JP4669695B2 - Method for producing fine hollow molded body - Google Patents

Description

  The present invention relates to a method for producing a micro / nanoscale fine hollow molded body.

  In recent years, methods for manufacturing micro / nanoscale microstructures at low cost have been proposed with the development of nanoscience and nanotechnology. For example, there are methods such as nano-imprint lithography and hot-embossing lithography.

  These are formed into a micro / nanoscale uneven shape by pressing a hard mold (mold) on a resin spin-coated on a hard flat substrate at a temperature higher than the glass transition temperature and releasing after cooling. Technology.

  The resolution of 6 nm has been verified so far, and various thermoplastic resin materials can be used depending on the purpose, and 8 inch batch transfer and step & repeat systems have been commercialized.

  Restrictions of these imprint lithography methods and hot embossing methods are as follows: (1) a hard substrate is required, (2) the object must be resin-coated by spin coating, and (3) a girder structure or a hollow structure. Can not be made.

Recently, a reversal imprinting method (reverse imprinting technique) has been disclosed as a method for compensating for these restrictions (see, for example, Patent Document 1).
WO03 / 096123

  In the reversal imprinting method, a resin having a micro / nanoscale unevenness is spin-coated with resin and pressed at a temperature not higher than the glass transition temperature to transfer the shape corresponding to the convex portion of the mold to the target substrate. .

The substrate used in the reversal imprinting method is not necessarily a hard and flat substrate, and may be a substrate having an uneven resin surface such as an LS pattern formed by the imprint method. It has also been shown that a multilayer three-dimensional structure such as a capillary channel can be formed by repeatedly applying the reversal imprinting method (see, for example, Non-Patent Document 1).
H. Ooe, M .; Morimatsu, T .; Yoshikawa, H .; Kawata and Y.K. Hirata, Abstract of EIPBN2004 (San Diego) PI11.

  However, the multilayer three-dimensional structure by the reversal imprinting method has a drawback that the bonding between the layers is weak because the thermoplastic resin is transferred at a temperature lower than the glass transition temperature. There may be no problem for optical applications, but it is fatal for microfluidic technology applications. Even in applications other than microfluidic technology, poor bonding has a negative impact on reliability.

  In view of the above-described drawbacks, an object of the present invention is to form a micro / nanoscale multilayer three-dimensional structure including a crossbeam, a mesh, a capillary channel, and the like with high precision and reproducibility so as to have excellent bonding strength. It is providing the manufacturing method of a hollow molded object.

The method for producing a fine hollow molded body of the present invention comprises applying a heat extinguishing composition mainly composed of a thermoplastic resin to a surface of a mold on which a predetermined fine pattern is formed. Then, a step of laminating the heat extinguishing composition layer, and a mold on which the heat extinguishing composition layer is laminated by a reversal imprinting method is pressed onto a substrate at a temperature lower than the glass transition temperature of the thermoplastic resin. a step of transferring the heated extinguishing composition layer corresponding to a fine pattern on a substrate, such that at least a portion of the heat-extinguishing composition layer is exposed to the outside, a resin layer to a heating extinguishing composition layer It comprises a step of forming and a step of heating to remove the heat extinguishing composition to form a fine hollow.

  The heat-extinguishing composition used in the present invention is a composition mainly composed of a thermoplastic resin, and the thermoplastic resin decomposes and gasifies and disappears by heating, and is heated to 150 to 350 ° C. A 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.

  Moreover, as a chemical crosslinking method, the method of bridge | crosslinking the polyoxyalkylene resin which has a crosslinkable functional group with a crosslinking agent is mentioned, for example.

  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 above-mentioned polyoxyalkylene resin is preferable as the thermoplastic resin forming the heat-extinguishing composition used in the present invention, but the polyoxyalkylene resin may be uncrosslinked or 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-mentioned crosslinking agent, it may be crosslinked at the time most suitable for the production process, for example, before the resin composition is laminated on the surface of the mold, Cross-linking may be performed after the transfer to the substrate or after transfer to the substrate.

  As the heat extinguishing composition 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 a crosslinked product thereof. A suitable resin composition can be 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, the resin composition may be crosslinked before being laminated on the surface of the mold, after being laminated, or after being transferred to the substrate.

  The heat extinguishing composition 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 composition, the decomposition of the heat extinguishing composition is promoted, but when the inorganic peroxide or the organic peroxide is added as a decomposition accelerator, the heat extinguishing composition It is preferable because generation of carbides as decomposition residues can be suppressed, and 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 composition when the heat extinguishing composition is heated. For example, a mercapto compound, an amine compound, organic tin, organic boron Etc.

  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 100 parts by weight of the heat extinguishing composition. 10 parts by weight.

  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-aminopropyltriethoxysilane, 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- (triethoxysilyl) propyl] hexaethylenediamine, and the like, 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 mainly composed of a thermoplastic resin is applied to a surface of a mold on which a predetermined fine pattern is formed , and the heat extinguishing is applied. It is the process of laminating a 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, it has the advantage of transferring the shape of the transfer mold more faithfully, has excellent heat resistance, and exhibits a low linear expansion coefficient and a low molding shrinkage ratio. It can be used advantageously. As such a thermosetting resin, an epoxy resin can be advantageously used from the viewpoint of cost and easy handling.

  In order to transfer the heat extinguishing composition layer according to the fine pattern onto the substrate by the reversal imprinting method, the heat extinguishing composition layer is preferably a uniform and thin layer. A spin coat method is preferable for uniformly and thinly laminating 0.1 to 40 μm, preferably 0.2 to 20 μm on the mold. Moreover, when a heat extinction composition layer contains the organic solvent, it dries after application | coating.

  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 imprinting 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 method of transferring a heat extinguishing composition layer having a predetermined fine pattern to a substrate.

  Next, the reversal imprinting 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 mold surface on which a predetermined fine 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 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 fine pattern is a portion of the convex portion 11. In the figure, reference numeral 2 denotes a heat extinguishing composition layer laminated by a spin coating method.

  In the reversal imprinting method, a mold formed by laminating a heat extinguishing composition layer is pressed onto a substrate at a temperature not higher than the glass transition temperature of the thermoplastic resin, and a predetermined fine pattern is formed on the substrate. The heat extinguishing composition layer is transferred.

  Since the press temperature is to transfer the heat extinguishing composition layer on the fine pattern (projection 11 of the mold 1) formed on the surface of the mold 1, the temperature of the thermoplastic resin constituting the heat extinguishing composition layer is changed. It is a temperature below the glass transition temperature.

  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 imprinting method, the heat extinguishing composition on the concave portion 12 of the mold 1 remains in the mold 1 as shown in FIG. 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.

  When the heat extinguishing composition is uncrosslinked, as described above, when the heat extinguishing composition layer is laminated on the mold or transferred to the substrate, it is crosslinked by heating or light irradiation. Good. In addition, when bridge | crosslinking with heat, 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 third step of the present invention is a step of forming a resin layer on the heat extinguishing composition layer such that at least a part of the heat extinguishing composition layer is exposed to the outside, and the fourth step is This is a step of removing the heat-extinguishing composition by heating to form a fine hollow.

  FIG. 3 is a cross-sectional view showing an example of a state in which a resin layer is formed on the heat extinguishing composition layer, and FIG. 4 is a cross-sectional view showing an example of the obtained fine hollow molded body. In the figure, 4 is a resin layer, and 5 is a fine hollow.

  After the resin layer is formed on the heat extinguishing composition layer, the heat extinguishing composition is heated and removed, so that the heat extinguishing composition is heated and extinguished so that the decomposed gas escapes to the outside. The resin layer formed on the composition layer needs to have at least a part of the heat extinguishing composition layer exposed to the outside. The exposed part is not particularly limited. For example, the end part may be exposed, and an appropriate part such as the center part may be exposed as necessary.

  As the resin constituting the resin layer, any conventionally known resin can be used, and examples thereof include a thermoplastic resin, a thermosetting resin, a photocurable resin, and the like. Resins with excellent heat resistance are preferred because they are heated to remove the composition.

  Therefore, as the thermoplastic resin, for example, a resin having excellent heat resistance such as methyl methacrylate resin, imide resin, amide resin, polycarbonate resin, and polysulfone resin is preferable.

Examples of the thermosetting resin include an epoxy resin, a phenol resin, a silicon resin, an unsaturated polyester resin, a melamine resin, and a urea resin. Examples of the photocurable resin include polyester acrylate, epoxy acrylate, and urethane. Examples thereof include photo-curing resins mainly composed of resins such as acrylate resins such as acrylates, epoxy resins, vinyl ether resins, and silicone resins.

  Since the resin layer is preferably formed uniformly and thinly, it is preferably formed by spin coating. Therefore, the thermoplastic resin is preferably dissolved in an organic solvent and applied as a solution. The thermo / photo curable resin is preferably a solventless type that does not require an organic solvent volatilization step. However, if the viscosity is high and spin coating is difficult, the organic solvent may be added to increase the viscosity to allow easy spin coating. It may be lowered.

  When the resin layer contains an organic solvent, it is heated after application to evaporate the organic solvent. In the case of a thermosetting resin, the thermosetting resin is cured by heating. In the case of a photocurable resin, light is irradiated. To cure the photocurable resin.

  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, it is removed by heating to extinguish the heat extinguishing composition, and a fine hollow molded body in which the place where the heat extinguishing composition exists is hollow is obtained.

  The structure of the method for producing a fine hollow molded body of the present invention is as described above, and a micro / nanoscale multilayer three-dimensional structure including a cross beam, a mesh, a capillary channel, etc. is accurately and accurately reproduced so as to have excellent bonding strength. It can be formed with good properties.

  In the present invention, since the heat extinguishing composition layer is transferred onto the substrate by the reversal imprinting method, if a micron-order fine pattern is formed on the mold, the width and depth of the order of microns. A fine hollow molded body having a hollow having the following is obtained. Such a fine hollow structure can be used for applications such as optical elements, microchannels for microchemistry, infusion devices, reaction vessels, electrophoresis columns, membrane separation mechanisms, and liquid chromatograph columns.

  Furthermore, in the present invention, since the heat extinguishing composition layer is transferred onto the substrate by the reversal imprinting method, the fine pattern formed on the mold can be transferred onto many substrates with high accuracy. Suitable for mass production.

  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, trade name “PTMG1000”) and initiation of photocation 3 parts by weight of an agent (trade name “SP-170” manufactured by Asahi Denka Co., Ltd.) 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 made of a silicon wafer, and the surface of a mold having a 10 μm wide and 2 μm deep recess formed at 40 μm intervals on the surface by photolithography is 1 μm thick. It applied so that it might become.

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 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 imprinting method at a pressure of 20 MPa and a heating temperature of 40 ° C.

  34 parts by weight of an alicyclic epoxy resin (manufactured by Daicel Chemical Industries, trade name “Celoxide 2021”), bisphenol F type epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd., trade name “Epicoat 806L”, and photocation initiator ( Asahi Denka Co., Ltd., trade name "SP-170") 5 parts by weight of an epoxy resin composition on a substrate on which a heat extinguishing composition layer is laminated so that the thickness becomes 100 μm by spin coating. It was applied to.

The epoxy resin composition layer was irradiated with ultraviolet light of 365 nm using a high pressure mercury lamp at an irradiation intensity of 40 mW / cm ² for 60 seconds to cure the epoxy resin composition layer, and then heated at 150 ° C. for 8 minutes. The composition layer disappeared, and a fine hollow molded body in which fine hollows having a width of 10 μm and a depth of 1 μm were formed at intervals of 40 μm was obtained.

(Example 2)
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 (trade name “PTMG1000” by Mitsubishi Chemical Corporation) and photocation initiation 3 parts by weight of an agent (trade name “SP-170” manufactured by Asahi Denka Co., Ltd.) was mixed in a beaker at 50 ° C. under light shielding, and then cooled to room temperature, and 1,1-bis (t-hexylperoxy) 3 parts by weight of 3,3,5-trimethylcyclohexane (manufactured by NOF Corporation, trade name “Perhexa TMH”) was added and mixed 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 alkoxysilyl-modified polypropylene glycol was 40 ° C.

  The obtained mold was brought into contact with a silicon wafer as a substrate, and the heat extinguishing composition layer was transferred onto the substrate by a reversal imprinting method at a pressure of 20 MPa and a heating temperature of 40 ° C. Similarly, after laminating and curing the epoxy resin composition layer, it is heated to extinguish the heat extinguishing composition layer, thereby obtaining a fine hollow molded body in which fine hollows having a width of 10 μm and a depth of 1 μm are formed at intervals of 40 μm. It was.

(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 Toa Gosei Co., Ltd.) and diacylphosphine oxide (Ciba Specialty) 1 part by weight of a chemical company, trade name “Irgacure 819”) was 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 substrate, and the heat extinguishing composition layer was transferred onto the substrate by a reversal imprinting method at a pressure of 20 MPa and a heating temperature of 30 ° C. Similarly, after laminating and curing the epoxy resin composition layer, it is heated to extinguish the heat extinguishing composition layer, thereby obtaining a fine hollow molded body in which fine hollows having a width of 10 μm and a depth of 1 μm are formed at intervals of 40 μm. It was.

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 substrate, and the heat extinguishing composition layer was transferred onto the substrate by a reversal imprinting method at a pressure of 20 MPa and a heating temperature of 40 ° C. Similarly, after the epoxy resin composition layer was laminated and cured, when heated at 150 ° C. for 5 minutes, the heat extinguishing composition layer disappeared, and a fine hollow having a width of 10 μm and a depth of 1 μm formed at intervals of 40 μm. A hollow molded body was obtained.

(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 substrate, and the heat extinguishing composition layer was transferred onto the substrate by a reversal imprinting method at a pressure of 20 MPa and a heating temperature of 40 ° C. Similarly, after the epoxy resin composition layer was laminated and cured, when heated at 150 ° C. for 14 minutes, the heat extinguishing composition layer disappeared, and a fine hollow having a width of 10 μm and a depth of 1 μm formed at intervals of 40 μm. A hollow molded body was obtained.

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

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 4 Resin layer 5 Fine hollow

Claims (19)

A step of applying a heat extinguishing composition mainly composed of a thermoplastic resin to a surface on which a predetermined fine pattern is formed and laminating a heat extinguishing composition layer. The mold having the heat extinguishing composition layer laminated by the reversal imprinting method is pressed onto a substrate at a temperature lower than the glass transition temperature of the thermoplastic resin, and the heat extinguishing composition layer according to the fine pattern A step of transferring the composition onto the substrate, a step of forming a resin layer on the heat extinguishing composition layer so that at least a part of the heat extinguishing composition layer is exposed to the outside, and a heating extinction composition by heating. A process for producing a fine hollow molded body comprising a step of forming a fine hollow by removing the metal.   The method for producing a fine hollow molded body according to claim 1, wherein the thermoplastic resin is a polyoxyalkylene resin having an oxygen content of 15 to 55% by weight.   The method for producing a fine hollow molded article according to claim 2, wherein the polyoxyalkylene resin has a number average molecular weight of 5,000 to 5,000,000.   4. The fine material according to claim 2, 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. A method for producing a hollow molded body.   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. Or it is the crosslinked resin composition, The manufacturing method of the fine hollow molded object of any one of Claims 1-4 characterized by the above-mentioned. The method for producing a fine hollow molded article according to claim 5, wherein the crosslinking agent is a photoreactive crosslinking agent having a functional group represented by the general formula (1).
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.) The heat extinguishing composition comprises a resin composition comprising a resin having a hydrolyzable silyl group and a photoreactive crosslinking agent having a functional group represented by the general formula (1) or a crosslinked resin composition thereof. The manufacturing method of the fine hollow molded object of Claim 1 characterized by these.
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.)   The method for producing a fine hollow molded article according to any one of claims 1 to 7, wherein the heat extinguishing composition contains a thermal decomposition accelerator.   The method for producing a fine hollow molded article according to claim 8, wherein the thermal decomposition accelerator is an inorganic peroxide or an organic peroxide.   The method for producing a fine hollow molded article according to any one of claims 1 to 9, wherein the heat extinguishing composition contains a thermal decomposition retarder.   The method for producing a fine hollow molded article according to claim 10, wherein the thermal decomposition retarder is a mercapto compound, an amine compound, organotin, or organoboron. The method for producing a fine hollow molded article according to any one of claims 1 to 11 , wherein the heat extinguishing composition is a solvent solution. The method for producing a fine hollow molded article according to claim 12 , wherein the lamination method of the heat extinguishing composition is a spin coating method. The method for producing a fine hollow molded body according to any one of claims 1 to 13 , wherein the pressing temperature is from a glass transition temperature of a thermoplastic resin to -30 ° C to a glass transition temperature. Press pressure The method for producing a fine hollow molded body of any one of claims 1 to 14 you being a 1～40MPa. The method for producing a fine hollow molded article according to any one of claims 1 to 15 , wherein a plurality of heat extinguishing composition layers are laminated. Resin which comprises a resin layer is a heat | fever or photocurable resin, The manufacturing method of the fine hollow molded object of any one of Claims 1-16 characterized by the above-mentioned. 18. The method for producing a fine hollow molded article according to claim 17 , wherein the heat or photocurable resin is a solventless type heat or photocurable resin. The method for producing a fine hollow molded body according to any one of claims 1 to 18 , wherein the resin layer is formed by a spin coating method.

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