JP5471376B2 - Photosensitive paste for forming organic-inorganic composite conductive pattern and method for producing organic-inorganic composite conductive pattern - Google Patents

Description

  The present invention relates to a photosensitive paste for forming an organic-inorganic composite conductive pattern for forming a conductive pattern.

  The organic-inorganic composite conductive pattern in the present invention refers to a conductive pattern containing both an organic component containing a resin and an inorganic component containing a conductive filler and the like. In general, an inorganic conductive pattern can be obtained by applying and drying a paste containing a resin binder and a conductive filler, followed by baking, but it is necessary to bake at a high temperature of 500 ° C. or higher. It has a drawback that it cannot be provided. On the other hand, the organic-inorganic composite conductive pattern can be formed by processing at a relatively low temperature, but it has been relatively difficult to achieve high conductivity.

  Conventionally, so-called conductive pastes in which a large amount of fine particles of silver flakes, copper powder, or carbon particles are mixed in a resin or adhesive to form an organic-inorganic composite conductive pattern as described above have been put into practical use. Has been. Many of these are formed by a screen printing method and formed into a conductive pattern by heat curing (see, for example, Patent Documents 1 and 2). However, it has been difficult to achieve high definition patterns by screen printing. In order to solve this problem, an ultraviolet curable conductive paste has been developed. For example, a paste in which conductive fine particles are dispersed in photosensitive polyimide is applied, dried, exposed, developed, and after forming a fine pattern, the conductive fine particles are brought into contact with each other by shrinking the resin by curing. A bump forming method for developing conductivity (for example, see Patent Document 3), a method for producing a conductive pad, wiring, and the like using a photosensitive conductive paste in which silver powder is dispersed in a photosensitive phenoxy resin. (For example, refer to Patent Documents 4 and 5).

Japanese Patent Application No. Sho 63-79727 Japanese Patent Application No. 2004-73740 Japanese Patent Application No. 4-327423 Japanese Patent Application No. 58-17510 Japanese Patent Application No. Hei 3-238020

  In Patent Document 3, which is a conventional technique, it is necessary to heat at about 400 ° C. in order to develop conductivity, and there is a problem that a base material to be used is limited. In Patent Documents 4 and 5, a photosensitive phenoxy resin or a photosensitive acrylic-modified epoxy resin can be used to develop conductivity at a low temperature, but the resulting conductive pattern has a high specific resistance value and is 50 μm or less. There is a problem that fine patterning is difficult. An object of the present invention is to solve the problem that high temperature heating is required for the development of conductivity, and the resulting conductive pattern exhibits a high specific resistance.

  The present invention comprises a compound (A) having at least one unsaturated double bond and an alkoxy group, a photosensitive component (B) having an unsaturated double bond, a photopolymerization initiator (C) and a conductive filler (D). It is the photosensitive paste for organic-inorganic composite conductive pattern formation characterized by including.

  According to the present invention, an organic-inorganic composite conductive pattern having a low specific resistivity can be obtained even under low-temperature curing conditions, and fine patterning is possible due to high photosensitive characteristics. Wiring and the like can be easily formed.

  Furthermore, the use of a photopolymerization initiator or acid generator having a benzoyl skeleton, which is another aspect of the present invention, makes it possible to develop conductivity even under lower temperature curing conditions.

It is the schematic diagram which showed the translucent pattern of the photomask used for the specific resistivity evaluation of an Example.

  The photosensitive paste for forming an organic-inorganic composite conductive pattern of the present invention is obtained by dispersing conductive filler (D) particles in a photosensitive resin containing compounds (A), (B), and (C). It is. The paste is applied on a substrate, dried to remove the solvent, and then subjected to exposure, development, and curing processes to obtain a desired conductive pattern on the substrate for forming an organic-inorganic composite conductive pattern. It is a photosensitive paste. The obtained conductive pattern is an organic-inorganic composite, and the conductive properties are exhibited when the conductive fillers come into contact with each other by curing shrinkage during curing.

  The compound (A) having one or more unsaturated double bonds and alkoxy groups of the present invention has at least one alkoxy group in the molecule that is condensed with an unsaturated double bond that causes a polymerization reaction by the action of a photopolymerization initiator. It is a compound having two or more. Examples of the unsaturated double bond include an acrylic group, a methacryl group, and a vinyl group having a carbon-carbon double bond. Examples of the alkoxy group include a methoxy group, an ethoxy group, a butoxy group, and an isobutoxy group. The alcohol having a relatively high molecular weight is preferable, and an ethoxy group, a butoxy group, an isobutoxy group, and the like are preferable. Of these, a butoxy group and an isobutoxy group are particularly preferable. Specific examples of such compound (A) include N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylacrylamide, N-ethoxymethylmethacrylamide, Nn-butoxymethylacrylamide, Nn- Examples include butoxymethyl methacrylamide, N-isobutoxymethyl acrylamide, N-isobutoxymethyl methacrylamide, and the like. Among these, N-ethoxymethylacrylamide, N-ethoxymethylmethacrylamide, Nn-butoxymethylacrylamide, Nn-butoxymethylmethacrylamide, N-isobutoxymethylacrylamide, and N-isobutoxymethylmethacrylamide are preferable. Nn-butoxymethyl acrylamide, Nn-butoxymethyl methacrylamide, N-isobutoxymethyl acrylamide, and N-isobutoxymethyl methacrylamide are more preferable.

  The amount of the compound (A) added is preferably 10 to 300 parts by weight, more preferably 50 to 200 parts by weight per 100 parts by weight of the photosensitive component (B) having an unsaturated double bond. Part. By making the addition amount with respect to 100 parts by weight of the photosensitive component (B) having an unsaturated double bond 50 parts by weight or more, it is possible to increase the shrinkage particularly during curing, and increase the contact probability between the conductive fillers. can do. As a result, the specific resistivity of the organic-inorganic composite conductive pattern that is the final composition can be lowered. Further, by making the addition amount with respect to 100 parts by weight of the photosensitive component (B) having an unsaturated double bond 200 parts by weight or less, the tackiness of the paste composition film after removal of the solvent can be particularly reduced. It works preferentially in patterning, such as suppressing the occurrence of defects in the conductive pattern.

  The photosensitive component (B) having an unsaturated double bond of the present invention means a monomer, oligomer or polymer having at least one unsaturated double bond in the molecule, and one or more of them are used. Can do. The photosensitive component (B) having an unsaturated double bond is not particularly limited, but it is desirable to include an alkali-soluble polymer for the development of the pattern processing of the present invention, because development with an alkaline aqueous solution rather than an organic solvent is preferable.

  Examples of the alkali-soluble polymer include acrylic copolymers. The acrylic copolymer is a copolymer containing at least an acrylic monomer as a copolymerization component. Specific examples of the acrylic monomer include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n -Butyl acrylate, sec-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-pentyl acrylate, allyl acrylate, benzyl acrylate, butoxyethyl acrylate, butoxytriethylene glycol acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl Acrylate, 2-ethylhexyl acrylate, glycerol acrylate, glycidyl acrylate, heptadecafrodecyl acrylate 2-hydroxyethyl acrylate, isobornyl acrylate, 2-hydroxypropyl acrylate, isodexyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene glycol acrylate, methoxydiethylene glycol acrylate, octafluoropentyl acrylate, Acrylic monomers such as phenoxyethyl acrylate, stearyl acrylate, trifluoroethyl acrylate, acrylamide, aminoethyl acrylate, phenyl acrylate, phenoxyethyl acrylate, 1-naphthyl acrylate, 2-naphthyl acrylate, thiophenol acrylate, benzyl mercaptan acrylate, and the like Acrylate Such as those instead acrylate and the like.

  As the copolymerization component other than the acrylic monomer, any compound having a carbon-carbon double bond can be used, but preferably styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, α- Examples thereof include styrenes such as methylstyrene, chloromethylstyrene, and hydroxymethylstyrene, γ-methacryloxypropyltrimethoxysilane, and 1-vinyl-2-pyrrolidone.

  In order to impart alkali solubility to the acrylic copolymer, it is achieved by using an unsaturated acid such as an unsaturated carboxylic acid as a monomer. Specific examples of the unsaturated acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetate, and acid anhydrides thereof. By adding these to the molecular chain, the acid value of the polymer can be adjusted. The acid value of the polymer is preferably in the range of 80 to 140 from the viewpoint of developability.

  Specific examples of the polyfunctional monomer having two or more unsaturated double bonds in the molecule include allylated cyclohexyl diacrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, and ethylene glycol diacrylate. Acrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, dipentaerythritol hexaacrylate, dipentaerythritol monohydroxypentaacrylate, ditrimethylolpropane tetraacrylate, glycerol diacrylate, methoxylated cyclohexyl diacrylate, neopentyl glycol Diacrylate, propylene glycol diacrylate, polypropylene glycol diacrylate, trig Serol diacrylate, trimethylolpropane triacrylate, bisphenol A diacrylate, diacrylate of bisphenol A-ethylene oxide adduct, diacrylate of bisphenol A-propylene oxide adduct, or one part or all of acrylic group of the above compound And the like.

  In addition, a part of the unsaturated acid in the acrylic polymer obtained by using the unsaturated acid such as the unsaturated carboxylic acid as a monomer as a monomer, a group that reacts with the unsaturated acid such as glycidyl (meth) acrylate, and the unsaturated group. An alkali-soluble polymer having a reactive unsaturated double bond in the side chain obtained by reacting a compound having both groups having a double bond can also be preferably used.

  The photopolymerization initiator (C) of the present invention refers to a compound that absorbs light of a short wavelength such as ultraviolet rays and decomposes to generate a radical. Specific examples include 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)], 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2, 4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, ethanone, 1- [9-ethyl-6-2 (2-methylbenzoyl) -9H -Carbazol-3-yl] -1- (O-acetyloxime), benzophenone, methyl o-benzoylbenzoate, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4 , 4'-dichlorobenzophenone, 4-benzoyl-4'-methyldiphenyl ketone, di Benzyl ketone, fluorenone, 2,2'-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyl, benzyldimethyl ketal, benzyl-β-methoxyethyl acetal, benzoin, benzoin methyl ether, benzoin butyl ether, anthraquinone, 2-t-butylanthraquinone, 2-amylanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibenzosuberone, methyleneanthrone, 4-azidobenzalacetophenone, 2,6- (P-azidobenzylidene) cyclohexanone, 6-bis (p-azidobenzylidene) -4-methylcyclohexanone, 1-phenyl-1,2-butanedione-2- (o-methoxycarbonyl) oxime, 1-phenyl-propanedione 2- (o-ethoxycarbonyl) oxime, 1-phenyl-propanedione-2- (o-benzoyl) oxime, 1,3-diphenyl-propanetrione-2- (o-ethoxycarbonyl) oxime, 1-phenyl- 3-Ethoxy-propanetrione-2- (o-benzoyl) oxime, Michler's ketone, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, naphthalenesulfonyl chloride, quinolinesulfonyl chloride, N-phenyl Thiacridone, 4, 4 -Photoreducing dyes such as azobisisobutyronitrile, diphenyl disulfide, benzthiazole disulfide, triphenylphosphine, camphorquinone, carbon tetrabromide, tribromophenyl sulfone, benzoin peroxide and eosin, methylene blue, ascorbic acid, tri A combination of reducing agents such as ethanolamine can be mentioned, but the invention is not particularly limited thereto. In the present invention, one or more of these can be used. Among them, those having a benzoyl skeleton in the molecule are preferable from the viewpoint of promoting the condensation reaction by the alkoxy group of the compound (A), and 1,2-octanedione, 1- [4- (phenylthio) -2 -(O-benzoyloxime)], 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,4,6-trimethyl) Benzoyl) -phenylphosphine oxide, ethanone, or 1- [9-ethyl-6-2 (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) is particularly preferred.

  The addition amount of the photopolymerization initiator (C) is preferably 0.05 to 30 parts by weight, more preferably 100 parts by weight of the photosensitive component (B) having an unsaturated double bond, and more preferably 5 to 20 parts by weight. By setting the addition amount of the photopolymerization initiator (C) to 5 parts by weight or more with respect to 100 parts by weight of the photosensitive component (B) having an unsaturated double bond, the cured density in the exposed area is increased, and after development, The remaining film rate can be increased. Moreover, the coating film by a photoinitiator (C) especially is made by making the addition amount of a photoinitiator (C) into 20 weight part or less with respect to 100 weight part of photosensitive components (B) which have an unsaturated double bond. Excessive light absorption in the upper part can be suppressed, and the conductive pattern can be prevented from becoming an inversely tapered shape and the adhesiveness to the substrate being lowered.

  The paste of the present invention can be improved in sensitivity by adding a sensitizer together with the photopolymerization initiator (C), or can expand the wavelength range effective for the reaction.

  As a photoinitiator (C) and a sensitizer, what has a sensitivity to a comparatively long wavelength is suitable. Since the shorter the wavelength of the light beam, the more easily affected by absorption and scattering, it is preferable to have sensitivity up to a relatively long wavelength in order to cure the inside of the coating film. Since many sensitizers have a sensitivity up to a relatively long wavelength, when used in combination with the photopolymerization initiator (C), the workability of a thick film is superior.

  Specific examples of the sensitizer include 2,4-diethylthioxanthone, isopropylthioxanthone, 2,3-bis (4-diethylaminobenzal) cyclopentanone, 2,6-bis (4-dimethylaminobenzal) cyclohexanone, 2,6-bis (4-dimethylaminobenzal) -4-methylcyclohexanone, Michler's ketone, 4,4-bis (diethylamino) benzophenone, 4,4-bis (dimethylamino) chalcone, 4,4-bis (diethylamino) Chalcone, p-dimethylaminocinnamylidene indanone, p-dimethylaminobenzylidene indanone, 2- (p-dimethylaminophenylvinylene) isonaphthothiazole, 1,3-bis (4-dimethylaminophenylvinylene) isonaphthothiazole 1,3-bis (4-dimethyl) Minobenzal) acetone, 1,3-carbonylbis (4-diethylaminobenzal) acetone, 3,3-carbonylbis (7-diethylaminocoumarin), N-phenyl-N-ethylethanolamine, N-phenylethanolamine, N- Examples include tolyldiethanolamine, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 3-phenyl-5-benzoylthiotetrazole, and 1-phenyl-5-ethoxycarbonylthiotetrazole. In the present invention, one or more of these can be used. When a sensitizer is added to the paste of the present invention, the amount added is usually in the range of 0.05 to 10 parts by weight with respect to 100 parts by weight of the photosensitive component (B) having an unsaturated double bond. Is more preferable, and 0.1 to 10 parts by weight is more preferable. The effect of improving the photosensitivity is easily exerted by setting the addition amount to 100 parts by weight of the photosensitive component (B) having an unsaturated double bond to 0.1 parts by weight or more, and has an unsaturated double bond. By making the addition amount with respect to 100 parts by weight of the photosensitive component (B) 10 parts by weight or less, excessive light absorption occurs particularly at the upper part of the coating film, the conductive pattern becomes a reverse taper shape, and adhesion to the substrate. Can be suppressed.

  The conductive filler (D) of the present invention preferably contains at least one of Ag, Au, Cu, Pt, Pb, Sn, Ni, Al, W, Mo, ruthenium oxide, Cr, Ti, and indium. These conductive fillers can be used alone, as an alloy, or as a mixed powder. Moreover, the electroconductive particle which coat | covered the surface of the insulating particle or electroconductive particle with the above-mentioned component can be used similarly. Among these, Ag, Cu and Au are preferable from the viewpoint of conductivity, and Ag is more preferable from the viewpoint of cost and stability.

  The average particle diameter of the conductive filler (D) is preferably 0.5 to 10 μm, more preferably 1 to 6 μm. When the average particle size is 1 μm or more, the contact probability between the conductive fillers is improved, the specific resistance value of the produced organic-inorganic composite conductive pattern, and the disconnection probability can be lowered, and the ultraviolet rays at the time of exposure Can pass through the film smoothly and facilitates fine patterning. If the average particle size is 6 μm or less, the surface smoothness, pattern accuracy, and dimensional accuracy of the printed circuit pattern are improved. The average particle diameter can be determined by a Coulter counter method, a photon correlation method, a laser diffraction method, or the like.

  The addition amount of the conductive filler (D) is preferably in the range of 70 to 95% by weight, more preferably 80 to 90% by weight, based on the total solid content in the paste. By setting it to 80% by weight or more, the contact probability between the conductive fillers particularly during curing shrinkage during curing can be improved, and the specific resistance value and the disconnection probability of the produced organic-inorganic composite conductive pattern can be lowered. it can. In addition, by setting it to 90% by weight or less, particularly ultraviolet rays at the time of exposure can smoothly pass through the film, and fine patterning becomes easy. Moreover, solid content removes a solvent from paste.

  The acid generator (E) of the present invention refers to a substance that reacts with light or heat to generate an acid. Due to the catalytic effect of the acid generated, it has the effect of accelerating the condensation reaction of the alkoxy group in the compound (A) having one or more unsaturated double bonds and alkoxy groups at a low temperature. As a result, it is possible to develop conductivity under a lower temperature curing condition and reduce the specific resistivity.

  Examples of the photoacid generator (E) include quinonediazide, diazodisulfone, and triphenylsulfonium substances, and examples of the thermal acid generator include sulfonium salts. Since the photoacid generator generates an acid in the exposed portion by exposure, a difference in solubility between the exposed portion and the unexposed portion is reduced, and there is a possibility that the patterning property may be adversely affected. From the viewpoint of acid strength, a sulfonium salt is more preferable.

  The addition amount of the acid generator (E) is preferably within a range of 0.01 to 5 parts by weight, more preferably 0 with respect to 100 parts by weight of the photosensitive component (B) having an unsaturated double bond. 0.05 to 5 parts by weight. By adding 0.05 parts by weight or more with respect to 100 parts by weight of the photosensitive component (B) having an unsaturated double bond, the compound (A) having at least one unsaturated double bond and one or more alkoxy groups can be used. The function as a catalyst for the condensation reaction of the alkoxy group becomes remarkable.

  The paste of the present invention may contain a solvent. Examples of the solvent include N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, dimethylimidazolidinone, dimethyl sulfoxide, γ-butyrolactone, ethyl lactate, 1-methoxy-2-propanol, 1 -Ethoxy-2-propanol, ethylene glycol mono-n-propyl ether, diacetone alcohol, tetrahydrofurfuryl alcohol, propylene glycol monomethyl ether acetate and the like. A solvent can be used individually by 1 type, or 2 or more types can be mixed and used for it. The solvent may be added later for the purpose of adjusting the viscosity after preparing the paste.

  The paste of the present invention is a non-photosensitive polymer, crosslinking agent, plasticizer, leveling agent, surfactant, silane coupling agent that does not have an unsaturated double bond in the molecule as long as the desired properties are not impaired. Additives such as antifoaming agents and pigments can also be blended. Specific examples of the non-photosensitive polymer include epoxy resin, novolac resin, phenol resin, polyimide precursor, and closed ring polyimide.

  Examples of the crosslinking agent include methylated melamine resins and methylated urea resins.

  Specific examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, polyethylene glycol, glycerin and the like. Specific examples of the leveling agent include a special vinyl polymer and a special acrylic polymer.

  As silane coupling agents, methyltrimethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, hexamethyldisilazane, 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane Etc.

  The paste of the present invention is produced using a disperser, a kneader or the like. Specific examples of these include, but are not limited to, a three-roller, a ball mill, and a planetary ball mill.

  Next, the manufacturing method of the organic-inorganic composite conductive pattern using the paste of the present invention will be described. In order to produce an organic-inorganic composite conductive pattern, the paste of the present invention is applied on a substrate, heated to volatilize the solvent and dried. Thereafter, exposure is performed through a pattern formation mask, and a desired pattern is formed on the substrate through a development process. And it cures and produces an organic-inorganic composite conductive pattern.

Examples of the substrate used in the present invention include a silicon wafer, a ceramic substrate, and an organic substrate. Examples of the ceramic substrate include a glass substrate, an alumina substrate, an aluminum nitride substrate, and a silicon carbide substrate. Examples of the organic substrate include an epoxy substrate, a polyetherimide resin substrate, a polyetherketone resin substrate, a polysulfone resin substrate, and a polyimide. Although a film, a polyester film, etc. are mentioned, it is not limited to these.
Examples of the method of applying the paste of the present invention to a substrate include spin coating using a spinner, spray coating, roll coating, screen printing, blade coater, die coater, calendar coater, meniscus coater, and bar coater. Further, the coating film thickness varies depending on the coating method, the solid content concentration of the composition, the viscosity, and the like, but it is usually applied such that the film thickness after drying is in the range of 0.1 to 50 μm.

  Next, the solvent is removed from the paste composition film coated on the substrate. Examples of the method for removing the solvent include heat drying using an oven, a hot plate, infrared rays, and vacuum drying. Heat drying is preferably performed in the range of 50 ° C. to 180 ° C. for 1 minute to several hours.

  On the paste composition film after removal of the solvent, pattern processing is performed by photolithography. As a light source used for exposure, it is preferable to use i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a mercury lamp.

  After exposure, a desired pattern is obtained by removing an unexposed portion using a developer. Developer solutions for alkali development include tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate An aqueous solution of a compound such as dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine or hexamethylenediamine is preferred. In some cases, these aqueous solutions may contain polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, and γ-butyrolactone, and alcohols such as methanol, ethanol, and isopropanol. , Esters such as ethyl lactate and propylene glycol monomethyl ether acetate, and ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone may be used alone or as a developer. Moreover, what added surfactant to these alkaline aqueous solution can also be used as a developing solution. Developers for organic development include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, hexamethyl phosphortriamide, etc. Can be used alone or in combination with methanol, ethanol, isopropyl alcohol, xylene, water, methyl carbitol, ethyl carbitol and the like.

  The development can be performed by a method such as spraying the developer on the surface of the coating film while leaving or rotating the substrate, immersing the substrate in the developer, or applying ultrasonic waves while immersing.

  After development, a rinsing treatment with water may be performed. Here, alcohols such as ethanol and isopropyl alcohol, and esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to water for rinsing treatment.

  Next, the paste composition film is cured in order to conduct the condensation reaction of the alkoxy group in the compound (A) having at least one unsaturated double bond and one or more alkoxy groups. Examples of the curing method include oven drying, inert oven, hot plate, heat drying using infrared rays, vacuum drying, and the like. The curing temperature is preferably in the range of 130 to 400 ° C, more preferably 150 to 400 ° C. By setting the curing temperature to 150 ° C. or higher, the reaction rate of the condensation reaction of the compound (A) having at least one unsaturated double bond and an alkoxy group can be improved, and as a result, contact between the conductive fillers can be improved. The probability increases and the specific resistivity decreases. In addition, since the organic-inorganic composite conductive pattern forming photosensitive paste of the present invention can obtain high conductivity with a relatively low temperature cure of 400 ° C. or lower, the substrate has low heat resistance or low heat resistance. It can be used in combination with materials. Thus, an organic-inorganic composite conductive pattern can be produced through a curing process.

Examples of the present invention will be described below, but the present invention is not limited to these examples. The materials and evaluation methods used in each example and comparative example are as follows.
<Patternability evaluation method>
An organic-inorganic composite conductive pattern forming paste is applied on a substrate so that the dry thickness is 12 μm, dried, and a group of straight lines arranged in a constant line and space (L / S) is defined as one unit. An organic-inorganic composite conductive pattern was obtained by exposing, developing, and curing through a photomask having a translucent pattern having nine types of units having different values of S. The L / S values of each unit were 500/500, 250/250, 100/100, 50/50, 40/40, 30/30, 25/25, 20/20, and 15/15 (respective line widths). (Represents (μm) / interval (μm)). The pattern is observed using an optical microscope, a pattern having a minimum L / S value with no residue between the patterns and no pattern peeling is confirmed, and the minimum L / S value can be developed. S.
<Evaluation method of specific resistivity>
It exposed through the photomask which has the translucent part A of the pattern shown in FIG. 1, developed and cured, and the conductive pattern for a specific resistivity measurement was obtained. The line width of the conductive pattern is 0.400 mm, and the line length is 80 mm. The ends of the obtained pattern were connected with a surface resistance meter, the surface resistance value was measured, and the specific resistivity was calculated by applying to the following calculation formula. The film thickness was measured using a stylus step meter “Surfcom 1400” (trade name, manufactured by Tokyo Seimitsu Co., Ltd.). The film thickness was measured at three positions at random, and the average value of the three points was taken as the film thickness. The length measurement was 1 mm, and the scanning speed was 0.3 mm / s. The line width was determined by observing three positions at random with an optical microscope and analyzing the image data to obtain the average value of the three points as the line width.
Specific resistivity = surface resistance value × film thickness × line width / line length The materials used in Examples and Comparative Examples are as follows.
Compound (A) having at least one unsaturated double bond and alkoxy group
A-1: Nn-butoxymethylacrylamide (manufactured by Kasano Kosan Co., Ltd.)
A-2: N-isobutoxymethylacrylamide (manufactured by Kasano Kosan Co., Ltd.)
A-3: Nn-butoxymethyl methacrylamide (manufactured by Kasano Kosan Co., Ltd.)
A-4: N-isobutoxymethyl methacrylamide (manufactured by Kasano Kosan Co., Ltd.)
A-5: N-ethoxymethylacrylamide (manufactured by Kasano Kosan Co., Ltd.)
A-6: N-ethoxymethyl methacrylamide (manufactured by Kasano Kosan Co., Ltd.)
A-7: N-methoxymethylacrylamide (manufactured by Kasano Kosan Co., Ltd.)
A-8: N-methoxymethyl methacrylamide (manufactured by Kasano Kosan Co., Ltd.)
Photosensitive component (B) having an unsaturated double bond
B-1: Acrylic polymer AP-003: Addition reaction of 0.8 equivalent of glycidyl methacrylate to the carboxyl group of a copolymer consisting of methacrylic acid / methyl methacrylate / styrene = 40/30/30 (weight) Average molecular weight 29000, acid value 110) (Toray Industries, Inc.)
B-2: Ditrimethylolpropane tetraacrylate (manufactured by Kyoeisha Chemical Co., Ltd.)
B-3: Dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd.)
B-4: ZFR-1491H (acid-modified epoxy acrylate) (trade name, manufactured by Nippon Kayaku Co., Ltd.)
B-5: Triglycerol diacrylate (trade name, manufactured by Oil & Fat Products Co., Ltd.)
Photopolymerization initiator (C)
IRGACURE OXE-01 (trade name, manufactured by Ciba Japan Co., Ltd.)
Conductive filler (D)
The materials listed in Table 1 and those having an average particle size were used. The average particle size was determined by the following method.
<Measurement of average particle diameter>
The average particle size of the conductive filler (D) was measured by a dynamic light scattering particle size distribution meter manufactured by HORIBA.
Acid generator (E)
E-1: Sun-Aid SI-110 (trade name, manufactured by Sanshin Chemical Industry Co., Ltd.)
E-2: IRGACURE PAG103 (trade name, manufactured by Ciba Japan Co., Ltd.)
E-3: IRGACURE PAG108 (trade name, manufactured by Ciba Japan Co., Ltd.)
E-4: CGI-NIT (trade name, manufactured by Ciba Japan Co., Ltd.)
E-5: CGI-MDT (trade name, manufactured by Ciba Japan Co., Ltd.)
Solvent: γ-butyrolactone (Mitsubishi Gas Chemical Co., Ltd.)
Additive non-photosensitive polymer: Alkali-soluble closed ring polyimide represented by the following formula having an acidic group in the structural unit of a general polyimide or at the end of the main chain

(A represents an acidic group.)
Polyimide precursor: Polyimide copolymer phenol resin obtained by reacting 4,4′-diaminodiphenyl sulfide, 4,4′-diaminodiphenyl ether and pyromellitic dianhydride: PSF-2808 (trade name, Gunei) Chemical Industry Co., Ltd.)
Epoxy resin: 828 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.)
Crosslinking agent: Nicalac MW-390 (trade name, manufactured by Sanwa Chemical Co., Ltd.)
Plasticizer: Dimethyl phthalate (Tokyo Chemical Industry Co., Ltd.)
Surfactant: Emulgen A-60 (trade name, manufactured by Kao Corporation)
Silane coupling agent: KBM-503 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.)
Leveling agent: L-1980 (trade name, manufactured by Enomoto Kasei Co., Ltd.)
Pigment: Sudan IV (manufactured by Tokyo Chemical Industry Co., Ltd.)
Example 1
In a 100 ml clean bottle, 20 g of alkali-soluble acrylic polymer AP-003 (manufactured by Toray Industries, Inc., A-1), 20 g of Nn-butoxymethylacrylamide (manufactured by Kasano Kosan Co., Ltd., B-1), photopolymerization initiator OXE 4 g of -01 (manufactured by Ciba Japan Co., Ltd.), 0.6 g of acid generator SI-110 (manufactured by Sanshin Chemical Industry Co., Ltd., E-1) and 10 g of γ-butyrolactone (manufactured by Mitsubishi Gas Chemical Company, Inc.) And “Awatori Nertaro” (trade name: ARE-310, manufactured by Sinky Co., Ltd.) to obtain 45.6 g of a photosensitive resin solution (solid content: 97.8 wt%). 30.99 g of the obtained photosensitive resin solution and 26.1 g of Ag particles having an average particle diameter of 2 μm are mixed and kneaded using a three-roller “EXAKT M-50” (trade name, manufactured by EXAKT). 1 g of an organic-inorganic composite conductive pattern forming photosensitive paste was obtained.

The obtained paste was applied on a glass substrate by screen printing, and prebaked in a drying oven at 120 ° C. for 10 minutes. Thereafter, full line exposure is performed using an exposure apparatus “PEM-6M” (trade name, manufactured by Union Optics Co., Ltd.) with an exposure amount of 150 mJ / cm ² (wavelength 365 nm conversion), and 0.5% Na ₂ CO ₃ solution is used. Immersion development was performed for 2 minutes, rinsed with ultrapure water, and then cured at 180 ° C. for 1 hour in a drying oven. The film thickness of the patterned organic-inorganic composite conductive pattern was 10 μm. When the line-and-space (L / S) pattern of the organic-inorganic composite conductive pattern was confirmed using an optical microscope, the pattern was satisfactorily processed without any inter-pattern residue and pattern peeling up to 15/15 μm. I confirmed. And when the specific resistivity of the organic-inorganic composite conductive pattern was measured, it was 5.5 × 10 ⁻⁵ Ωcm.
Examples 2-69
The photosensitive paste for forming an organic-inorganic composite conductive pattern shown in Tables 1 to 4 was manufactured by the same method as in Example 1 (see Tables 5 and 6 for substrate types and curing conditions), and the evaluation results are shown. 5 and shown in Table 6.
Comparative Examples 1-7
The photosensitive paste for forming an organic-inorganic composite conductive pattern shown in Tables 1 to 4 was manufactured by the same method as in Example 1 (see Tables 5 and 6 for substrate types and curing conditions), and the evaluation results are shown. 5 and shown in Table 6.

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Claims (6)

Nn-butoxymethylacrylamide, Nn-butoxymethylmethacrylamide, N-isobutoxymethylacrylamide, N-isobutoxymethylmethacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylacrylamide And a compound (A) selected from the group consisting of N-ethoxymethylmethacrylamide , a photosensitive component (B) having an unsaturated double bond, a photopolymerization initiator (C) and a conductive filler (D). A photosensitive paste for forming an organic-inorganic composite conductive pattern. The photopolymerization initiator (C) is an organic claim 1 Symbol mounting, characterized in that it comprises benzoyl skeleton in the molecule - inorganic composite conductive pattern forming photosensitive paste. The photopolymerization initiator (C) is 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)], 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) - phenyl phosphine oxide, bis (2,4,6-trimethylbenzoyl) - phenyl phosphine oxide, was or, 1- [9-ethyl -6-2 (2 The photosensitive paste for forming an organic-inorganic composite conductive pattern according to claim 1 or 2, which is -methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime). The photosensitive paste for forming an organic-inorganic composite conductive pattern according to any one of claims 1 to 3 , further comprising an acid generator (E). The photosensitive paste for forming an organic-inorganic composite conductive pattern according to claim 4 , wherein the acid generator (E) is a sulfonium salt. The organic-inorganic composite conductive pattern forming photosensitive paste according to any one of claims 1 to 5 is applied on a substrate, dried, exposed, developed, and then cured at a temperature of 150 ° C to 400 ° C. The manufacturing method of the organic-inorganic composite conductive pattern characterized by the above-mentioned.

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