JP4568105B2 - Manufacturing method of conductive fine pattern - Google Patents

Manufacturing method of conductive fine pattern Download PDF

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JP4568105B2
JP4568105B2 JP2004361922A JP2004361922A JP4568105B2 JP 4568105 B2 JP4568105 B2 JP 4568105B2 JP 2004361922 A JP2004361922 A JP 2004361922A JP 2004361922 A JP2004361922 A JP 2004361922A JP 4568105 B2 JP4568105 B2 JP 4568105B2
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fine pattern
heat
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producing
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JP2006173277A (en
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一喜 山本
弘司 福井
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積水化学工業株式会社
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  The present invention relates to a method for producing a conductive fine pattern.

  Recently, along with the downsizing of electronic equipment and electronic components, it has been demanded that the circuit wiring pattern formed on the wiring board is further miniaturized, and a conductive metal paste is applied to a substrate to form a wiring pattern. The method of forming is actively researched.

  For example, there is a method of forming a wiring pattern by applying a conductive metal paste made of fine metal powder having an average particle diameter of about 0.5 to 20 μm, metal nanoparticles, and an epoxy resin to a base material and curing it. Then, the wiring width and the wiring interval could only be set to about 50 μm.

In order to reduce the wiring width and the wiring interval, the coating layer of the fine wiring pattern to be drawn is prepared by using a paste-like dispersion liquid containing metal nanoparticles whose average particle diameter is selected in the range of 1 to 100 nm. A step of forming on the substrate surface, and a step of firing the metal nanoparticles contained in the coating layer to form a sintered body layer between the metal nanoparticles, the metal As a paste-like dispersion containing nanoparticles, the dispersion is obtained by uniformly dispersing metal nanoparticles in a dispersion solvent, and the surface of the metal nanoparticles is coordinated with the metal elements contained in the metal nanoparticles. A group that includes a nitrogen, oxygen, or sulfur atom as a group capable of a simple bond, and is coated with one or more compounds having a group that can be coordinated by a lone pair of electrons of the atom, Particle 10 10 parts by mass or more of a compound having a group containing nitrogen, oxygen, or sulfur atom as a sum, and 10 to 30 parts by mass with respect to parts by mass. When the dispersion solvent is heated to 100 ° C. or more, the dispersion One or two or more organic solvents having high solubility, capable of dissolving 50 parts by mass or more of the compound having a group containing nitrogen, oxygen or sulfur atoms covering the surface of the metal nanoparticles per 100 parts by mass of the solvent It is a mixed solvent composed of a liquid organic substance, containing 8 to 220 parts by mass of the dispersion solvent with respect to 100 parts by mass of the metal nanoparticles, and one or two or more liquids constituting the dispersion solvent In the temperature range of 20 ° C. to 300 ° C., the organic substance does not exhibit reactivity with the compound having a group containing nitrogen, oxygen, or sulfur atoms, and the nitrogen, oxygen, or The compound having a group containing a sulfur atom has a boiling point in the range of 150 ° C. to 300 ° C., a melting point of 20 ° C. or less, and one organic solvent constituting the dispersion solvent or two or more liquid forms The organic material has a boiling point in the range of 150 ° C. to 300 ° C. and has a melting point of 20 ° C. or less, and the conductive nanoparticle paste is used to form a sintered body layer between the metal nanoparticles. Is formed by heating the coating layer to a temperature not exceeding 300 ° C., and when the heating in the baking treatment is performed, a compound having a group containing nitrogen, oxygen, and sulfur atoms that coats the surface of the metal nanoparticles, Dissociation and elution from the surface of the metal nanoparticles are performed in a dispersion solvent using a highly soluble organic solvent or a mixed solvent composed of two or more liquid organic substances, and surface contact between the metal nanoparticles is achieved. A method for forming a fine wiring pattern has been proposed, characterized in that the metal nanoparticles are sintered together and the dispersion solvent is removed by evaporation, and a coating layer of the wiring pattern is formed on the substrate surface. As the process to perform, an inkjet printing method and a screen printing method have been proposed (for example, see Patent Document 1). ) Has been proposed.
JP 2004-273205 A

  However, the wiring width and the wiring interval of the wiring pattern obtained by the above method are about 20 μm, and a fine wiring pattern having a wiring width and a wiring interval of 10 μm or less could not be obtained.

  In view of the above-described drawbacks, an object of the present invention is a method for producing a conductive fine pattern capable of easily and accurately obtaining a fine wiring pattern having a wiring width and a wiring interval of 0.2 μm or more and 10 μm or less with high accuracy and reproducibility. Is to provide.

  The method for producing a conductive fine pattern of the present invention comprises applying a heat extinguishing composition comprising a heat extinguishing material mainly composed of a thermoplastic resin and conductive metal nanoparticles to a mold on which a predetermined fine pattern is formed. The step of laminating the heat extinguishing composition layer, the step of transferring the heat extinguishing composition layer according to the fine pattern onto the substrate by the reversal imprint method, and removing the heat extinguishing material by heating, It consists of the process of forming a conductive fine pattern on a base material.

  The heat extinguishing material used in the present invention is a resin composition mainly composed of a thermoplastic resin, which decomposes and gasifies and disappears when heated. When heated to 150 to 350 ° C., it is 10 A resin composition that disappears by 95% by weight or more within a minute is preferable.

  The thermoplastic resin is not particularly limited as long as it decomposes and gasifies and disappears by heating, but a polyoxyalkylene resin having an oxygen content of 15 to 55% by weight is preferable.

  As said polyoxyalkylene resin, the polymer etc. which contain polyalkylene glycol and polyoxyalkylene as a segment are mentioned, for example.

  Examples of the polyalkylene glycol include polypropylene glycol, polyethylene glycol, polytetramethylene glycol, and the like. These may be used alone or in combination of two or more. When using 2 or more types together, it is preferable to add 50 weight% or more of polypropylene glycol.

  The polymer containing the polyoxyalkylene as a segment is, for example, a polymer containing a polyoxyalkylene such as polyoxymethylene, polyoxyethylene, polyoxypropylene, polyoxytrimethylene, polyoxytetramethylene or the like as a segment. Examples thereof include polyurethane, polyester, polyamide, polyimide, poly (meth) acrylate, polystyrene and the like containing the above polyoxyalkylene as a segment.

  The number average molecular weight of the polyoxyalkylene resin is preferably 5,000 to 5,000,000 because it becomes more volatile when it becomes smaller and becomes difficult to decompose when it becomes larger.

  The polyoxyalkylene resin may be cross-linked. Crosslinking may be physical crosslinking or chemical crosslinking.

  Examples of the physical crosslinking method include, for example, a method of selecting and crystallizing a crystalline segment as a polymerization segment, a method of increasing molecular chain entanglement using a high molecular weight segment, a functional group such as a hydroxyl group, an amino group, and an amide group. For example, a method of forming a hydrogen bond using a segment having the same may be used.

  Examples of the chemical crosslinking method include a method of crosslinking a polyoxyalkylene resin having a crosslinkable functional group with a crosslinking agent.

  Examples of the crosslinkable functional groups include hydrolyzable silyl groups; isocyanate groups; epoxy groups; oxetanyl groups; acid anhydride groups; carboxyl groups; hydroxyl groups; and (meth) acryloyl groups and styryl groups. Examples thereof include a hydrogen group, and a hydrolyzable silyl group, an isocyanate group, an epoxy group, a (meth) acryloyl group or a styryl group is preferable.

  Examples of the polyoxyalkylene resin having a hydrolyzable silyl group include, for example, trade names “MS polymer S-203”, “MS polymer S-303”, “MS polymer S-903” manufactured by Kaneka Chemical Co., Ltd. “Epion EP-103S”, “Epion EP-303S”, “Epion EP-505S”, “Syryl SAT-200”, “Syryl MA-403”, “Syryl MA-447”, trade names “EXE” manufactured by Asahi Glass Co., Ltd. Star ESS-2410 "," Exester ESS-2420 "," Exester ESS-3630 ", trade name" (N-trimethoxysilylpropyl) -O-polyethylene oxide urethane PS077 "manufactured by Chisso Corporation, and the like.

  Examples of the polyoxyalkylene resin having an isocyanate group include urethanization under conditions in which a diisocyanate such as 1,6-hexamethylene diisocyanate, TDI, MDI, and polypropylene glycol are used and the amount of isocyanate is larger than the amount of hydroxyl. Obtained by reacting.

  Examples of the polyoxyalkylene resin having an epoxy group include a product name “Epolite” series manufactured by Kyoei Chemical Co., Ltd.

  Examples of the polyoxyalkylene resin having the (meth) acryloyl group or styryl group include α, ω-di (meth) acryloyloxypolypropylene glycol, α, ω-di (meth) acryloyloxypolyethylene glycol, α- (meta ) Acryloyloxypolypropylene glycol, α- (meth) acryloyloxypolyethylene glycol and the like.

  Moreover, as a commercially available polyoxyalkylene resin having a (meth) acryloyl group or a styryl group, for example, “Blemmer” series manufactured by Nippon Oil & Fats Co., Ltd., “NK Ester M” manufactured by Shin-Nakamura Chemical Co., Ltd. Series, “NK Ester AMP” series, “NK Ester PEB” series, “NK Ester A” series, “NK Ester APG” series, trade names “Aronix M-240” and “Aronix M-245” manufactured by Toa Gosei Co., Ltd. , “Aronix M-260”, “Aronix M-270”, trade name “PE” series, “BPE” series, “BPP” series, manufactured by Daiichi Kogyo Co., Ltd., “Light Ester 4EG” manufactured by Kyoei Chemical Co., Ltd. , “Light ester 9EG”, “light ester 14EG”, “light acrylate MTG-A”, Light Acrylate DPM-A "," Light Acrylate P-200A "," Light Acrylate 9EG ", and" LIGHT-ACRYLATE BP-EPA "and the like.

  Examples of the crosslinking agent that crosslinks the polyoxyalkylene resin having a crosslinkable functional group include, for example, a crosslinking agent that reacts with the crosslinkable functional group of the polyoxyalkylene resin and is incorporated into the crosslinked resin (hereinafter referred to as “crosslinking agent”). (1) "), a crosslinking agent having an action as a catalyst for reacting the crosslinkable functional groups of the polyoxyalkylene resin (hereinafter referred to as" crosslinking agent (2) "), the crosslinking agent ( Examples thereof include a crosslinking agent having the functions of both 1) and crosslinking agent (2) (hereinafter referred to as “crosslinking agent (3)”).

As said crosslinking agent (1), the following crosslinking agent is mentioned, for example.
Examples of the crosslinking agent for crosslinking the polyoxyalkylene resin having an isocyanate group include compounds having a plurality of active hydrogens such as a compound having a plurality of hydroxyl groups and a compound having a plurality of amino groups.

  Examples of the compound having a plurality of hydroxyl groups include ethylene glycol, butylene glycol, glycerin, neopentyl glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, pentaerythritol, and polyester polyol.

  Examples of the compound having a plurality of amino groups include hexamethylenediamine, tetramethylenediamine, α, ω-diaminopropylene glycol, and the like.

  Examples of the crosslinking agent that crosslinks the polyoxyalkylene resin having an oxetanyl group include a photocation initiator that generates an acid by ultraviolet rays or visible light, and a thermal cation initiator that generates an acid by heat.

As said crosslinking agent (2), the following crosslinking agent is mentioned, for example.
Examples of the crosslinking agent that crosslinks a polyoxyalkylene resin having a hydrolyzable silyl group include a photoreactive crosslinking agent having a functional group represented by the general formula (1), and a photocation that generates an acid by ultraviolet rays or visible light. Initiators, organometallic compounds, amine compounds, acidic phosphates, tetraalkylammonium halides (halides: fluoride, chloride, bromide, iodide), inorganic acids such as carboxylic acid, hydrochloric acid, sulfuric acid, nitric acid, etc. A photoreactive crosslinking agent having the functional group represented by (1) is preferred.

O Y n-2 O
| | ‖ (1)
-C-X-C-
(Wherein X is an atom of group IVB, VB or VIB of the periodic table, Y is hydrogen, hydrocarbon group, mercapto group, amino group, halogen group, alkoxy group, alkylthio group, carbonyloxy group or oxo group. , N represents the valence of X.)

  In the formula, X is an atom of group IVB, VB or VIB of the periodic table, and examples thereof include oxygen, sulfur, nitrogen, phosphorus, and carbon. n is the valence of X, 2 when X is oxygen and 4 when carbon.

  Y represents hydrogen, a hydrocarbon group, a mercapto group, an amino group, a halogen group, an alkoxy group, an alkylthio group, a carbonyloxy group, or an oxo group. Examples of the hydrocarbon group include an aliphatic hydrocarbon group, an unsaturated group, and the like. Examples thereof include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. These hydrocarbon groups have a substituent such as an amino group, a hydroxyl group, an ether group, an epoxy group, a urethane group, a urea group, an imide group, an ester group, and a polymerizable unsaturated group as long as the object of the present invention is not impaired. You may do it.

  The photoreactive crosslinking agent having a functional group represented by the general formula (1) may be a cyclic compound. As a cyclic compound, the compound which has a functional group represented by the said general formula (1) of 1 type or 2 or more types same or different in a cyclic chain is mentioned, for example. Further, a compound in which a plurality of the same or different types of cyclic compounds are bonded with an appropriate organic group, and a bicyclic compound containing at least one or more of the same or different types of cyclic compounds as a unit may be mentioned.

Examples of the photoreactive crosslinking agent having a functional group represented by the general formula (1) in which X is oxygen include acetic anhydride, propionic anhydride, butyric anhydride, isobutyric anhydride, and valeric anhydride. 2-methylbutyric acid anhydride, trimethylacetic acid anhydride, hexanoic acid anhydride, heptanoic acid anhydride, decanoic acid anhydride, lauric acid anhydride, myristic acid anhydride, palmitic acid anhydride, stearyl acid anhydride, docosan Acid anhydride, crotonic acid anhydride, (meth) acrylic acid anhydride, oleic acid anhydride, linolenic acid anhydride, chloroacetic acid anhydride, iodoacetic acid anhydride, dichloroacetic acid anhydride, trifluoroacetic acid anhydride, chlorodifluoro Acetic anhydride, trichloroacetic anhydride, pentafluoropropionic anhydride, heptafluorobutyric anhydride, succinic anhydride, Succinic anhydride, 2,2-dimethyl succinic anhydride, isobutyl succinic anhydride, 1,2-cyclohexanedicarboxylic anhydride, hexahydro-4-methylphthalic anhydride, itaconic anhydride, 1,2,3 , 6-tetrahydrophthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, maleic anhydride, 2-methylmaleic anhydride, 2,3-dimethylmaleic anhydride, 1-cyclopentene- 1,2-dicarboxylic anhydride, glutaric anhydride, 1-naphthyl acetic anhydride, benzoic anhydride, phenyl succinic anhydride, phenyl maleic anhydride, 2,3-diphenyl maleic anhydride, phthalic acid Anhydride, 4-methylphthalic anhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 4,4 ′-(hexafluoropro Redene) acid anhydrides such as diphthalic anhydride, 1,2,4,5-benzenetetracarboxylic anhydride, 1,8-naphthalenedicarboxylic anhydride, 1,4,5,8-naphthalenetetracarboxylic anhydride And a copolymer of maleic anhydride and a compound having a radical polymerizable double bond, for example, a copolymer of (meth) acrylate, styrene, vinyl ether, or the like. These photoreactive crosslinking agents may be used alone or in combination of two or more.

  Moreover, as a commercial item of the said photoreactive crosslinking agent, Asahi Denka Kogyo Co., Ltd. brand name "ADEKA HARDNER EH-700", "ADEKA HARDNER EH-703", "ADEKA HARDNER EH-705A", Shin Nippon Product names “Rikacid TH”, “Rikacid HT-1”, “Rikacid HH”, “Rikacid MH-700”, “Rikacid MH-700H”, “Rikacid MH”, “Rikacid SH”, “Rikaresin TMEG” manufactured by Rika Co., Ltd. "Trade names" HN-5000 "and" HN-2000 "made by Hitachi Chemical Co., Ltd., trade names" Epicure 134A "," Epicure YH306 "," Epicure YH307 "," Epicure YH308H "manufactured by Yuka Shell Epoxy, A trade name “SumiCure MS” manufactured by Sumitomo Chemical Co., Ltd. may be mentioned.

  Examples of the photoreactive crosslinking agent having a functional group represented by the general formula (1) in which X is nitrogen include succinimide, N-methylsuccinimide, α, α-dimethyl-β-methylsuccinimide, α-methyl-α-propyl succinimide, maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-tert-butylmaleimide, N-laurylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N- (2-chlorophenyl) maleimide, N-benzylmaleimide, N- (1-pyrenyl) maleimide, 3-methyl-N-phenylmaleimide, N, N′-1,2-phenylenedimaleimide, N, N′- 1,3-phenylene dimaleimide, N, N′-1,4-phenylene dimaleimide, N, N ′-( 4-methyl-1,3-phenylene) bismaleimide, 1,1 ′-(methylenedi-1,4-phenylene) bismaleimide, phthalimide, N-methylphthalimide, N-ethylphthalimide, N-propylphthalimide, N-phenyl Examples thereof include phthalimide, N-benzylphthalimide, pyromellitic acid diimide, and the like, and compounds having N-alkylmaleimide and a radical polymerizable double bond, such as a copolymer of (meth) acrylate, styrene, vinyl ether, and the like. These photoreactive crosslinking agents may be used alone or in combination of two or more.

  Examples of the photoreactive crosslinking agent having a functional group represented by the general formula (1) in which X is phosphorus include bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, And acylphosphine oxides such as bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide. These photoreactive crosslinking agents may be used alone or in combination of two or more.

  Examples of the photoreactive crosslinking agent having a functional group represented by the general formula (1) in which X is carbon include 2,4-pentanedione, 3-methyl-2,4-pentanedione, 3-ethyl- 2,4-pentanedione, 3-chloro-2,4-pentanedione, 1,1,1-trifluoro-2,4-pentanedione, 1,1,1,5,5,5-hexafluoro-2 , 4-pentanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, diketones such as 1-benzoylacetone, dibenzoylmethane; dimethylmalonate, diethylmalonate, dimethylmethylmalonate, Polycarboxylic acid esters such as tetraethyl-1,1,2,2-ethanetetracarboxylic acid; methylacetylacetonate, ethylacetylacetonate, methylpropio α- carbonyl acetate esters such as Le acetate, and the like. These photoreactive crosslinking agents may be used alone or in combination of two or more.

  Among the photoreactive crosslinking agents, diacylphosphine oxide and derivatives thereof are preferably used because they disappear when heated and have very little residue.

  When the amount of the photoreactive crosslinking agent added decreases, crosslinking of the polyoxyalkylene resin having hydrolyzable silyl groups does not proceed. When the amount increases, the light transmittance of the polyoxyalkylene resin having hydrolyzable silyl groups decreases. Since only the surface is crosslinked and the inside is not crosslinked, the amount is preferably 0.01 to 30 parts by weight, more preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the polyoxyalkylene resin having a hydrolyzable silyl group. It is.

  Examples of the organometallic compound include dibutyltin dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin phthalate, bis (dibutyltin laurate) oxide, dibutyltin bisacetylacetonate, dibutyltin bis (monoester maleate) ), Tin compounds such as tin octylate, dibutyltin octoate and dioctyltin oxide; and titanium compounds such as tetra-n-butoxy titanate and tetraisopropoxy titanate. These organometallic compounds may be used alone or in combination of two or more.

  Although the addition amount of the organometallic compound is not particularly limited, it is preferably 0.01 to 10 parts by weight, more preferably 0 to 100 parts by weight of the polyoxyalkylene resin having a hydrolyzable silyl group. .1-8 parts by weight.

  As a crosslinking agent for crosslinking the polyoxyalkylene resin having an epoxy group, for example, a photocationic initiator that generates an acid by ultraviolet rays or visible light, a thermal cationic initiator that generates an acid by heat, an amine compound curing agent, Examples include amide-based curing agents, acid anhydride-based curing agents, mercapto-based curing agents, thermal latent curing agents such as ketimine and DICY, and photoamine generators having a carbamoyloxyimino group.

  Examples of the photocation initiator include iron-allene complex compounds, aromatic diazonium salts, aromatic iodonium salts, aromatic sulfonium salts, onium salts, pyridinium salts, aluminum complexes / silanol salts, and trichloromethyltriazine derivatives. It is done.

Examples of the counter anion of the onium salt or pyridinium salt include SbF 6 , PF 6 , AsF 6 , BF 4 , tetrakis (pentafluoro) borate, trifluoromethane sulfonate, methane sulfonate, and trifluoro. Examples include acetate, acetate, sulfonate, tosylate, and nitrate.

Moreover, as a commercial item of the said photocation initiator, the brand name "Irgacure 261" by Ciba Geigy Co., Ltd., the brand names "Optomer SP-150", "Optomer SP-151", "Optomer" by Asahi Denka Co., Ltd. are mentioned, for example. "SP-170", "Optomer SP-171", product name "UVE-1014" manufactured by General Electronics Co., Ltd., product name "CD-1012" manufactured by Sartomer Company, and product name "Sun-Aid SI-" manufactured by Sanshin Chemical Industry Co., Ltd. "60L", "Sun-Aid SI-80L", "Sun-Aid SI-100L", trade names "CI-2064", "CI-2639", "CI-2624", "CI-2481", manufactured by Nippon Soda Co., Ltd., Rhone The product name “RHODORSIL PHOTOINITITOR 2074” manufactured by Poulen and the product name “UV” manufactured by Union Carbide -6990 ", trade names" BBI-103 "," MPI-103 "," TPS-103 "," MDS-103 "," DTS-103 "," NAT-103 "," NDS- "manufactured by Midori Chemical Co., Ltd. 103 "and the like. These photocationic initiators may be used alone or in combination of two or more.

  Examples of the thermal cation initiator include ammonium salts having at least one alkyl group, sulfonium salts, iodonium salts, diazonium salts, boron trifluoride / triethylamine complexes, and the like.

Examples of counter anions of these thermal cation initiators include SbF 6 , PF 6 , AsF 6 , BF 4 , tetrakis (pentafluoro) borate, trifluoromethanesulfonate, methanesulfonate, and trifluoroacetate. , Acetate, sulfonate, tosylate, nitrate and the like.

  Examples of the photoamine generator having a carbamoyloxyimino group include a compound having a carbamoyloxyimino group, a cobaltamine complex, carbamate-o-nitrobenzyl, o-acyloxime, and the like.

  Examples of the crosslinking agent for crosslinking the polyoxyalkylene resin having a polymerizable unsaturated hydrocarbon group include thermal radical initiators such as peroxides and azo compounds; photoradical initiators by ultraviolet rays and visible rays; heat or light. Examples include an initiator obtained by combining a radical initiator and a compound having a plurality of mercapto groups.

  Examples of the thermal radical initiator include diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, tert-hexyl hydroperoxide, tert-butyl hydroperoxide, and the like. Hydroperoxides: α, α′-bis (tert-butylperoxy-m-isopropyl) benzene, dicumyl peroxide, 2,5-dimethyl-2,5-bis (tert-butylperoxy) hexane, tert Dialkyl peroxides such as butyl cumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-bis (tert-butylperoxy) hexyne-3; ketone peroxides; Diacyl peroxides; peroxydicarbonates; organic peroxides such as peroxyesters, 2,2′-azobisisobutyronitrile, 1,1 ′-(cyclohexane-1-carbonitrile ), 2,2′-azobis (2-cyclopropylpropionitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), and the like. These thermal radical initiators may be used alone or in combination of two or more.

Examples of the photo radical initiator include 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone, α-hydroxy-α-α'-dimethylacetophenone, methoxyacetophenone, and 2,2-dimethoxy. Acetophenone derivatives such as 2-phenylacetophenone; benzoin ether compounds such as benzoin ethyl ether and benzoin propyl ether; ketal derivatives such as benzyldimethyl ketal; halogenated ketones, acyl phosphine oxides, acyl phosphonates, 2-methyl- 1- [
4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-N, N-dimethylamino-1- (4-morpholinophenyl) -1-butane, bis (2,4 , 6-Trimethylbenzoyl) -phenylphosphine oxide bis- (2,6-dimethoxybenzoyl) 2,4,4-trimethylpentylphosphine oxide, bis (η5-cyclopentadienyl) -bis (pentafluorophenyl)- Titanium, bis (η5-cyclopentadienyl) -bis [2,6-difluoro-3- (1H-py-1-yl) phenyl] -titanium, anthracene, perylene, coronene, tetracene, benzanthracene, phenothiazine, flavin, Acridine, ketocoumarin, thioxanthone derivatives, benzophenone, aceto Tophenone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, isopropylthioxanthone and the like can be mentioned. These thermal radical initiators may be used alone or in combination of two or more.

  Examples of the crosslinking agent (3) include α, ω-diaminopolyoxypropylene.

  The thermoplastic resin forming the heat extinguishing material used in the present invention is preferably the above polyoxyalkylene resin, but the polyoxyalkylene resin may be uncrosslinked or may be crosslinked.

  Moreover, the resin composition of an uncrosslinked polyoxyalkylene resin and the said crosslinking agent may be sufficient. In the case of a resin composition of an uncrosslinked polyoxyalkylene resin and the above crosslinking agent, it may be crosslinked at the most suitable time for the production process, but before or after the resin composition is laminated on the mold surface. It is preferred to crosslink later.

  As a heat extinguishing material used in the present invention, a resin composition comprising a resin having a hydrolyzable silyl group and a photoreactive cross-linking agent having a functional group represented by the general formula (1) or the crosslinked resin composition A resin composition can be suitably used.

  The resin having a hydrolyzable silyl group is not particularly limited as long as it has the hydrolyzable silyl group described above. For example, a polyester resin having an ester bond, a polyamide resin having an amide bond, a polyimide resin, Examples include polysiloxane resins, polycarbonate resins having a carbonate bond, poly (meth) acrylate resins, polybutadiene resins, polystyrene resins, polyolefin resins, and the like, and compounds in which a hydrolyzable silyl group is contained in these copolymers. The hydrolyzable silyl group may be located at the terminal of the polymer or copolymer, may be located in the side chain, or may be located in the terminal and side chain.

  As the resin having a hydrolyzable silyl group, for example, trade names “acetoxy-terminated polydimethylsiloxane PS363.5”, “dimethylamino-terminated polydimethylsiloxane PS383”, “ethoxy-terminated polydimethylsiloxane PS393” manufactured by Chisso Corporation, “Stearyloxy-terminated polydimethylsiloxane PS053.5”, “Triethoxysilyl-modified poly (1,2-butadiene) PS078.5”, “(N-trimethoxysilylpropyl) polyazamid PS075”, “(N-trimethoxysilylpropyl) ) Polyethyleneimine PS076 "and the like.

  The photoreactive crosslinking agent having the functional group represented by the general formula (1) is as described above.

When the amount of the photoreactive crosslinking agent having the functional group represented by the general formula (1) is reduced, crosslinking of the resin having hydrolyzable silyl groups does not proceed, and when the amount is increased, the resin having hydrolyzable silyl groups. The light transmittance is reduced, only the surface is crosslinked, and the inside is not crosslinked. Therefore, the amount is preferably 0.01 to 30 parts by weight, more preferably 0.1 to 100 parts by weight of the resin having a hydrolyzable silyl group. ~ 20 considerations.

  In the case of a resin composition comprising a resin having a hydrolyzable silyl group and a photoreactive cross-linking agent having a functional group represented by the general formula (1), if crosslinking is performed at the time most suitable for the production process, For example, it is preferable to crosslink before or after laminating the resin composition on the surface of the mold.

  The heat extinguishing material used in the present invention may contain a decomposition accelerator, a decomposition retarder, and the like in order to control the extinction rate, the extinction temperature, and the like.

  The decomposition accelerator is not particularly limited as long as it can accelerate the decomposition of the heat extinguishing composition when the heat extinguishing composition is heated. For example, inorganic peroxide; organic peroxide; sulfuric acid Heavy metal compounds such as iron, sodium nitrate and cobalt naphthenate, carboxylic acids such as oxalic acid, linolenic acid and ascorbic acid; hydroquinone, tin oxide and the like.

  Examples of the inorganic peroxide include potassium persulfate, sodium persulfate, ammonium persulfate, potassium perchlorate, sodium perchlorate, ammonium perchlorate, and potassium periodate.

  The organic peroxide preferably has a 10-hour half-life temperature of 100 ° C. or higher. For example, P-menthane hydroxy peroxide, diisopropylbenzene hydroxy peroxide, 1,1,3,3-tetramethylbutyl hydroxyper Hydroxide peroxides such as oxide, cumene hydroxy peroxide, t-hexyl hydroxy peroxide, t-butyl hydroxy peroxide; dicumyl peroxide, α, α′-bis (t-butylperoxy-m-isopropylbenzene), 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t-butyl Peroxy) diaxins such as hexyne-3 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-butylperoxide) Oxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) cyclododecane, 2,2-bis (t-butyl) Peroxyketals such as peroxy) butane, n-butyl-4,4-bis (t-butylperoxy) valerate, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane; t -Hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3,5,5-trimethylhexa Ate, t-butylperoxylaurate, 2,5-dimethyl-2,5-bis (m-toluylperoxy) hexane, t-butylperoxyisopropyl monocarbonate, t-hexylperoxybenzoate, 2,5- Dimethyl-2,5-bis (m-benzoylperoxy) hexane, t-butylperoxyacetate, t-butylperoxybenzoate, bis-t-butylperoxyisophthalate, t-butylperoxyallyl monocarbonate, etc. Examples include peroxyesters.

  When the decomposition accelerator is added to the heat extinguishing material, the decomposition of the heat extinguishing material is promoted. However, when the inorganic peroxide or the organic peroxide is added as a decomposition accelerator, the decomposition residue of the heat extinguishing material is reduced. The generation of certain carbides is preferable because it can be suppressed, and the organic peroxide is more preferable because generation of ash residues can also be suppressed.

  The decomposition retarder is not particularly limited as long as it can delay the decomposition of the heat extinguishing material when the heat extinguishing material is heated, and examples thereof include mercapto compounds, amine compounds, organic tin, and organic boron. Can be mentioned.

  Examples of the mercapto compound include propanethiol, butanethiol, pentanethiol, 1-octanethiol, dodecanethiol, cyclopentanethiol, cyclohexanethiol, 1,3-propanedithiol, and the like.

  Examples of the amine compound include propylamine, butylamine, hexylamine, dodecylamine, isopropylamine, hexamethylenediamine, cyclohexylamine, benzylamine, aniline, and methylaniline.

  Examples of the organic tin include dimethyltin dilaurate, dibutyltin dilaurate, dibutyltin dioctate, dibutyltin diacetate, dibutyltin bis (2,4-pentanedione), and dilauryltin dilaurate.

  Examples of the organic boron include trimethyl borate, tripropyl borate, tributyl borate, trimethoxyboroxine, trimethylene borate and the like.

  The addition amount of the decomposition accelerator and the decomposition retarder is not particularly limited, and may be appropriately determined according to the use form, but is generally 0.1 to 10 with respect to 100 parts by weight of the heat extinguishing material. Parts by weight.

  Since the conductive metal nanoparticles used in the present invention form a fine pattern, a metal having excellent conductivity is preferable. For example, gold, silver, copper, platinum, palladium, nickel, aluminum, and alloys thereof Is mentioned.

  Since the average particle diameter of the conductive metal nanoparticles used in the present invention forms a fine pattern, it is preferably finer, preferably 1 to 100 nm, more preferably 2 to 10 nm.

  The heat extinguishing composition used in the present invention is composed of the above heat extinguishing material and conductive metal nanoparticles. When the amount of the conductive metal nanoparticles is reduced, sufficient conductivity is imparted to the fine pattern. Therefore, a large amount of the heat extinguishing composition must be laminated on the substrate, and a fine pattern cannot be formed.

  Further, when the amount of the conductive metal nanoparticles added is increased, it becomes difficult to accurately transfer the heat extinguishing composition to the substrate by the reversal imprint method. Therefore, the addition amount of the conductive metal nanoparticles is preferably 5 to 100 parts by weight, more preferably 10 to 80 parts by weight with respect to 100 parts by weight of the heat extinguishing material.

  Since the above heat extinguishing composition is preferably uniformly coated and laminated on the mold surface by spin coating, when the heat extinguishing composition is solid or has a high viscosity, it is dissolved in an organic solvent to form a solution. preferable.

  The organic solvent is not particularly limited as long as it can dissolve the heat extinguishing composition uniformly. For example, methanol, ethanol, propanol, benzene, xylene, toluene, acetone, methyl ethyl ketone, 2-heptanone, methyl isobutyl. Ketone, diisobutyl ketone, tetrahydrofuran, mesitylene, diphenyl ether, ethyl acetate, isobutyl acetate, ethyl lactate, propylene glycol monomethyl ether and the like can be mentioned.

  In the above-mentioned heat extinguishing composition, for example, a thickener, a physical property adjuster, a bulking agent, an organometallic compound, a thixotrope, a plasticizer, an oxidation can be used as long as it does not inhibit the achievement of the object of the present invention. Inhibitors (anti-aging agents), heat stabilizers, light stabilizers, UV absorbers, colorants, etc. may be added, but those that do not disappear by heating should not be added, or the addition amount should be made small. Is preferred.

  The thickener is preferably a polymer compound having good compatibility with the heat extinguishing composition, for example, (meth) acrylic resin, polyvinyl alcohol derivative, polyvinyl acetate, polystyrene derivative, polyesters, polyethers, Polyolefins, polyurethanes, polyamides, natural rubber, polybutadiene, polyisoprene, polyisobutene, NBR, SBS, SIS, SEBS, hydrogenated NBR, hydrogenated SBS, hydrogenated SIS, hydrogenated SEBS, and copolymers thereof And functional group-modified products.

  Examples of the physical property modifier include vinyltrimethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, 3-aminopropyltrimethyl. Methoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltri Ethoxysilane, N, N′-bis- [3- (trimethoxysilyl) propyl] ethylenediamine, N, N′-bis- [3- (triethoxysilyl) propyl] ethylenediamine, N, N′-bis- [3 -(Trimethoxysilyl ) Propyl] hexaethylenediamine, N, N'-bis - [3- (or triethoxysilyl) propyl] silane coupling such hexaethylenediamine agents, titanium coupling agents, aluminum coupling agents and the like.

  Examples of the filler include inorganic fillers such as talc, clay, calcium carbonate, magnesium carbonate, anhydrous silicon, hydrous silicon, calcium silicate, titanium dioxide, and carbon black.

  As the organometallic compound, for example, a titanium compound such as tetra-n-butoxy titanate or tetraisopropoxy titanate, a metal element such as germanium, lead, aluminum, gallium, indium, titanium or zirconium is substituted with an organic group. And organometallic compounds. These organometallic compounds may be used alone or in combination of two or more.

  The thixotropic agent is preferably a substance having a surface having a high affinity for the gas generating resin composition, and examples thereof include colloidal silica, polyvinyl pyrrolidone, hydrophobized calcium carbonate, glass balloons, and glass beads. These thixotropic agents may be used alone or in combination of two or more.

  Examples of the plasticizer include phosphate esters such as tributyl phosphate and tricresyl phosphate; phthalate esters such as dioctyl phthalate; fatty acid-basic acid esters such as glycerol monooleate; dioctyl adipate; And fatty acid dibasic acid esters; polypropylene glycols and the like. These plasticizers may be used alone or in combination of two or more.

  In the first step of the present invention, a heat extinguishing composition comprising a heat extinguishing material mainly composed of the thermoplastic resin and conductive metal nanoparticles is applied to a mold on which a predetermined fine pattern is formed and heated. This is a step of forming an extinct composition layer.

  The mold is formed with a predetermined fine pattern. As a method for forming a fine pattern, any conventionally known method may be adopted. However, since a fine pattern is formed, a method such as photolithography or electron beam lithography used in laser beam processing or semiconductor manufacturing is used. Is preferably formed.

  The material of the above type is not particularly limited as long as it is a base material that does not deform at the temperature at which the heat extinguishing composition is transferred. For example, conventionally used inorganic materials such as glass, quartz, and silicon, metals , Thermoplastic resins and thermosetting resins. These materials may be laminated.

  The above-mentioned inorganic materials are excellent in accuracy, workability, etc. For example, if optical lithography technology widely used in semiconductor microfabrication technology is used, micron-order grooves can be freely formed on glass or silicon substrates. Is preferable.

  Examples of the thermoplastic resin include polyolefin resins, polystyrene resins, polylactic acid resins, polyacrylic resins, polycarbonate resins, and the like, and polyolefin resins that are thermoplastic resins having acid resistance and alkali resistance. And polyacrylic resins are preferred.

  In addition, since the thermosetting resin is a liquid precursor, there is an advantage that the shape of the transfer mold is transferred more faithfully, it is easy to form a fine pattern, heat resistance is excellent, low linear expansion coefficient, low Since the mold shrinkage is shown, it can be advantageously used. As such a thermosetting resin, an epoxy resin can be advantageously used from the viewpoint of cost and easy handling.

  In order to transfer a heat extinguishing composition layer corresponding to a fine pattern onto a substrate by a reversal imprint method, the heat extinguishing composition layer is preferably a uniform and thin layer. As a method for applying the film to a mold on which a predetermined fine pattern is formed, a spin coating method is preferable. When the heat extinguishing composition layer contains an organic solvent, it is dried after coating.

  The thickness of the heat extinguishing composition layer may be appropriately determined depending on the size of the fine pattern. However, in order to obtain a fine wiring pattern having a wiring width and a wiring interval of 10 μm or less, it is preferably 40 μm or less, more preferably 20 μm or less.

  When the heat extinguishing composition is uncrosslinked, as described above, the heat extinguishing composition layer may be crosslinked by heating or light irradiation after the heat extinguishing composition layer is laminated on the mold. In addition, when bridge | crosslinking with a heat | fever, it is necessary to heat in the temperature range which does not decompose | disassemble a heat extinction composition.

  The light source for light irradiation is not particularly limited. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a light emitting diode (LED), an all solid state laser, an excimer laser, a cold cathode ray tube, a chemical lamp, Examples thereof include a black light lamp, a microwave excitation mercury lamp, a metal halide lamp, a sodium lamp, a halogen lamp, a xenon lamp, a fluorescent lamp, sunlight, and an electron beam irradiation device. These light sources may be used alone or in combination of two or more.

  The second step of the present invention is a step of transferring a heat extinguishing composition layer corresponding to a fine pattern onto a substrate by a reversal imprint method.

The material of the base material is not particularly limited as long as it is a base material that does not deform at the temperature when the heat extinguishing composition is heated and extinguished. For example, conventionally used inorganic materials such as glass, quartz, and silicon , Metals, thermoplastic resins, thermosetting resins, and the like. These materials may be laminated.

  Examples of the thermoplastic resin include polyolefin-based resins, polystyrene-based resins, polylactic acid-based resins, polyacrylic-based resins, polycarbonate-based resins, polyimide resins, and the like, and are thermoplastic resins having acid resistance and alkali resistance. Polyolefin resins and polyacrylic resins are preferred.

  Thermosetting resins are excellent in heat resistance and can be advantageously used because they exhibit a low linear expansion coefficient and a low molding shrinkage ratio. As such a thermosetting resin, an epoxy resin can be advantageously used from the viewpoint of cost and easy handling.

  In the reversal imprinting method, a mold in which a heat extinguishing composition layer is laminated on a surface on which a predetermined fine pattern is formed is pressed onto a substrate at a temperature lower than the glass transition temperature of the thermoplastic resin. And a printing method for transferring a heat-extinguishing composition layer having a predetermined fine pattern to a substrate.

  Next, the reversal imprint method will be described with reference to the drawings. FIG. 1 is a cross-sectional view showing an example of a state in which a heat extinguishing composition mainly composed of a thermoplastic resin is laminated on a surface on which a fine predetermined pattern is formed, and FIG. 2 is a heat extinguishing composition. It is sectional drawing which shows an example in the state by which the physical layer was transcribe | transferred.

  In the figure, reference numeral 1 denotes a mold on which a predetermined fine pattern is formed. The mold 1 has a convex portion 11 and a concave portion 12 to form a fine pattern. The pattern is a portion of the convex portion 11. In the figure, 2 is a heat extinguishing composition layer applied and laminated by spin coating, and 3 is a substrate.

  In the reversal imprint method, a mold in which a heat extinguishing composition layer is laminated is pressed onto a substrate at a temperature lower than the glass transition temperature of the thermoplastic resin, and the heat extinguishing composition having a predetermined pattern is formed on the substrate. Transfer the layer.

  Since the press temperature is to transfer the heat extinguishing composition on the pattern (projection 11 of the mold 1) formed on the surface of the mold 1, the glass transition temperature of the thermoplastic resin constituting the heat extinguishing composition. The temperature is as follows.

  When the press temperature is higher than the glass transition temperature of the thermoplastic resin, the entire heat extinguishing composition layer is transferred, and when the temperature is lower, the transfer is not performed. Therefore, the press temperature is from the glass transition temperature -30 ° C to the glass transition. A temperature range is preferred.

  Also, the press pressure is not transferred when it is low, and when it is high, the heat extinguishing composition layer is deformed and precise transfer cannot be performed, or the entire heat extinguishing composition layer is transferred, so 1 to 40 MPa is preferable. More preferably, it is 10-30 MPa.

  When the heat extinguishing composition layer is transferred by the reversal imprint method, as shown in FIG. 2, the heat extinguishing composition on the concave portion 12 of the mold 1 remains in the mold 1 and remains on the convex portion 11 of the mold 1. The heat extinguishing composition is transferred to the base material 3, and the fine pattern formed on the mold 1 by the transferred heat extinguishing composition 21 is formed on the base material 3. The fine pattern formed by the reversal imprint method can be made fine up to about 200 nm.

  The third step of the present invention is a step of removing the heat extinguishing material by heating to form a conductive fine pattern on the substrate.

  The above heat extinguishing composition generates gas within 10 minutes and disappears by heating at a predetermined temperature of 150 to 300 ° C. in an oxygen atmosphere. Moreover, in an anaerobic atmosphere, by heating at a predetermined temperature of 150 to 350 ° C., when the pressure is reduced within 10 minutes, gas is generated and disappears within 5 minutes. That is, the heat extinguishing composition is removed by heating to eliminate the heat extinguishing composition, and a conductive fine pattern is formed where the heat extinguishing composition layer is present.

  In general, metal fine particles having an average particle diameter of several nanometers to several tens of nanometers are sintered at a temperature considerably lower than the melting point thereof (for example, silver is 200 ° C.). The sintering may be performed in the same step, or after the heat extinguishing composition disappears in the low temperature part, the metal fine particles may be sintered at a high temperature.

  The structure of the method for producing a conductive fine pattern of the present invention is as described above, and a fine wiring pattern having a wiring width and a wiring interval of 10 μm or less can be obtained easily and accurately with good reproducibility.

  Furthermore, in the present invention, since the heat extinguishing composition is transferred onto the substrate by the reversal imprint method, a large number of patterns formed on the mold can be accurately transferred onto the substrate for mass production. Is suitable.

  EXAMPLES Next, although an Example is given and this invention is demonstrated further in detail, this invention is not limited only to these Examples.

Example 1
70 parts by weight of polytetramethylene glycol diglycidyl ether (manufactured by Yokkaichi Chemical Co., Ltd., trade name “PTMG # 650-EDP”), 30 parts by weight of polytetramethylene glycol (manufactured by Mitsubishi Chemical Corporation, PTMG1000), photocation initiator (Asahi Denka) Made by trade name "SP-170") and 100 parts by weight of a silver particle dispersion liquid (35 parts by weight of silver particles, 7 parts by weight of dodecylamine and 58 parts by weight of toluene) having an average particle diameter of 3 nm. The mixture was mixed in a beaker at 50 ° C. under light shielding to obtain a heat extinguishing composition.

  The heat extinguishing composition obtained by spin coating is applied to the surface of a mold which is made of a silicon wafer and has a surface of a mold having 2 μm wide and 2 μm deep recesses formed at 3 μm intervals by photolithography. Then, it was air-dried at 70 ° C.

Next, a type in which a heat extinguishing composition layer is laminated by irradiating 365 nm ultraviolet rays with an irradiation intensity of 40 mW / cm 2 for 60 seconds using a high-pressure mercury lamp to cause a chain reaction of polytetramethylene glycol diglycidyl ether. Got. The glass transition temperature of polytetramethylene glycol diglycidyl ether after photoreaction was 40 ° C.

The obtained mold was brought into contact with a silicon wafer as a base material, and the heat extinguishing composition layer was transferred onto the base material by a reversal imprint method at a pressure of 20 MPa and a heating temperature of 40 ° C.
When the film was heated at 250 ° C. for 15 seconds after the transfer, the heat extinguishing composition layer disappeared, and a silicon wafer in which silver fine patterns having a wiring width and a wiring interval of 2 μm were laminated was obtained. The volume resistivity of the obtained fine pattern was 46 μΩ · cm.

(Example 2)
Polytetramethylene glycol diglycidyl ether (manufactured by Yokkaichi Chemical Co., Ltd., trade name “PT
MG # 650-EDP ") 70 parts by weight, polytetramethylene glycol (Mitsubishi Chemical Co., Ltd., PTMG1000) 30 parts by weight and photocation initiator (Asahi Denka, trade name" SP-170 ") 3 parts by weight and average particles 100 parts by weight of a 3 nm diameter silver particle dispersion (35 parts by weight of silver particles, 7 parts by weight of dodecylamine and 58 parts by weight of toluene) were mixed in a beaker at 50 ° C. in the dark and then cooled to room temperature. Then, 3 parts by weight of 1,1-bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane (trade name “PerhexaTMH” manufactured by NOF Corporation) was added and mixed to obtain a heat extinguishing composition. It was.

  Using the obtained heat extinguishing composition, it was applied to a mold made of a silicon wafer in the same manner as in Example 1, and a mold in which a heat extinguishing composition layer was laminated was obtained by crosslinking. The glass transition temperature of the crosslinked alkoxysilyl-modified polypropylene glycol was 40 ° C.

The obtained mold was brought into contact with a silicon wafer as a base material, and the heat extinguishing composition layer was transferred onto the base material by a reversal imprint method at a pressure of 20 MPa and a heating temperature of 40 ° C.
When the film was heated at 250 ° C. for 15 seconds after the transfer, the heat extinguishing composition layer disappeared, and a silicon wafer in which silver fine patterns having a wiring width and a wiring interval of 2 μm were laminated was obtained. The volume resistivity of the obtained fine pattern was 49 μΩ · cm.

(Example 3)
98 parts by weight of polypropylene glycol monomethacrylate (manufactured by NOF Corporation, trade name “Blenmer PP1000”), 2 parts by weight of polypropylene glycol diacrylate (trade name “Aronix M270”, manufactured by Toagosei Co., Ltd.), diacylphosphine oxide (Ciba Specialty) 100 parts by weight of 1 part by weight of a chemical company, trade name "Irgacure 819" and a dispersion of silver particles having an average particle diameter of 3 nm (a dispersion comprising 35 parts by weight of silver particles, 7 parts by weight of dodecylamine and 58 parts by weight of toluene) Were mixed in a beaker, and dissolved oxygen was removed by bubbling with nitrogen gas for 10 minutes to obtain a heat extinguishing composition.

  Using the obtained heat extinguishing composition, it was applied to a mold made of a silicon wafer in the same manner as in Example 1, and a mold in which a heat extinguishing composition layer was laminated was obtained by crosslinking. The glass transition temperature of the crosslinked heat extinguishing composition was 30 ° C.

The obtained mold was brought into contact with a silicon wafer as a base material, and the heat extinguishing composition layer was transferred onto the base material by a reversal imprint method at a pressure of 20 MPa and a heating temperature of 30 ° C.
After the transfer, the film was heated at 250 ° C. for 25 seconds. As a result, the heat extinguishing composition layer disappeared, and a silicon wafer on which silver fine patterns having a wiring width and a wiring interval of 2 μm were laminated was obtained. The volume resistivity of the obtained fine pattern was 49 μΩ · cm.

Example 4
A heat extinguishing composition was obtained in the same manner as in Example 1 except that 2 parts by weight of cumene hydroxy peroxide was added. Using the obtained heat extinguishing composition, it was applied to a mold made of a silicon wafer in the same manner as in Example 1, and a mold in which a heat extinguishing composition layer was laminated was obtained by crosslinking. The glass transition temperature of the crosslinked heat extinguishing composition was 40 ° C.

The obtained mold was brought into contact with a silicon wafer as a base material, and the heat extinguishing composition layer was transferred onto the base material by a reversal imprint method at a pressure of 20 MPa and a heating temperature of 40 ° C.
When the film was heated at 250 ° C. for 12 seconds after the transfer, the heat extinguishing composition layer disappeared, and a silicon wafer in which silver fine patterns having a wiring width and a wiring interval of 2 μm were laminated was obtained. The volume resistivity of the obtained fine pattern was 39 μΩ · cm.

(Example 5)
A heat extinguishing composition was obtained in the same manner as in Example 1 except that 3 parts by weight of dodecyl mercaptan was added. Using the obtained heat extinguishing composition, it was applied to a mold made of a silicon wafer in the same manner as in Example 1, and a mold in which a heat extinguishing composition layer was laminated was obtained by crosslinking. The glass transition temperature of the crosslinked heat extinguishing composition was 40 ° C.

The obtained mold was brought into contact with a silicon wafer as a base material, and the heat extinguishing composition layer was transferred onto the base material by a reversal imprint method at a pressure of 20 MPa and a heating temperature of 40 ° C.
After the transfer, the film was heated at 250 ° C. for 30 seconds. As a result, the heat extinguishing composition layer disappeared, and a silicon wafer on which silver fine patterns having a wiring width and a wiring interval of 2 μm were laminated was obtained. The volume resistivity of the obtained fine pattern was 76 μΩ · cm.

It is sectional drawing which shows an example of the state by which the heat extinction composition which mainly has a thermoplastic resin was laminated | stacked on the surface in which the predetermined fine pattern is formed. It is sectional drawing which shows an example in the state by which the heat extinction composition layer was transcribe | transferred.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Type | mold 11 Convex part 12 Concave part 2 Heat extinction composition layer 21 Heat extinction composition 3 Base material

Claims (13)

  1. A heat-extinguishing composition comprising a heat-extinguishing material containing a polyoxyalkylene resin having an oxygen content of 15 to 55% by weight and conductive metal nanoparticles having an average particle diameter of 1 to 100 nm comprises predetermined irregularities. Applying to the surface of the mold on which the fine pattern is formed and laminating the heat extinguishing composition layer , heating and extinguishing on the surface of the mold on which the obtained fine pattern is formed The layered product in which the heat-dissipating composition layer is laminated is stacked so that the heat-disappearing composition layer is in contact with the substrate, and then pressed, whereby the heat-disappearing composition layer on the convex portion of the fine pattern is formed as a base material the reversal imprinting of transferring includes the steps of transferring the heat extinguishing composition layer corresponding to the convex portion of the fine pattern on the substrate, and, 150 to 300 ° C. in an oxygen atmosphere, or, anaerobic ambient atmosphere Method for producing a conductive fine pattern, comprising the step of heating to a temperature of 150 to 350 ° C. under a heating extinguishing material is removed, thereby forming a conductive micropattern on the substrate.
  2. The method for producing a conductive fine pattern according to claim 1 , wherein the polyoxyalkylene resin has a number average molecular weight of 5,000 to 5,000,000.
  3. 3. The conductive material according to claim 1 , wherein the polyoxyalkylene resin has a functional group selected from the group consisting of a hydrolyzable silyl group, an isocyanate group, an epoxy group, a (meth) acryloyl group, and a styryl group. Method for producing a conductive fine pattern.
  4. A resin composition comprising a polyoxyalkylene resin having a functional group selected from the group consisting of a hydrolyzable silyl group, an isocyanate group, an epoxy group, a (meth) acryloyl group and a styryl group and a crosslinking agent, 4. The method for producing a conductive fine pattern according to claim 1, 2, or 3 , wherein the resin composition is a crosslinked resin composition.
  5. The method for producing a conductive fine pattern according to claim 4 , wherein the crosslinking agent is a photoreactive crosslinking agent having a functional group represented by the general formula (1).
    (Wherein X is an atom of group IVB, VB or VIB of the periodic table, Y is hydrogen, hydrocarbon group, mercapto group, amino group, halogen group, alkoxy group, alkylthio group, carbonyloxy group or oxo group. , N represents the valence of X.)
  6. The method for producing a conductive fine pattern according to claim 1, 2, 3, 4 or 5 , wherein the heat extinguishing material contains a thermal decomposition accelerator.
  7. The method for producing a conductive fine pattern according to claim 6 , wherein the thermal decomposition accelerator is an inorganic peroxide or an organic peroxide.
  8. The method for producing a conductive fine pattern according to claim 1, 2, 3, 4, 5, 6 or 7 , wherein the heat extinguishing material contains a thermal decomposition retarder.
  9. The method for producing a conductive fine pattern according to claim 8 , wherein the thermal decomposition retarder is a mercapto compound, an amine compound, organic tin, or organic boron.
  10. The conductive metal nanoparticles are nanoparticles made of gold, silver, copper, platinum, palladium, nickel, aluminum, or an alloy of these metals . The method for producing a conductive fine pattern according to 7, 8 or 9 .
  11. The method for producing a conductive fine pattern according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, wherein the heat extinguishing composition is a solvent solution.
  12. Claim a method of coating the surface of the mold having a fine pattern made of a heat-extinguishing composition from a predetermined unevenness is formed, characterized in that a spin-coating method 1,2,3,4,5,6 , 7, 8, 9, 10 or 11 A method for producing a conductive fine pattern.
  13. 13. The method for producing a conductive fine pattern according to claim 1 , wherein the pressing pressure is 1 to 40 MPa.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04240792A (en) * 1991-01-24 1992-08-28 Matsushita Electric Ind Co Ltd Manufacture of circuit board
JP2004055439A (en) * 2002-07-23 2004-02-19 Mitsubishi Electric Corp Forming method of composition for conductor layer formation and wiring circuit
JP2004172282A (en) * 2002-11-19 2004-06-17 Sumitomo Rubber Ind Ltd Method of manufacturing circuit, and circuit board equipped with the circuit
JP2004193594A (en) * 2002-11-29 2004-07-08 Sekisui Chem Co Ltd Circuit formation transfer sheet, and manufacturing method for circuit board

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04240792A (en) * 1991-01-24 1992-08-28 Matsushita Electric Ind Co Ltd Manufacture of circuit board
JP2004055439A (en) * 2002-07-23 2004-02-19 Mitsubishi Electric Corp Forming method of composition for conductor layer formation and wiring circuit
JP2004172282A (en) * 2002-11-19 2004-06-17 Sumitomo Rubber Ind Ltd Method of manufacturing circuit, and circuit board equipped with the circuit
JP2004193594A (en) * 2002-11-29 2004-07-08 Sekisui Chem Co Ltd Circuit formation transfer sheet, and manufacturing method for circuit board

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