy-2-propanol, ethylene glycol mono-n-propyl ether, diacetone alcohol, tetrahydrofurfuryl alcohol or propylene glycol monomethyl ether acetate. One type of the solvent may be used, or two or more types may be used in combination. The content of the solvent is not particularly limited, but is usually 2% by mass to 40% by mass, preferably 5% by mass to 30% by mass based on the paste.

The photosensitive conductive paste of the present invention can be produced, for example, by using a disperser or a kneading machine such as a three-roll mill, a ball mill, or a planetary ball mill.

The method for producing a pattern on the ceramic green sheet of the present invention includes a coating step, a drying step, and an exposure and development step. The coating step is the invention The photosensitive conductive paste was coated on the ceramic green sheet to obtain a coating film. In the drying step, the above coating film is dried to obtain a dried film. In the exposure and development step, the dried film is exposed and developed to form a pattern.

In the coating step, the above-described conductive paste of the present invention is applied onto a ceramic green sheet. The coating system can be carried out by a conventional method of roll coating, spin coating, dip coating or the like. The coating thickness is not particularly limited, and since the conductive paste of the present invention has an excellent feature of forming a pattern even with a thick film of 10 μm or more, the coating film thickness is preferably 10 μm or more. Of course, it may be less than 10 μm.

As the coating film obtained by the coating step, a method of drying and volatilizing the solvent in the drying step can be carried out, for example, by heat drying or vacuum drying using an oven, a hot plate or infrared rays. The heating temperature is preferably 60 to 120 °C. If the drying temperature is above 60 ° C, the solvent can be sufficiently volatilized to remove. On the other hand, when the drying temperature is 120 ° C or lower, thermal crosslinking of the photosensitive conductive paste can be suppressed, and the residue of the developing non-exposed portion can be reduced. The heating time is preferably from 5 minutes to several hours.

The dried film obtained by the drying step is exposed and developed in the exposure and development step. The exposure method is generally a method in which exposure is performed through a photomask as in general optical lithography, but a method of performing direct drawing using laser light or the like may be employed without using a photomask. The exposure device can be, for example, a stepper or a proximity exposure machine. The active light source used at this time may be, for example, near ultraviolet rays, ultraviolet rays, electron beams, X-rays or laser light, and is preferably ultraviolet rays. The ultraviolet light source may be, for example, a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a halogen lamp or a germicidal lamp, preferably an ultra high pressure mercury lamp.

The dried film after exposure is subjected to development by using a developing solution to dissolve and remove the non-exposed portion, whereby a desired pattern can be formed. The developer to be subjected to alkali development may, for example, be tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide or hydrogen. Potassium oxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexyl An aqueous solution of an amine, ethylenediamine or hexamethylenediamine, in which, for example, N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N- may also be added. a polar solvent such as dimethylacetamide, dimethyl hydrazine or γ-butyrolactone; an alcohol such as methanol, ethanol or isopropanol; an ester such as ethyl lactate or propylene glycol monomethyl ether acetate; cyclopentanone, A ketone or a surfactant such as cyclohexanone, isobutyl ketone or methyl isobutyl ketone. The developer to be subjected to organic development may, for example, be N-methyl-2-pyrrolidone, N-ethinyl-2-pyrrolidone, N,N-dimethylacetamide, N,N- a polar solvent such as dimethylformamide, dimethyl sulfoxide or hexamethylsulfonamide; or the polar solvent, and methanol, ethanol, isopropanol, xylene, water, methyl carbitol or B A mixed solution of carbabitol.

As a method of developing, for example, a method of spraying a developing solution onto a surface of a coating film while allowing the substrate to stand or rotate, a method of immersing the substrate in a developing solution, or immersing the substrate in a developing solution The method of applying ultrasonic waves in the state.

The pattern obtained by development can also be subjected to a rinsing treatment using a rinsing liquid. Here, as the rinse liquid, for example, water may be added; or an aqueous solution of an alcohol such as ethanol or isopropyl alcohol, an ester such as ethyl lactate or propylene glycol monomethyl ether acetate may be added to the water.

The above method is a method in which a conductive paste of the present invention is directly applied to a ceramic green sheet to perform pattern formation, but the conductive paste of the present invention is first coated with a conductive paste on a temporary support such as a film (usually a resin film). After the pattern is formed and transferred onto the ceramic green sheet, a conductive pattern on the ceramic green sheet can be produced. The method includes a coating step, a drying step, an exposure ‧ development step, and a transfer step. This coating step applies a photosensitive conductive paste to a temporary support to obtain a coated film. Dry step The coating film was dried to obtain a dried film. In the exposure and development step, the dried film is exposed and developed to form a pattern. The transfer step transfers the pattern to form a pattern on the ceramic green sheet. Here, the coating step, the drying step, the exposure, and the development step may be carried out in the same manner as described above.

The pattern formed on the temporary support after development is transferred to form a pattern on the ceramic green sheet. As a transfer method, for example, a film having a pattern and a ceramic green sheet are subjected to a pressurization at a pressure of 1 to 30 MPa in a heated state at 50 to 150 ° C using a vacuum laminator.

The method for producing a ceramic member of the present invention comprises forming a pattern on a ceramic green sheet by using the method for producing a conductive pattern of the present invention. A stacking step and a calcining step are usually included. In the lamination step, the ceramic green sheets on which the conductive patterns have been formed are laminated and thermocompression bonded to obtain a laminated body. This calcination step calcins the above laminate to obtain a ceramic member. The pattern formed on the green sheet forms a composite of the organic component and the conductive powder (A), and the conductive powder (A) is in contact with each other at the time of firing to exhibit conductivity, and is suitably used as a ceramic member or the like. wiring.

A specific example of the method for producing a ceramic member of the present invention will be described below with respect to a method of manufacturing a laminated wafer inductor.

First, a via hole is formed in the green sheet, and an interlayer connection wiring is formed by burying the conductor therein. An internal wiring is formed on the green sheet by the manufacturing method of the pattern of the present invention, and a dielectric or insulator pattern is formed as needed. The green sheets on which the interlayer connection wiring and the internal wiring have been formed are laminated and thermocompression bonded to obtain a laminated body. The obtained laminate is subjected to calcination after being cut into a desired wafer size, and a plating process is performed after coating the terminal electrodes to obtain a laminated wafer inductor.

A method of forming a via hole in a green sheet can be, for example, laser irradiation.

The method of burying the conductor in the through hole can be performed by, for example, screen printing a method in which the conductive paste is buried in the through hole and then dried. As the conductive paste, for example, a paste containing copper, silver or silver-palladium can be used, and the interlayer connection wiring and the internal wiring can be formed at one time, and the photosensitive conductive paste of the present invention is preferably used from the viewpoint of simplifying the process.

A method of forming a dielectric or insulator pattern can be, for example, a screen printing process.

A method of laminating the green sheets on which the interlayer connection wiring and the internal wiring have been formed is, for example, a method in which the number of necessary vias is overlapped. Further, the subsequent thermocompression bonding method can be carried out by, for example, using a hydraulic press, at a temperature of 90 to 130 ° C and 5 to 20 MPa.

A method of cutting the laminated body obtained by thermocompression bonding can be, for example, a method using a die cutter. The method of calcining the cut layered body can be carried out, for example, at 300 to 600 ° C for 5 minutes to several hours, and further at 850 to 900 ° C for 5 minutes to several hours.

The method of coating the terminal electrodes can be, for example, sputtering. Further, the metal subjected to the plating treatment may be, for example, nickel or tin.

[Examples]

Hereinafter, the present invention will be described in more detail by way of examples and comparative examples, but the invention is not limited thereto.

<Materials of Photosensitive Conductive Paste>

The raw materials used are as follows:

Conductive powder (A-1): Ag particles with a D50 of 2.5 μm

Conductive powder (A-2): W particles with a D50 of 2 μm

Alkali-soluble resin: 0.4 equivalent of glycidyl methacrylate is added to the carboxyl group of the copolymer composed of methacrylic acid/methacrylic acid methyl/styrene=54/23/23

Reactive Compound (C-1) to (C-5): pentaerythritol tetrakis(mercaptoacetate), dipentaerythritol hexaacrylate, and dipentaerythritol of the weight (g) shown in Table 1 were added to a four-necked flask having a volume of 1 L. Pentaacrylate, hydroquinone and benzyldimethylamine were obtained by reacting at 60 ° C for 12 hours. With respect to the dendrimer obtained, it was confirmed by iodine titration that the sulfhydryl group had disappeared. The molecular weight was confirmed by using a gel permeation chromatography (device: manufactured by Tosoh Corporation, HLC-8220GPC, column: Shodex KF-804L+KF-803L, column temperature: 40 ° C, solvent: tetrahydrofuran). The molecular weights shown in Table 1 were confirmed by the iodine titration, and the double bond equivalents were shown in Table 1.

Reactive Compound (C-6): ARONIX M402 manufactured by East Asia Synthetic (molecular weight: 565, double bond equivalent: 100)

Photopolymerization initiator: N1919 (made by ADEKA)

Even coating agent: L1980 (made by Nanben Chemical Co., Ltd.)

Solvent: dipropylene glycol n-butyl ether (manufactured by Daicel)

<Manufacture of photosensitive conductive paste>

In the glass flask, an alkali-soluble resin (B), a reactive compound (C), a photopolymerization initiator, a leveling agent, a dispersing agent, and a solvent were used in the form of a volume % shown in Table 2 at 60 ° C. The mixture was stirred for 60 minutes to obtain a photosensitive organic component. In the photosensitive organic component, the conductive powder (A) was added so as to have a volume % shown in Table 1, and after stirring, a three-roller (EXAKT M-50; manufactured by EXAKT Co., Ltd.) was used for kneading. A photosensitive conductive paste P1 was obtained.

The photosensitive conductive pastes P2 to P9 were separately produced in the same manner except that the composition was changed to that described in Table 2.

[Example 1]

On the green sheet (GCS71F; manufactured by Yamamura Photonics Co., Ltd.), the photosensitive conductive paste P1 was applied by a screen printing method to a film thickness of 10 μm and 15 μm after drying, and the obtained coating film was applied. 10 minutes using a 80 ° C hot air dryer Dry to obtain a dried film P1 on the green sheet. The same operation was repeated, and a plurality of dried film P1 were prepared on two kinds of embryos of different film thicknesses.

In each of the two types of the dried film P1, two kinds of exposure masks each having a line width/line pitch (hereinafter referred to as "L/S") of a coil pattern of 20 μm/20 μm and 100 μm/100 μm are used, and 21 mW/ are used. The ultrahigh pressure mercury lamp outputted by cm ^{2 was} subjected to an exposure of 400 mJ/cm ² (converted wavelength: 365 nm).

Then, using 0.1% by mass of a sodium carbonate aqueous solution as a developing solution, and performing a shower development until the non-exposed portion is completely dissolved (hereinafter referred to as "full dissolution time"), four patterns having different film thicknesses from L/S are obtained. A sheet P1 is formed.

The four kinds of pattern forming sheets P1 having different film thicknesses and L/S were observed by an optical microscope, and the pattern processing properties were evaluated according to the following criteria. The results were all "○".

No pattern defects: ○

There are cracks and flaking in the pattern: ×

The cross-sectional shape of the pattern was evaluated by a scanning electron microscope (S2400; manufactured by Hitachi, Ltd.), and the results were all "○".

Topmost width - bottommost width <5μm: ○

5μm≦ top width - bottom width ≦10μm: △

Further, since the cross-sectional shape is smaller than the difference between the topmost width and the bottommost width, the volume of the conductive pattern can be maintained, so that the target resistance value can be maintained. Further, since the pattern is close to a rectangle, it is possible to prevent the occurrence of pattern deformation or the like during the lamination of the laminate.

In addition, four types of pattern forming sheets P1 having different film thicknesses and L/S ratios were prepared, and these were stacked using the guide holes, and pressure-bonded at 90 ° C and 15 MPa using a hydraulic press. Four four-layer laminated sheets P1 having different film thicknesses and L/S were obtained.

The four kinds of four-layer laminated sheets P1 obtained were cut into 0.3 mm × 0.6 mm × 0.3 mm size by a die cutter, and were kept at 350 ° C for 10 hours, and further calcined at 880 ° C for 10 minutes to obtain four. The laminated layer calcined sheet P1.

The cross section of each of the laminated calcined sheets P1 was observed by a scanning electron microscope (S2400; manufactured by Hitachi, Ltd.), and the presence or absence of defects was evaluated according to the following criteria. The results were all "○".

No in-layer defects, and no internal disconnection of internal conductive patterns: ○

There are defects in the layer and the internal conductive pattern is broken: ×

[Examples 2 to 9 and Comparative Example 1]

A pattern forming sheet or the like was produced in the same manner as in Example 1 except that the photosensitive conductive paste described in Table 2 was used, and the pattern processability, the pattern cross-sectional shape, and the presence or absence of defects of the laminated calcined sheet were evaluated. The evaluation results are shown in Table 3.

[Embodiment 10]

In the film (PEN; manufactured by Teijin Co., Ltd.), the photosensitive conductive paste P1 was applied by a screen printing method to a thickness of 15 μm, and the obtained coating film was applied by a hot air dryer at 80 ° C. The dry film P1 on the film was obtained by drying in minutes.

For dry film P1, via the L / S was 20 / 20μm coiled exposure pattern mask, using 21mW / cm ² pressure mercury lamp output, the purposes of the irradiation exposure amount 400mJ / cm ² (in terms of wavelength 365nm). Then, 0.1% by mass of an aqueous sodium carbonate solution was used as a developing solution, and shower development was carried out until the total dissolution time, and the pattern-forming sheet P1 was obtained. The pattern of the pattern forming sheet P1 was transferred to a through-hole blank (GCS71F; manufactured by Yamamura Photonics Co., Ltd.) at 2 MPa while being heated at 80 ° C using a vacuum laminator to obtain a transfer pattern sheet P1. . A total of 10 sheets of the transfer pattern sheet P1 were prepared, and they were superposed by using a guide hole, and then pressure-bonded by a hydraulic press at 90 ° C and 15 MPa to obtain ten laminated sheets P1. The obtained ten-layer laminated sheet P1 was cut into a size of 0.3 mm × 0.6 mm × 0.3 mm using a die cutter, and after being kept at 350 ° C for 10 hours, and further maintained at 880 ° C for 10 minutes, calcination was carried out to obtain ten layers. Laminated calcined sheet P1.

A terminal electrode is coated on the obtained ten-layer laminated calcined sheet P1 by sputtering, and then nickel and tin are subjected to plating treatment to obtain a laminated wafer inductor. After evaluating the electrical characteristics of the laminated chip inductor, there were no problems such as disconnection or short circuit.

(industrial availability)

The photosensitive conductive paste of the present invention is suitably used for the production of internal wiring patterns of ceramic members and the like.

Claims (9)

A photosensitive conductive paste comprising: a conductive powder (A), an alkali-soluble resin (B), and one or more reactive compounds (C) having one or more carbon-carbon double bonds; At least one of the two or more reactive compounds (C) is a dendritic compound (C1). The photosensitive conductive paste of claim 1, wherein the dendritic compound (C1) has a double bond equivalent of 110 to 150 and a weight average molecular weight of 15,000 to 25,000. The photosensitive conductive paste according to claim 1 or 2, wherein the dendritic compound (C1) is a polyfunctional (meth) acrylate compound represented by the general formula (1), and is represented by the general formula (2) a reactant of a polyvalent quinone compound; In the general formula (1), R ¹ represents hydrogen or an alkyl group having 1 to 4 carbon atoms; and R ² represents a remainder of the compound R ³ (OH) _{m in} which n hydroxyl groups are supplied to the ester bond in the formula. R ³ (OH) _m represents a polyol based on a non-aromatic linear or branched hydrocarbon skeleton having 2 to 8 carbon atoms, or a dehydration condensation of an alcohol from a plurality of molecules of the polyol, and via an ether bond a phase-linked polyol ether, or an ester of the polyol or polyol ether, and a hydroxy acid, wherein m represents an integer of 2 to 50, m≧n, and n represents an integer of 2 to 20; In the general formula (2), R ⁴ is a single bond, or a hydrocarbon group having a carbon number of 1 or a carbon number of 2 to 5 and further containing an oxygen atom, or a linear or branched hydrocarbon group, or Further, the hydrocarbon group is further bonded to a group of at least a part of the methylthio group of the formula (2) and having a carbonyloxy group; and p is an integer of 2 to 6, but if R ⁴ represents a single bond, the p-system represents 2, when the number of carbon atoms ^1:04 based R, p represents an integer of 2 to 4 lines of. The photosensitive conductive paste according to any one of claims 1 to 3, wherein the proportion of the reactive compound (C) in the solid portion of the paste is 5 to 30% by volume, and the tree in the reactive compound (C) The proportion of the branched compound (C1) is 50% by volume or more. The photosensitive conductive paste according to any one of claims 1 to 4, wherein the conductive powder (A) is from silver, gold, copper, platinum, palladium, tin, nickel, aluminum, tungsten, molybdenum, cerium oxide, The metal particles selected from the group consisting of chromium, titanium, and indium, and alloys of the metals. The photosensitive conductive paste according to any one of claims 1 to 5, wherein the ratio of the conductive powder (A) to the solid content of the paste is 25 to 45 vol%. A method for producing a conductive pattern on a ceramic green sheet, comprising: a coating step of applying the photosensitive conductive paste of any one of claims 1 to 6 onto a ceramic green sheet to obtain a coating film; a drying step of drying the coating film to obtain a dried film, and an exposure and development step of exposing and developing the dried film to form a pattern. A method for producing a conductive pattern on a ceramic green sheet, comprising: a coating step of applying the photosensitive conductive paste according to any one of claims 1 to 6 to a temporary support to obtain a coating film a drying step of drying the coating film to obtain a dried film; and exposing the developing film to exposing and developing the dried film to form a pattern; A transfer step of transferring the pattern to form a pattern on the ceramic green sheet. A manufacturing method of a ceramic member, comprising: a laminating step of forming a laminated body by laminating and crimping a ceramic green sheet having a conductive pattern formed by the manufacturing method of claim 7 or 8; and a calcining step, It is obtained by calcining the above laminated body to obtain a ceramic member.