JP2009227923A - Manufacturing method for article having negative pattern - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To easily obtain an article having a negative pattern, usable as a permeation film, and changing continuously a volume fraction of a hole along a thickness direction. <P>SOLUTION: This manufacturing method for the article having the negative pattern comprises (1) a process for forming a positive pattern of a sublimable substance derived from a gas phase on a surface of a solidifiable and flowable material or ranging over from the surface to an inside, (2) a process for solidifying the flowable material, and (3) a process for removing the sublimable substance, according to this order, and manufacturing the article having the negative pattern on the surface of the flowable material or ranging over from the surface to the inside. The present invention discloses further a separator of a battery or a capacitor manufactured by the method, a separator blended with a foaming agent, and the battery and the capacitor blocking safely a current, by foaming the foaming agent in the separator, when run away thermally, to make distant a distance between electrodes. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention includes a step of forming a positive pattern of a solid sublimable substance derived from a gas phase from the surface of a solidifiable and fluid material or from the surface to the inside thereof, (2) a step of solidifying the material, (3) The step of removing a sublimable substance is performed in this order, the method of manufacturing an article having a negative pattern from the surface of the material or from the surface to the inside, and the article having a porous pattern manufactured by the manufacturing method is used as a separator. The present invention relates to a battery and a battery that further contains a foaming agent that foams at an arbitrary temperature in the article having the porous pattern, and that can safely block the flow of electricity when the separator is foamed above an arbitrary temperature.

  As a method for producing a porous material, there are a method of freeze-drying a water-soluble polymer containing water (Patent Document 1) and a method of freeze-drying a resin combined with a water-soluble polymer (Patent Document 2). As a method for forming a pattern on a fluid material surface using moisture in the air, there is a method using condensed water (Patent Document 3).

JP 2002-146084 A JP 2003-171696 A International Publication No. 2004/048064 Pamphlet

  In the conventional method for producing a porous material using lyophilization, it is necessary to include a substance that can be lyophilized in a solidified and fluid material, and the production method is applied to the substance containing the substance that can be lyophilized. For general examples where water is used for lyophilization, which is limited, the indication is further to a water-soluble substance or a composition that can stably contain water, such as by suspending a water-soluble substance. Limited.

  The pattern manufacturing method using condensed water does not require the substances necessary for patterning to be included in the flowable material, so the manufacturing method has a wide range of applications, but it uses condensation due to the latent heat of solvent evaporation. Therefore, it is necessary to contain a volatile solvent in the fluid material, and further, since the patterning is performed with droplets, the shape of the hole is limited to a part of the sphere.

  Since the holes of the pattern manufactured by the methods of these documents are oriented in a random direction or spherical, there is no anisotropy in the direction of the holes, and the properties as a permeable membrane are not in an ideal state.

  In addition, the method using freeze-drying produces a porous material, but the volatile substances in the porous body volatilize from the entire surface of the solidifiable and fluid material, so that it is in direct contact with the substrate or device surface. It is difficult to form a porous material, and it is necessary to install a porous material on a substrate or a device again.

  In the method using lyophilization, the pore distribution is substantially uniform in the porous material, and it is difficult to incline the pore distribution in the thickness direction of the porous material.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have (1) the surface of a solidifiable and fluid material (hereinafter referred to as fluid material) or the gas phase from the surface to the inside. The surface or surface of the material is formed by performing a step of forming a positive pattern with a solid sublimable substance derived from the above, (2) a step of solidifying the material, and (3) a step of removing the sublimable material in this order. Developed a method that can produce an article having a negative pattern from the inside to the inside, and found that this can be used as a battery separator. Further, by containing a foaming agent in the separator, the contained foaming agent foams during thermal runaway. The inventors have found that the current can be safely interrupted by separating the distance between the electrodes, and have completed the present invention.

  Therefore, the first aspect of the present invention is: (1) a step of forming a positive pattern of a solid sublimable substance derived from a gas phase from the surface of the solidifiable and fluid material or from the surface to the inside thereof; (2) The present invention relates to a method for producing an article having a negative pattern by performing a solidifying step and (3) a step of removing the sublimable substance in this order, and the surface of the material or from the surface to the inside thereof.

  In the second aspect of the present invention, the sublimable substance is a substance having anisotropy in dielectric constant and / or magnetic susceptibility, and at least before the material is solidified, the sublimable substance is further converted into an electric field and / or The present invention relates to a method for manufacturing an article having a negative pattern, including a step of aligning in an arbitrary direction with a magnetic field.

  The third aspect of the present invention is a method for producing an article having a negative pattern, wherein the negative pattern is a pattern in which the volume fraction of the pores is continuously changed from the surface of the fluid material to the inside thereof, And a method for producing an article having a refractive index that continuously changes from the surface to the inside of the fluid material.

  The fourth aspect of the present invention is: (1) a step of forming a positive pattern of a gas-derived solid sublimable substance from the surface of the fluid material applied to the electrode or from the surface to the inside; (2) The present invention relates to a method for producing an electrode having an article having a negative pattern formed on the surface thereof, wherein the step of solidifying the material and (3) the step of removing the sublimable substance are performed in this order.

  According to the method of manufacturing the article of the first aspect of the present invention, it is possible to manufacture an article in which a negative pattern is formed on the surface of the material or from the surface to the inside at a low speed and at a high speed.

  In addition, according to the first aspect of the present invention, as long as the solid sublimable substance is a substantially insoluble fluid material, the present invention can be applied to any combination of the sublimable substance and the fluid material. In particular, when ice is used as a sublimable substance, an article having a negative pattern can be produced in addition to a fluid material that can contain water necessary for conventional freeze-drying techniques, and has a porous pattern. Articles can be manufactured continuously and at high speed by using energy ray curable resin as a fluid material, and photocurable acrylic resin prepolymer or photocurable epoxy resin prepolymer can be used as energy ray curable resin. By using a polymer, it is also possible to easily produce an article having a negative pattern with a thermosetting material that is generally excellent in transparency and heat resistance.

  In addition, according to the first aspect of the present invention, since a fluid material can be solidified into an arbitrary shape, by forming a coating film made of a fluid material on the surface of an article having a complicated shape, It is possible to easily produce a porous pattern on the surface.

  Furthermore, by applying the first invention to the surface of a biomaterial having a complicated shape, an article having a porous pattern can be easily produced, and a material that does not contain water can be used as a fluid material. Therefore, an article having a porous pattern without worrying about dissolution due to humidity or moisture can be easily produced on the surface of the biomaterial.

  Moreover, when the material which can be solidified and has fluidity in the first invention has adhesiveness, an article having a porous pattern on the surface of any material can be directly produced.

  Further, according to the second aspect of the present invention, pattern anisotropy can be expressed in an arbitrary direction.

  Further, according to the third aspect of the present invention, an article having a pattern in which the volume fraction of the pores is continuously changed from the surface of the fluid material to the inside thereof can be manufactured, and the fluid material Articles having a refractive index that continuously changes from the surface to the inside can be manufactured.

  Further, according to the fourth aspect of the present invention, when a fluid material exhibits insulation after solidification, an article having a negative pattern can be used as a separator, and the separator having a porous pattern can be used as a battery or capacitor. It can be formed directly on the electrode surface.

  In the fourth aspect of the present invention, when an article having a negative pattern is used as an active material layer of a battery or a capacitor, an electrode having a large surface area of the battery active material layer can be manufactured.

  The method for producing an article having a negative pattern according to the present invention includes (1) a step of forming a positive pattern of a solid sublimable substance derived from a gas phase from the surface of a solidifiable and flowable material or from the surface to the inside thereof. 2) solidifying the material, and (3) removing the sublimable substance in this order to manufacture an article having a negative pattern from the surface of the material to the inside. .

  The material that can be solidified and has fluidity in the present invention refers to a material that has fluidity to form a negative pattern and can be solidified after the negative pattern is formed. Any material that can be solidified and has fluidity can be used, and examples thereof include liquids and powders having fluidity. In the case of liquid, solidification by cooling of the molten liquid, solidification by volatilizing the solvent of the solution in which the solid is dissolved, polymerization of various prepolymers having reactivity such as liquid epoxy resin prepolymer and acrylic resin prepolymer Solidification by can be used. In the case of powder, a fluid powder that can be solidified by pressure bonding or firing can be used. In addition to the fluid material exemplified herein, any material that can be solidified and fluid can be used. The liquid includes gel, paste, and the like.

  In addition, as a material having fluidity, an insulating material, a conductive material, or a mixture thereof can be used. As the fluid insulating material, a curable organic component and an inorganic component can be appropriately used. Among these, as the organic component, in addition to various epoxy compounds, acrylic compounds, siloxane compounds, etc., prepolymers such as curable monomers and oligomers can be used, and these are melted in a polymer state or dissolved in a solvent. Or a fine powder having fluidity can be used. For these, thermoplastic resins and thermosetting resins can be used. Examples of thermoplastic resins include vinyl acetate, vinyl alcohol, vinyl butyral, vinyl chloride, methacrylate, acrylic acid, methacrylic acid, styrene, ethylene, amide, cellulose, and isobutylene. And prepolymers and polymers made of vinyl ether, polyvinylidene fluoride, polyester and the like. Examples of the thermosetting resin include urea, melamine, phenol, resorcinol, epoxy, oxetane, episulfide, isocyanate, a mixture of polyvinyl alcohol and polycarboxylic acid, a prepolymer and a polymer made of imide and the like. These prepolymers and polymers can also be made photocurable depending on the type of curing agent and polymerization curing agent. These compounds can be used alone or in combination of two or more.

  When blending such a curable prepolymer, a curing agent and a polymerization initiator for curing the prepolymer can be blended as necessary. The kind of these hardening | curing agents and a polymerization initiator can be suitably selected according to the kind of prepolymer to mix | blend. As such a curing agent and polymerization initiator, a compound that initiates a reaction by energy rays can be preferably used. For example, a photo radical polymerization resin of acrylic monomer / oligomer, a photo-michael addition resin of polyene-thiol curing system, a photo cationic polymerization resin of epoxy, oxetane, and vinyl ether monomer / oligomer can be exemplified. Also, various known photosensitizers can be used for these formulations. By using such a photocurable resin, the shape at the time of pattern formation can be quickly fixed.

  When used as a battery separator, it is preferable to use a resin that is insoluble in an organic solvent used as an electrolytic solution, more preferably a water-soluble polymer, for example, a water-soluble polymer such as polyvinyl alcohol or polyvinyl. Examples include alcohols modified with polymerizable substituents such as epoxy, oxetane, or acrylic or methacrylic groups and polymerized three-dimensionally. Also, a type that softens and closes the pores when the battery abnormally generates heat is preferable, and an acrylic resin obtained by radical polymerization of a urethane-modified acrylic resin prepolymer that causes depolymerization by heat can be shown as an example. . In this case, it is possible to obtain a type in which the urethane bond site is cleaved by heat and the softening accompanying the decrease in molecular weight occurs.

  As the insulating material having fluidity to be solidified by heating, various materials such as a resin that is cured by heat, a resin that is solidified by volatilization of a solvent, and a metal oxide obtained by a sol-gel method can be used.

  A known hot melt resin can be used as the fluid insulating material (hereinafter referred to as fluid insulating material).

  In addition, as the inorganic component of the fluid insulating material, various metal alkoxides, various metal chlorides, water glass, colloidal silica, various silicon oxides, silicon nitrides, silicon fluorides, metal oxides, metal nitrides It is possible to use a solution of metal silicide, metal phosphate, or these fine powders having fluidity.

  Such a fluid insulating material containing an inorganic component can be solidified by using a sol-gel reaction or high-temperature baking, and a sol-gel reaction catalyst can be blended with the fluid material.

  As a catalyst for the sol-gel reaction, an acid such as hydrochloric acid; an alkali such as sodium hydroxide or ammonium hydroxide; an amine; or dibutyltin diacetate or dibutyltin dioctate which hydrolyzes and polycondenses inorganic components. , Dibutyltin dilaurate, dibutyltin dimaleate, dioctyltin dilaurate, dioctyltin dimaleate, tin octylate and other organotin compounds; isopropyl triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, bis (dioctyl pyrophosphate) oxyacetate titanate Organic titanate compounds such as tetraalkyl titanate; tetrabutyl zirconate, tetrakis (acetylacetonate) zirconium, tetraisobutyl zirconate, butto Organic zirconium compounds such as citrus (acetylacetonato) zirconium and zirconium naphthenate; organoaluminum compounds such as tris (ethylacetoacetate) aluminum and tris (acetylacetonato) aluminum; zinc naphthenate, cobalt naphthenate, cobalt octylate, etc. And organometallic catalysts. Among these, a dibutyltin compound (SCAT-24 manufactured by Sansha Machinery Chemical Co., Ltd.) can be specifically mentioned as a commercial product. These compounds can be used alone or in combination of two or more.

  These organic components and inorganic components can be used alone or in combination as appropriate, either alone or in combination of organic and inorganic.

  As a conductive material that can be solidified and fluidized (hereinafter referred to as a conductive material having fluidity), a molten metal, an alloy, or the like can be used. Alternatively, a conductive polymer that has been melted or dissolved in a solvent can be used. Further, these conductive materials can be used in the form of fluid powder and can be solidified by baking or compression.

  As such a metal or alloy, an alloy having a low melting point can be particularly preferably used, and examples thereof include Sn—Pb, Sn—In, Sn—Bi, Sn—Ag, and Sn—Zn alloys.

  Next, examples of such a conductive polymer include polyacetylene, polythiophene, polyaniline, poly (3,4-ethylenedioxythiophene) / poly (styrenesulfonate), and the like.

  When the fluid material is an insulator, the conductive material can be contained in the fluid material as long as it has fluidity. Examples of such conductive filler include Ag, Cu, Au, Al, Mg, Rh, W, Mo, Co, Ni, Pt, Pd, Cr, Ta, Pb, V, Zr, Ti, In, Fe, and Zn. Metal powder, flakes or colloids such as Sn—Pb, Sn—In, Sn—Bi, Sn—Ag, Sn—Zn alloy powders and flakes, acetylene black, furnace black Carbon black such as channel black, graphite, graphite fiber, graphite fibril, carbon fiber, activated carbon, charcoal, carbon nanotube, fullerene and other conductive carbon materials, metal oxide conductive fillers include zinc oxide and tin oxide , Indium oxide, titanium oxide (titanium dioxide, titanium monoxide, etc.), among these compounds Filler exhibiting conductivity and surplus electrons are produced by the presence of the child defects, lithium cobalt acid, lithium nickel acid, lithium iron phosphate, and alkali metal salts of conductivity, such as. Such fillers can be used singly or in appropriate combination of two or more, and it is also preferable to use a filler whose surface is treated with a coupling agent or the like. Moreover, ion conductivity can also be improved by mix | blending the graphite and / or clay layered compound which inserted the alkali metal between the layers. In this case, by blending to such an extent that electron conduction does not occur, it is possible to produce an article that is insulating for electron conduction and conductive for ion conduction. Articles having such characteristics can be preferably used as, for example, ion conductive fillers for battery separators.

  The conductive filler is preferably conductive particles, and the size of the particles is more preferably smaller than the size of the member to be formed. When the conductive particles are blended in an insulating composition that can be solidified and fluidized, the conductive particles can be imparted by contacting each other in the insulating composition that can be solidified and fluidized. As such conductive particles, powders or flakes of the above metals or alloys can be used.

  These conductive materials can be used alone or in combination of two or more as required.

  When a conductive article is prepared using conductive particles as described above, a conductive composition is prepared by solidifying a fluid material in which the particles of the insulating material and the conductive particles are combined. Is possible. Unlike the case where the insulating material is a liquid, the conductive particles are not covered by the insulating material, so that the conductive particles easily come into contact with each other, and the resistance value of the conductive particles themselves is low. The resistance value of the composition can be lowered. As a means for eliminating the fluidity of the particles of the insulating material and solidifying it, any means such as baking or compression fixation can be used.

  An example of a fluid conductive material is an ionic liquid. Examples of the liquid having ionicity include a liquid in which ions are dissolved. When the solvent is water, examples of the electrolyte include sodium chloride, potassium chloride, lithium chloride, sodium hydroxide, potassium hydroxide, and lithium hydroxide. When the solvent is an organic substance such as dimethyl carbonate, examples of the electrolyte include lithium hexafluorophosphate, lithium tetrafluoroborate, and lithium trifluoromethanesulfonate. As another example of the liquid having ionicity, an ionic liquid can be exemplified. Examples of ionic liquids include 1,3-dimethylimidazolium methyl sulfate, 1-ethyl-3-methylimidazolium bis (pentafluoroethylsulfonyl) imide, 1-ethyl-3-methylimidazole as imidazolium salt derivatives. Palladium bromide, pyridinium salt derivatives, 3-methyl-1-propylpyridium bis (trifluoromethylsulfonyl) imide, 1-butyl-3-methylpyridinium bis (trifluoromethylsulfonyl) imide, alkylammonium derivatives, tetra Examples of butylammonium heptadecafluorooctane sulfonate, tetraphenylammonium methanesulfonate, and phosphonium salt derivatives include tetrabutylphosphonium methanesulfonate. .

  By impregnating a porous material produced using the sublimable substance of the present invention with these ionic liquids, an electrically conductive article can be formed.

  Further, if necessary, the fluid material can contain a solvent appropriately selected according to the blending components. As such a solvent, a solvent in which a solidified sublimable substance is not substantially dissolved can be used. Specifically, hydrocarbons (propane, n-butane, n-pentane, isohexane, cyclohexane, n-octane, isooctane, benzene). , Toluene, xylene, ethylbenzene, amylbenzene, turpentine oil, pinene, etc.), halogenated hydrocarbons (methyl chloride, chloroform, carbon tetrachloride, ethylene chloride, methyl bromide, ethyl bromide, chlorobenzene, chlorobromomethane, bromobenzene , Fluorodichloromethane, dichlorodifluoromethane, difluorochloroethane, etc.), alcohol (methanol, ethanol, n-propanol, isopropanol, n-amyl alcohol, isoamyl alcohol, n-hexanol, n-heptanol, 2-octane) , N-dodecanol, nonanol, cyclohexanol, glycidol, etc.), ether, acetal (ethyl ether, dichloroethyl ether, isopropyl ether, n-butyl ether, diisoamyl ether, methylphenyl ether, ethyl benzyl ether, furan, furfural, 2 -Methylfuran, cineol, methylal), ketones (acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-amyl ketone, diisobutyl ketone, phorone, isophorone, cyclohexanone, acetophenone, etc.), esters (methyl formate, ethyl formate, formic acid) Propyl, methyl acetate, ethyl acetate, propyl acetate, n-amyl acetate, methyl cyclohexyl acetate, methyl butyrate, ethyl butyrate, propyl butyrate, stearin Butyl), polyhydric alcohols and their derivatives (ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, methoxymethoxyethanol, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monomethyl ether, propylene glycol, propylene Glycol monoethyl ether), fatty acids and phenols (formic acid, acetic acid, acetic anhydride, propionic acid, propionic anhydride, butyric acid, isovaleric acid, phenol, cresol, o-cresol, xylenol, etc.), nitrogen compounds (nitromethane, nitroethane, 1-nitropropane, nitrobenzene, monomethylamine, dimethylamine, trimethylamine, monoethylamine Min, diamylamine, aniline, monomethylaniline, o-toluidine, o-chloroaniline, cyclohexylamine, dicyclohexylamine, monoethanolamine, formamide, N, N-dimethylformamide, acetamide, acetonitrile, pyridine, α-picoline, 2,4 -Lutidine, quinoline, morpholine, etc.), sulfur, phosphorus, other compounds (carbon disulfide, dimethyl sulfoxide, 4,4-diethyl-1,2-dithiolane, dimethyl sulfide, dimethyl disulfide, methanethiol, propane sultone, triethyl phosphate , Triphenyl phosphate, diethyl carbonate, ethylene carbonate, amyl borate, etc.), inorganic solvents (liquid ammonia, silicone oil, etc.), water and the like.

  If necessary, the material having fluidity can be appropriately mixed with a stabilizer, a coupling agent and the like. Specific examples of such stabilizers include 2,6-di-tert-butyl-phenol, 2,4-di-tert-butyl-phenol, 2,6-di-tert-butyl-4-ethyl- Phenol-based antioxidants exemplified by phenol, 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-tert-butyl-anilino) -1,3,5-triazine and the like Agent, alkyldiphenylamine, N, N'-diphenyl-p-phenylenediamine, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, N-phenyl-N'-isopropyl-p-phenylenediamine, etc. Aromatic amine antioxidants, dilauryl-3,3'-thiodipropionate, ditridecyl-3,3'-thiodipropionate A sulfide hydroperoxide decomposer exemplified by bis [2-methyl-4- {3-n-alkylthiopropionyloxy} -5-tert-butyl-phenyl] sulfide, 2-mercapto-5-methyl-benzimidazole and the like; Tris (isodecyl) phosphite, phenyl diisooctyl phosphite, diphenyl isooctyl phosphite, di (nonylphenyl) pentaerythritol diphosphite, 3,5-di-tert-butyl-4-hydroxy-benzyl phosphate diethyl ester , Phosphorus hydroperoxide decomposing agents exemplified by sodium bis (4-tert-butylphenyl) phosphate, etc., salicylates exemplified by phenyl salicylate, 4-tert-octylphenyl salicylate, etc. Benzophenone-based light stabilizers exemplified by 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and the like, 2- (2'-hydroxy-5'-methylphenyl) Benzotriazole-based light exemplified by benzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol] and the like Stabilizers, hindered amine light stabilizers exemplified by phenyl-4-piperidinyl carbonate, bis- [2,2,6,6-tetramethyl-4-piperidinyl sebacate] and the like, [2,2′- Exemplified by thio-bis (4-t-octylphenolate)]-2-ethylhexylamine-nickel- (II) Examples thereof include Ni-based light stabilizers, cyanoacrylate-based light stabilizers, and oxalic acid anilide-based light stabilizers. As such a coupling agent, specifically, as a fluorine-based silane coupling agent, (tridecafluoro-1,1,2,2-tetrahydrooctyl) triethoxysilane, an epoxy-modified silane coupling agent Coupling agent (trade name: KBM-403) manufactured by Shin-Etsu Chemical Co., Ltd., coupling agent (trade name: TESOX) manufactured by Toagosei Co., Ltd. as an oxetane-modified silane coupling agent, or vinyltrimethoxysilane, vinyltriethoxy Silane, γ-chloropropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxy Silane, γ-glycidoxypropyltrimethoxysilane , Silane coupling agents such as β-glycidoxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, triethanolamine titanate, Titanium acetylacetonate, titanium ethyl acetoacetate, titanium lactate, titanium lactate ammonium salt, tetrastearyl titanate, isopropyl tricumyl phenyl titanate, isopropyl tri (N-aminoethyl-aminoethyl) titanate, dicumyl phenyloxyacetate titanate, isopropyl trio Kutanoyl titanate, isopropyl dimethacrylisostearoyl titanate, titanium lactate ethyl ester , Octylene glycol titanate, isopropyl triisostearoyl titanate, triisostearyl isopropyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, tetra (2-ethylhexyl) titanate, butyl titanate dimer, isopropyl isostearoyl diacryl titanate, isopropyl tri (dioctyl phosphate) ) Titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (di) -Tridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate Tochitaneto, mention may be made of bis (dioctyl pyrophosphate) ethylene titanate, tetra -i- propyl titanate, tetra -n- butyl titanate, titanium-based coupling agents such as diisostearoyl ethylene titanate. These compounds can be used alone or in combination of two or more.

  When the fluid material is a liquid, various surfactants can be contained in order to control wetting. Examples of such surfactants include soaps, lauryl sulfate, polyoxyethylene alkyl ether sulfate, alkyl benzene sulfonate, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl phenyl ether phosphate. Acid, N-acyl amino acid salt, α-olefin sulfonate, alkyl sulfate ester salt, alkyl phenyl ether sulfate ester salt, methyl taurate, and the like. Examples of amphoteric surfactants include alkyl diaminoethyl glycine hydrochloride, 2 -Alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, lauryldimethylaminoacetic acid betaine, coconut oil fatty acid amidopropyl betaine, fatty acid alkyl betaine, sulfobetaine, amino oxide, etc. Nonionic (nonionic) surfactants include polyethylene glycol alkyl ester compounds, alkyl ether compounds such as triethylene glycol monobutyl ether, ester compounds such as polyoxysorbitan esters, alkylphenol compounds, and fluorine compounds. Examples thereof include silicone compounds and silicone type compounds. These compounds can be used alone or in combination of two or more.

  In order to improve the mechanical strength and thermal characteristics after solidification, the material having fluidity can be blended with various fillers as necessary as long as other physical properties are not impaired. Insulating fillers include powders of metal oxides such as alumina, silica, zirconia and titania, sols such as colloidal silica, titania sol and alumina sol, clay minerals such as talc, kaolinite and smectite, and carbides such as silicon carbide and titanium carbide. , Nitrides such as silicon nitride, aluminum nitride and titanium nitride, borides such as boron nitride, titanium boride and boron oxide, complex oxides such as mullite, hydroxides such as aluminum hydroxide and magnesium hydroxide, polypropylene powder And resins such as polyethylene powder and aramid fibrous powder. A porous material produced using a fluid material with such filler added has high strength and can be used preferably as a battery separator. Dendrites generated between electrodes penetrate through the separator. The possibility of short circuiting can be reduced.

  The fluid material can be obtained as a solution, suspension, powder, or the like by mixing and stirring the above components. For the stirring, various stirring devices such as a propeller mixer, a planetary mixer, a hybrid mixer, a kneader, an emulsifier homogenizer, and an ultrasonic homogenizer can be appropriately selected. Moreover, it can stir, heating or cooling as needed.

  When the fluid material is a liquid, it can be easily printed or formed into an arbitrary shape by various devices such as a dispenser, a screen printer, and an ink jet printer. In addition, an extremely thin film of the material can be formed between the hollow supports like a soap sphere, and a pattern can be formed from one side or both sides of the membrane, from the surface to the inside, or through both sides.

  Sublimation refers to a phenomenon in which a substance undergoes a phase transition from a solid to a gas and from a gas to a solid without going through a liquid, and a sublimable substance in the present invention refers to a phase transition from a gas to a solid and a phase from a solid to a gas. Refers to the substance that is transferred. In the step (1), the property of phase transition from gas to solid is used. In step (3), the property of phase transition from solid to gas can be used. However, after solidifying a fluid substance, it can be removed after phase transition from solid to liquid. Examples of the sublimable substance include naphthalene, 1,7,7-trimethylbicyclo [2.2.1] heptan-2-one, solid carbon dioxide, iodine, and ice. The sublimable substance preferably has a higher vapor pressure from the viewpoint of easy phase transition. When the fluid material is a liquid, the sublimable substance is preferably insoluble in the liquid.

  The positive pattern in the present invention refers to a pattern formed by a solid sublimable substance derived from a gas phase, and the shape of a crystal of the sublimable substance is a positive pattern. This solid sublimable material can be formed to penetrate the surface of the flowable material and from the surface into the interior, giving the positive pattern shape a negative pattern to the flowable material. Here, the term “derived from the gas phase” means that the solid sublimable substance is derived from a gas. A solid sublimable substance derived from the gas phase is considered to enter the fluid material due to the gravity of the sublimate substance itself, electrostatic interaction between the sublimable substance and the fluid material, etc. .

  Formation of the positive pattern in step (1) can be achieved by cooling the sublimable substance to a temperature below the sublimation point. When the sublimable substance existing in the gas phase is cooled to a temperature below the sublimation point, it becomes solid on the surface of the fluid material and forms a positive pattern.

  It is preferable from a practical point of view that the sublimable substance is ice, and the formation of the positive pattern in the step (1) is to cool the fluid material below the frost point, and to convert moisture in the air to frost. This can be achieved by forming.

  Solidification of the fluid material in the step (2) of the present invention can be performed by curing the material by irradiation with energy rays or heating, cooling the material, or volatilization of a solvent in the material. Examples of energy rays include particle rays such as alpha rays, proton rays and neutron rays, electron rays such as beta rays, and electromagnetic waves such as gamma rays, X rays and ultraviolet rays. In particular, since the positive pattern of the sublimable substance sublimes at a high temperature, it is preferable to use curing using energy rays that generate less heat and can be solidified while being cooled.

  When the step (2) is performed by energy beam irradiation, an energy beam curable resin or an energy beam curable adhesive can be used as the fluid material. The above-mentioned prepolymer or the like can be used for the energy beam curable resin or the energy beam curable adhesive.

  When using a resin as a fluid insulating material that cures with active energy rays, less heat is generated during curing compared to heat curing, so use a sublimable material that is weak against heat or a sublimable material that has a low sublimation temperature. In the case of producing an article containing a foamable substance, a foaming agent having a low foaming temperature can be used. Examples of the active energy ray include the above-described proton beam, electron beam, and electromagnetic wave. Moreover, the atmosphere at the time of irradiating an active energy ray is not limited, It can irradiate in various atmospheres and temperature environments, such as air | atmosphere, inert gas, such as nitrogen and argon, and a vacuum.

  Step (2) can be performed by cooling when the fluid material is a molten polymer, metal, alloy, or the like.

  When a material having fluidity in a molten state is cooled and solidified, it is advantageous when the mass of the material having fluidity is fast and mass production is required. In addition, when the material having fluidity contains a foaming substance and the melting temperature is lower than the foaming temperature, foaming of the foaming substance can be performed quickly and efficiently. Generation | occurrence | production of the fragment | piece accompanying the fracture | rupture of the substance with the fluidity | liquidity with it can be prevented.

  When the fluid material contains a volatile solvent, the solidification of the fluid material in the step (2) can be achieved by volatilizing at least a part of the solvent in the material. . In addition, it is not necessary to complete step (2) only by this step, and curing by irradiation with energy rays is performed in a state where the density of the prepolymer or the like in the fluid material is increased by volatilization of the solvent. Thus, deformation, shrinkage, etc. during curing can be suppressed.

  Step (3) can be easily performed by subjecting the sublimable substance to heat sublimation or sublimation under reduced pressure. Moreover, although the solidified fluid material is not substantially dissolved, it can be carried out with a solvent that dissolves the sublimable substance.

  The above process is shown in the schematic diagram of FIG.

  Here, FIG. 1 shows (1) a positive pattern 4 of a solid sublimable substance by cooling a substrate 3 on which a coating film of a material 2 that can be solidified and fluidized in a vaporized sublimable substance atmosphere 1 is formed. Forming from the surface of the material 2 having fluidity or from the surface to the inside, and then (2) solidifying the material 2 having fluidity and then (3) sublimating and removing the sublimation material to form a negative pattern 5 It is the example which showed the method of manufacturing manufactured goods. (A) is a state in which a substrate 3 on which a coating film of fluid material 2 is formed in vaporized sublimable substance atmosphere 1, and (b) is a sublimation point of the sublimable substance below fluid material 2. (C) is a state in which the positive pattern 4 of the solid sublimable substance is formed from the surface of the fluid material 2 or from the surface to the inside, and (c) solidifies the fluid material and then removes the sublimable substance. The state in which the article in which the negative pattern 5 is formed is shown.

  In the case of the example in FIG. 1, the substrate 3 is a support for the material 2 having fluidity, but a film of the material having fluidity is stretched on the ring-like support, and a positive pattern of a solid sublimation substance is provided there. It is also possible to form the film and pattern it, or to form a film of fluid material on the surface of a complicated shape and pattern it, and the embodiment is not particularly limited.

  Moreover, a porous pattern can be illustrated as a negative pattern of the present invention, and when a positive pattern of a solid sublimable substance penetrates from the surface of a solid material that is solidified and fluid, it penetrated from the surface to the inside. A porous pattern can be formed.

  Next, FIG. 2 is an example schematically showing how the negative pattern penetrates to the back surface of the material that can be solidified and has fluidity.

  As shown in FIG. 2C, when the positive pattern 4 of the solid sublimable substance penetrates to the back surface of the material 2 having fluidity, the penetrating negative pattern 5 can be formed. Whether the positive pattern 4 of the solid sublimable substance penetrates the flowable material 2 depends on the amount of the positive pattern 4 of the solid sublimable substance and the degree of crystal growth, and the cooling time, temperature, and sublimable substance. It can be determined by adjusting the concentration of the sublimable substance in the atmosphere 1. In addition, the size of the positive pattern 4 of the solid sublimable substance also includes the cooling time and temperature, the concentration of the sublimable substance in the sublimable substance atmosphere 1, the specific gravity difference between the fluid material and the individual sublimable substance, It can be adjusted by electrical interaction and wettability.

  In one embodiment of the method for producing an article having a negative pattern according to the present invention, when the solid sublimable substance is a substance having anisotropy in dielectric constant and / or magnetic susceptibility, at least before solidifying the material. And orienting the solid sublimable substance in an arbitrary direction with an electric field and / or a magnetic field.

  Here, FIG. 3 shows a state in which a solid sublimable substance is oriented by applying an electric field and / or a magnetic field 6, and a positive pattern 7 of the oriented solid sublimable substance can be solidified and has fluidity. It is the example which showed typically a mode when a negative pattern was formed from the surface of a certain material or the surface to the inside.

  As shown in FIG. 3B, when the positive pattern 4 of the solid sublimable material has anisotropy in dielectric constant and / or magnetic susceptibility, an electric field and / or magnetic field 6 is applied by applying an electric field and / or a magnetic field 6. The negative pattern 8 oriented in the direction corresponding to the direction in which the magnetic field is applied can be formed.

Here, the magnetic field (magnetic field) H (unit: AT / m = ampere-turn / meter) in the present invention refers to a vortex-like field generated by the movement of electric charges, and exerts a force on the movement of electric charges. The strength of the magnetic field is represented by magnetic flux density B (unit: T = Tesla), and is the number of magnetic lines Φ (unit: Wb = Weber) penetrating the area S (m ² ) perpendicular to the magnetic field divided by the area. .

Formula 1 B = Φ / S (Wb / m ² = T)

  Such a magnetic field can be generated by passing an electric current as in an electromagnet, or can be generated by aligning the direction of the magnetic moment of an electron spin of a substance as in a permanent magnet. Further, the magnetic flux density B and the magnetic field H can be expressed by the following relational expression in a vacuum.

Formula 2 B = μ ₀ H

Here, μ ₀ is the permeability of vacuum, which is 4Π × 10 ⁻⁷ (Henry / meter = H / m) in rational units, and 1 (anonymous number) in non-rational units, and the magnetic flux density B and magnetic field strength H are It is a coefficient to tie. Further, the magnetic permeability K (Henry / meter = H / m) is obtained by dividing the ratio μ between the magnetic flux density B and the magnetic field strength H when a substance is placed in a magnetic field by μ ₀ .

Formula 3 K = μ / μ ₀

  The strength of the interaction of the material by the magnetic field is indicated by the magnetic susceptibility χ, and the larger the absolute value, the stronger the magnetic field is induced in the material, causing a strong magnetic interaction with the induced magnetic field. The above-described magnetic permeability K is a non-rational unit and the following relational expression is established.

            Equation 4 K = 1 + χ

  In the following explanation, unless otherwise specified, the magnetic susceptibility χ is shown in a non-rational unit. Next, Table 1 shows the magnetic anisotropy of typical substances. The examples shown here are magnetic anisotropy derived from the crystal structure, but artificially magnetic anisotropy, such as fibers obtained by stretching polymers and materials combining different magnetic susceptibility, etc. The material can be oriented by applying an appropriate magnetic field to a material having a shape or a material having shape anisotropy.

  The interaction between the magnetic field and the substance is determined by the strength of the magnetic field and the absolute value of the magnetic susceptibility χ, and the force to align the axis where the magnetic field is strong and the absolute value of the magnetic susceptibility χ is large is parallel to the magnetic field. Which direction it is actually oriented (easy magnetization axis) is determined by the balance of the three-axis magnetic anisotropy of the crystal.

  Also, magnetic anisotropy means that there is anisotropy in a substance with respect to magnetization excited by an external magnetic field. In the magnetic field, torque is generated by magnetic interaction, and in a more stable direction. Rotate. Substances that have anisotropy in the molecular structure also have magnetic anisotropy. For example, in a fiber made by drawing, molecular chains are aligned in the drawing direction, so the fiber direction (//) and perpendicular to it The magnetic susceptibility differs in the direction (率). When the fiber exhibits diamagnetism, the difference is called diamagnetic anisotropic magnetic susceptibility (χa), and is represented by the difference in magnetic susceptibility with respect to an arbitrary axis.

χ _a = χ // − χ⊥

When a diamagnetic material having such magnetic anisotropy is placed in a magnetic field of strength B, the material acquires magnetic energy E.

Here, μ ₀ is the vacuum permeability, V is the volume of the object, θ is the angle between the magnetic field and the fiber axis direction, and B is the external magnetic field strength.

When χ _a > 0, the magnetic energy becomes smaller and more stable when the fiber axis direction is parallel to the magnetic field. As a result, it is oriented parallel to the magnetic field.

  Such a uniaxially oriented fiber can be described as described above. On the other hand, the direction of orientation of substances having different magnetic anisotropy in three axes is spatially determined. In this case, the direction in which the substance is oriented with respect to the external field is determined from the value of the triaxial magnetic anisotropy.

  It can also be seen from the formula that when the external magnetic field is large and when the volume is large, the magnetic energy is received more strongly.

  Some substances having magnetic anisotropy have anisotropy in the electronic state in the substance. In the case of the fibers described above, anisotropy occurs in the flow of electrons through the bonds by arranging the molecules in the stretched direction. A substance having anisotropy in the crystal structure is also oriented in the magnetic field. On the other hand, even when there is no magnetic anisotropy, the material is oriented if it has anisotropy.

  When a magnetic field is applied to such a substance, it is oriented in a magnetically stable direction. However, when a magnetic field that rotates uniaxially is applied to a material having magnetic anisotropy, for example, the axis of hard magnetization of the substance is relative to the rotational axis. Oriented parallel to the rotation axis of the magnetic field. In addition, as described above, the magnetic field applied to the substance having magnetic anisotropy can be a magnetic field in which the application direction and strength of the magnetic field vary with time, including the rotating magnetic field.

  Although the behavior of a substance having magnetic anisotropy in a magnetic field has been described above, the behavior of a substance having dielectric anisotropy in an electric field can also be explained by an equivalent principle.

  Although it is possible to coat or combine other substances with a substance that performs such magnetic field orientation, it is necessary to perform the magnetic field orientation within a range that does not lose effective magnetic anisotropy.

  When a substance having magnetic and / or dielectric anisotropy is oriented in a magnetic material and / or electric field in a flowable material, it is necessary to overcome random rotational motion derived from thermal energy and viscous resistance. . In order to orient a substance having a small magnetic and / or dielectric anisotropy, it is advantageous to use a strong magnetic field and / or electric field, and the process can be completed in a short time by using a low-viscosity fluid. You can also.

  Moreover, it is preferable to orient using a magnetic field and / or an electric field in a fluid material whose specific gravity is adjusted so that a substance having magnetic and / or dielectric anisotropy does not settle.

  As another method of orienting a material having no magnetic anisotropy, a method of orienting and attaching a substance having anisotropy to a material having no magnetic anisotropy can be used. In this case, a material without magnetic anisotropy can be indirectly magnetically oriented by the anisotropy of the substance having anisotropy attached to the orientation. For example, a flat substance having no magnetic anisotropy in which a surfactant is aligned and adhered by the intermolecular force can be aligned even in a static magnetic field due to the magnetic anisotropy of the surfactant.

  In particular, in terms of orientation using a magnetic field and / or electric field, the fluid material is preferably a liquid, and the lower the viscosity of the liquid, the smaller the viscous resistance to orientation using the magnetic field and / or electric field. As a result, the orientation by the magnetic field and / or the electric field can be smoothly performed, which is more preferable. Besides this, it can be applied to fluid powder and gas, and is not restricted by the type of material.

  In addition, a magnetic field or an electric field can be absorbed by a substance having a high magnetic susceptibility or a substance having a high dielectric constant, and the lines of magnetic force or lines of electric force can be bent. Using these characteristics, magnetic lines of force or electric lines of force are bent along a pattern made of a material having a high magnetic susceptibility or dielectric constant, and anisotropic to the magnetic anisotropy or dielectric constant along the bent lines of magnetic force or electric lines of force. It is also possible to tilt and align the material having the property.

  In another embodiment of the method for producing an article having a negative pattern according to the present invention, the negative pattern is a pattern in which the volume fraction of pores from the surface to the inside of the fluid material is continuously changed. It is a method of manufacturing. Since the shape of the positive pattern formed in the step (1) is formed as a negative pattern, the negative pattern becomes a shape when the positive pattern enters from the surface to the inside. Therefore, it is possible to form a pattern in which the porosity of the pattern changes continuously from the surface to the inside, and it can be applied to the production of a gradient material.

  As an example of this application, when the obtained article has pores having a diameter equal to or less than the wavelength of light and a depth equal to or greater than the wavelength of light whose volume fraction continuously changes from the surface of the fluid material to the inside thereof, A gradient material having a continuously changing refractive index can be obtained. In this case, the hole diameter is preferably 100 nm or less, more preferably 50 nm or less, and the hole depth is preferably 500 nm or more, and more preferably 1 μm or more. Such a material becomes a gradient material having a continuous refractive index proportional to the volume fraction of the air and the solidified material, and light reflection at the air interface can be reduced.

  In another embodiment of the method for producing an article having a negative pattern according to the present invention, a fluid material is applied to the glass surface, and the negative pattern is formed on the glass surface by the steps (1) to (3). It is a method to be formed. Since an air layer exists in this negative pattern, it can be preferably applied to the production of glass having a heat insulating effect due to the negative pattern on the glass surface. The negative pattern is more preferably a porous pattern, and the size of the negative pattern is more preferably less than the wavelength of light from the viewpoint of transparency. Moreover, a super-water-repellent surface can be formed by lowering the surface tension of the negative pattern surface with a surface treatment agent or the like.

  Moreover, the aspect of the method for producing an electrode having an article having a negative pattern according to the present invention formed on the surface is such that the fluid material has adhesiveness and at least exhibits insulation after solidification, 1) A step of forming a positive pattern of a solid sublimable substance derived from a gas phase from the surface to the inside of the fluid material applied to the electrode, (2) a step of solidifying the material, and (3) the sublimation. The step of removing the active substance is performed in this order. An article in which the inner hole of the article having an insulating negative pattern penetrates to the back surface can be used as a separator. In this case, by coating the electrode with a fluid material and then forming a porous pattern, it is possible to manufacture a separator-integrated electrode that causes only electric conduction by ions without being in contact with the counter electrode. In this way, since the positive pattern of the solid sublimable material enters from the surface to the inside, a porous pattern penetrating from the front surface to the back surface can be easily formed, and can be used as an article having permeability by the porous pattern. In particular, it can be preferably applied to an application as a separator for a battery or a capacitor. In addition, it is possible to coat and form a material with fluidity, so it is possible to cover the electrode surface with a film of an article having an extremely thin porous pattern. Can be effectively used for development of a battery having a large capacity by developing a battery capable of performing the above, developing a thin battery, and packing a thinned active material. Furthermore, since the electrode and the separator can be integrally formed, the process can be simplified. Furthermore, the separator which mix | blended the foamable substance can be used also as a safety mechanism which foams at the time of thermal runaway and stops the flow of electricity safely. Furthermore, according to this method, a separator can be continuously produced using a thermosetting photo-radical curable acrylic resin, a photo-cation curable epoxy resin and an oxetane resin that are polymerized in a tertiary manner, so that the separator dissolves during abnormal heat generation. Thus, it is possible to easily manufacture a separator having high heat resistance and low possibility of thermal runaway.

  FIG. 4 is a schematic view of an electrode manufacturing method in which a separator is integrally formed. (A) is a state in which the surface of the electrode 9 is coated with a solidified and fluid material 2 having adhesiveness, and (b) A state in which a positive pattern 4 made of a solid sublimable substance is formed on the surface of the fluid material 2, and (c) shows a state in which pores 10 having a porous pattern are formed by removing the sublimable substance. Yes.

  As shown in FIG. 4, it is possible to easily produce an electrode in which a porous material is integrated, and the number of steps for installing a separator or a separator can be reduced. Moreover, since the entire electrode surface can be protected by the separator, the probability of an accident due to a short circuit with the counter electrode can be reduced.

  In a battery or capacitor, the electrode area and volume determine its electrical capacity, output and / or efficiency, so it is generally difficult to incorporate a safety device on the entire surface because the electrode area is widened. . On the other hand, a safety device can be simply installed on the entire surface of the electrode by using a porous material having a foamable substance as a separator. In addition, since the current flow is blocked by foaming in the present invention, even when a conductive foreign matter enters between electrodes or a dendrite is generated and a short circuit occurs, the foreign matter and dendrite are pushed up by expansion due to foaming. Can solve the short circuit.

  In another embodiment of the method for producing an article having a negative pattern of the present invention, the flowable material contains a foamable substance that fires at an arbitrary temperature, so that the obtained article is foamed at a predetermined temperature. It is characterized by doing.

  The foamable substance generally has a large volume expansion coefficient when it becomes a gas from a solid or liquid, and is preferably a solid or liquid that vaporizes at the predetermined temperature. The vaporization includes chemical decomposition, sublimation, You can choose what happens by boiling. Foaming efficiency can be increased by selecting a foamable substance having a large expansion ratio, and a substance having a volume expansion coefficient of 10 times or more is preferable, and a substance having a volume expansion coefficient of 50 times or more is more preferable.

  When the foaming substance that causes chemical decomposition when it reaches a predetermined temperature, for example, when a substance consisting of one molecule is chemically decomposed into two or more molecules, the volume expansion coefficient further increases. The foaming efficiency can be increased by increasing the foaming ratio. Substances causing such chemical decomposition include sodium hydrogen carbonate, p, p′-oxybisbenzenesulfonylhydrazide, azodicarboxylic acid amide, N, N′-dinitrosopentamethylenetetramine, 4,4′-oxybis ( And benzenesulfonyl hydrazide).

  Examples of the foaming substance that sublimes when reaching a predetermined temperature include naphthalene, 1,7,7-trimethylbicyclo [2.2.1] heptan-2-one, solid carbon dioxide, iodine and the like.

  Foamable substances that boil when they reach a certain temperature include hydrocarbons (propane, n-butane, n-pentane, isohexane, cyclohexane, n-octane, isooctane, benzene, toluene, xylene, ethylbenzene, amylbenzene, turpentine oil. , Pinene, etc.), halogenated hydrocarbons (methyl chloride, chloroform, carbon tetrachloride, ethylene chloride, methyl bromide, ethyl bromide, chlorobenzene, chlorobromomethane, bromobenzene, fluorodichloromethane, dichlorodifluoromethane, difluorochloroethane, etc.) Alcohol (methanol, ethanol, n-propanol, isopropanol, n-amyl alcohol, isoamyl alcohol, n-hexanol, n-heptanol, 2-octanol, n-dodecanol, nonanol, Lohexanol, glycidol, etc.), ether, acetal (ethyl ether, dichloroethyl ether, isopropyl ether, n-butyl ether, diisoamyl ether, methylphenyl ether, ethylbenzyl ether, furan, furfural, 2-methylfuran, cineol, methylal) , Ketones (acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-amyl ketone, diisobutyl ketone, phorone, isophorone, cyclohexanone, acetophenone, etc.), esters (methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, Propyl acetate, n-amyl acetate, methyl cyclohexyl acetate, methyl butyrate, ethyl butyrate, propyl butyrate, butyl stearate, etc.), polyhydric alcohols and their derivatives ( Tylene glycol, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, methoxymethoxyethanol, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monomethyl ether, propylene glycol, propylene glycol monoethyl ether, etc.), fatty acids and phenols ( Formic acid, acetic acid, acetic anhydride, propionic acid, propionic anhydride, butyric acid, isovaleric acid, phenol, cresol, o-cresol, xylenol, etc., nitrogen compounds (nitromethane, nitroethane, 1-nitropropane, nitrobenzene, monomethylamine, dimethyl) Amine, trimethylamine, monoethylamine, diamylamine, aniline, monomethyl Aniline, o-toluidine, o-chloroaniline, cyclohexylamine, dicyclohexylamine, monoethanolamine, formamide, N, N-dimethylformamide, acetamide, acetonitrile, pyridine, α-picoline, 2,4-lutidine, quinoline, morpholine, etc. ), Sulfur, phosphorus, other compounds (carbon disulfide, dimethyl sulfoxide, 4,4-diethyl-1,2-dithiolane, dimethyl sulfide, dimethyl disulfide, methanethiol, propane sultone, triethyl phosphate, triphenyl phosphate, carbonic acid Examples thereof include liquids such as diethyl, ethylene carbonate, and amyl borate), inorganic solvents (such as liquid ammonia and silicone oil), liquid metals, and water.

  The gas generated from the foamable material is preferably flame retardant, and damage when burned as a result of abnormal heat generation can be minimized.

  The foamable material can be coated with a softening material that softens above the predetermined temperature. It is preferable that this softening material coating does not rupture as a result of foaming of the foaming material, and confines and expands the gas generated inside, and the foaming efficiency is increased by inflating the softening material like a balloon by foaming. Can do. Further, when the temperature drops after foaming or when stress is applied from the outside, shrinkage can be prevented by the expanded softening substance.

  The softening temperature of the softening material is preferably as close as possible to the foaming temperature, and more preferably higher than the foaming temperature. The temperature difference between the softening temperature and the foaming temperature is preferably within 100 ° C. Examples of such softening substances include various thermoplastic polymers that are organic substances, and examples thereof include polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyvinyl alcohol, polyvinyl acetate, and acrylonitrile butadiene styrene resin. .

  Furthermore, the surface of the foamable substance is densely covered with a conductive material, so that the gas generated gradually from the foamable substance before foaming can be contained, and the foaming characteristics of the foamable substance can be maintained over a long period of time. The prescription as described above is effective for applications that require maintenance of foaming characteristics over a long period of time (such as home appliances and in-vehicle electronic devices). The conductive material covered with foaming of the foamable material breaks, but when the foamable material is covered with a softening material, the softening material foams due to the leakage of gas generated from the foamable material. It is possible to prevent the efficiency from decreasing and maintain the foaming efficiency.

  Any amount of foamable material can be added, but the conductive composition is insulative by foaming, especially when it is used for applications where the current runaway of the battery or capacitor is blocked by foaming to block the current flow. That is, an amount necessary for at least an electric resistance higher than that before foaming, or a state in which a current does not flow substantially under use conditions is added. This amount is the type of conductive material, particle size, shape, etc., type of foamable material, particle size, shape, etc., foaming temperature, rate of temperature rise to foaming temperature, holding time at foaming temperature, pressure in foaming environment Depends on the amount of moisture in the foaming environment, etc., especially depending on the type of conductive particles, the type of foaming material, and the foaming temperature, but the change in electrical resistance can be easily measured by measuring the resistance before and after foaming. Can be sought.

  As an example, when using silver powder as a conductive material, a substance that decomposes and vaporizes at a predetermined temperature into a foamable substance (for example, sodium bicarbonate), and a synthetic resin (for example, an epoxy resin) as an insulator Is preferably 0.1 to 0.8 part by weight, more preferably 0.16 to 0.24 part by weight, based on 1 part by weight of the conductive material. In the following example, the conductive material is silver powder, and the foaming material is a softening material that softens at a predetermined temperature or higher and is coated with a material that is chemically decomposed and vaporized at a predetermined temperature (for example, Nippon Philite) Co., Ltd., trade name: EXPANCEL), when using a synthetic resin (for example, epoxy resin) as an insulator, the preferred amount of foaming material added is 0.3 to 0 with respect to 1 part by weight of the conductive material. 0.5 parts by weight, more preferably 0.36 to 0.44 parts by weight. As another example, the conductive material is silver powder, the foamable material is a softening material that softens at a predetermined temperature or more, and the material that is chemically decomposed and vaporized at a predetermined temperature is coated with the softening material. (For example, Nihon Philite Co., Ltd., trade name: EXPANCEL) further coated with a conductive material (for example, nickel-phosphorus plating), or when using a synthetic resin (epoxy resin) for the insulator, the conductive material The amount of the foamable material added is preferably 0.4 to 1.6 parts by weight, more preferably 0.4 to 0.6 parts by weight with respect to 1 part by weight. In the above example, the amount of synthetic resin added is preferably 0.1 to 0.2 parts by weight.

  These foamable substances can be used alone or in appropriate combination of two or more as required.

  FIG. 5 (a) shows a state in which electricity is flowing between the electrodes 9 through the pores 10 of the porous pattern in which the separator includes the foamable substance 11 and impregnated with the electrolytic solution, and between the electrodes 9. It is a schematic diagram, and (b) is an example showing a state in which the distance between the electrodes is expanded by the foamable substance 13 after foaming to prevent conduction.

  As shown in FIG. 5B, ionic conduction can be stopped by largely separating the distance between the electrodes by foaming. Further, if a core-shell type foaming agent is used, the foaming agent after foaming becomes an insulator containing air, so that the flow of electricity between the electrodes can be more reliably stopped. The term “insulation” as used herein refers to a state where the resistance value is at least larger than that before foaming, and preferably refers to a state where no substantial electricity flows.

  Examples of the battery or capacitor that can be preferably applied include a type in which a separator is impregnated with an electrolyte. Specifically, a manganese dry battery, an alkaline manganese dry battery, a lithium ion secondary battery, a dye-sensitized solar cell, and an electric double layer A type capacitor etc. can be illustrated.

  Another embodiment of the method for producing an article having a negative pattern according to the present invention is characterized in that the electrically conductive article is produced using at least a solidifiable and flowable material having electrical conductivity after solidification. .

  The conductive particles preferably have a flat shape that can be oriented by an electric field, a magnetic field, or both. In that case, the conductive composition can be solidified in a state where the conductive particles are oriented. The solidified product of the conductive composition has anisotropy in the electrical resistance value corresponding to the direction oriented by the electric field and / or magnetic field, and forms a member having a low electrical resistance value. This is a preferred embodiment for increasing the electrical efficiency of the electronic device. Further, when the foamable substance is a flat particle and has magnetic anisotropy or dielectric anisotropy, it can be oriented by an electric field and / or a magnetic field.

  In another embodiment of the method for producing an electrode having an article having a negative pattern of the present invention formed on the surface, a solidifiable and fluid material exhibits conductivity after at least solidification, (1 ) A step of forming a positive pattern of a solid sublimable substance derived from a gas phase from the surface of the material applied to the electrode or from the surface to the inside thereof; (2) a step of solidifying the material; and (3) the sublimable substance. The removal step is performed in this order. For example, when a material having fluidity capable of solidifying and forming an active material layer of a battery is applied and formed on the surface of the current collector, an electrode having a large specific surface area can be produced by forming a negative pattern on the surface of the coating film. A battery having such an electrode improves the electrical characteristics of the battery, such as the charge / discharge rate, by increasing the surface area. In addition, a battery or a capacitor including an electrode on the surface of which an article having a negative pattern manufactured by this method is formed can be manufactured.

  A case where a porous material made of a fluid material has adhesiveness and includes an active material will be described. FIG. 6 is a schematic diagram of a battery manufacturing method, in which (a) shows a state in which a coating film of an adhesive 16, which is a fluid material containing the active material 14 and the conductive filler 15, is formed on the electrode 9. (B) is a state in which the positive pattern 4 is oriented from the surface of the film containing the active material 14 and the conductive filler 15 with the magnetic field applied or from the surface to the inside, and (c) is a solid sublimable material. The state is shown in which the positive pattern 4 is removed and an electrode in which an oriented active material, a conductive material, and a hole pattern are formed is produced.

  Here, when the battery is a lithium ion battery as the active material 14, lithium cobalt oxide, lithium manganate, lithium iron phosphate, or the like can be used for the anode, and graphite, carbon fiber, Si alloy, titanic acid can be used for the cathode. Lithium or the like can be used. In the case of a capacitor, activated carbon or the like can be used. In the case of a solar cell, titania particles adsorbed with a ruthenium dye, potassium niobate with a cationic porphyrin inserted between layers, and the like can be used. Of these active materials, materials having magnetic anisotropy and / or dielectric anisotropy are advantageous in terms of electrical characteristics by a magnetic field and / or electric field, or light absorption efficiency is improved for solar cells. Orientation and / or orientation that is advantageous in terms of electrical properties. In the case of potassium niobate in which a cationic porphyrin is inserted between layers, the magnetic anisotropy of the interlayer porphyrin can be performed in a direction in which light absorption is advantageous by utilizing the magnetic anisotropy of potassium niobate. The conductive filler 15 can be blended in any amount as necessary. In the case of a material having magnetic anisotropy and / or dielectric constant anisotropy as described above, a magnetic field and / or an electric field is used. Can be oriented in an advantageous direction in terms of electrical characteristics. On the other hand, a conductive material having no magnetic anisotropy can be magnetically oriented by using a time-varying magnetic field. As used herein, “time-varying magnetic field” means a magnetic field in which the amount of magnetic flux penetrating the conductive material changes with time. More specifically, by applying a time-varying magnetic field to the conductive material, an induced current is generated in the conductive material, and the induced current generates an induced magnetic field in a direction that cancels the change in magnetic flux. At this time, a magnetic interaction occurs between the induced magnetic field and the time-varying magnetic field, and the conductive material moves or rotates in a direction in which the change in magnetic flux is reduced. If orientation using an induced magnetic field is used, even a material having no magnetic anisotropy can be oriented as long as it has conductivity. For example, when a uniaxial rotating magnetic field is applied to rod-shaped cubic metal particles, the long axis of the rod and the axis of the rotating magnetic field are arranged in parallel. When a uniaxial rotating magnetic field is applied to the disk-shaped metal particles, the normal line of the disk and the axis of the rotating magnetic field are arranged in parallel. Such an orientation using an induced magnetic field can be used for a cubic metal having no magnetic anisotropy, and therefore has a wide range of applications, increasing the chances of selecting a material having excellent electrical characteristics.

  One or more of these active materials, conductive materials, and sublimable materials can be oriented in an electric field and / or magnetic field, and can be shaped or electrically The member can be oriented in a particularly advantageous direction to increase the efficiency of the electrode.

  Moreover, when the material having fluidity contains a foaming agent, when the battery abnormally generates heat during charging and discharging, the current can be safely interrupted at any part of the electrode by foaming. In the above-described use in which a foaming agent is blended with a material exhibiting conductivity at least after solidification, a foamable material coated with a conductive material can be preferably used. When an insulative material is mixed with a foamable material or a foamable material coated with the softening material, the electrical resistance increases and the electrical efficiency decreases. However, an increase in electrical resistance can be suppressed by coating the surface of the foamable material or the foamable material coated with the softening material with a conductive material. Specifically, it can be obtained by plating the surface of a foamable material coated with a foamable material or a softening material, or attaching conductive particles. As the conductive material, the aforementioned metals, alloys, carbon-based materials, and various inorganic materials having conductivity can be used. When the conductive material is a metal, a dense metal layer is formed on the surface of the foamable material by plating. it can. Thus, by providing conductivity, the content of the foaming substance can be increased, and the range of selection of the foaming ratio can be expanded.

  When the solid sublimable substance formed on the surface of the solidifiable and flowable material has anisotropy in dielectric constant and / or magnetic susceptibility, it can be similarly oriented by an electric field and / or a magnetic field. In this case, it is possible to provide anisotropy in the direction of the positive pattern and the negative pattern. When the negative pattern is a porous pattern, ion conduction can be caused through the porous pattern impregnated with the electrolytic solution. Therefore, the orientation of the porous pattern can be oriented in a direction in which ion conduction is likely to occur. Alternatively, an article having conductivity anisotropy in an arbitrary direction can be manufactured by plating or pouring a low melting point metal into pores of a porous pattern oriented in an arbitrary direction.

  In addition, particles with a high dielectric constant can be combined for the purpose of reducing impedance, and particles of barium titanate can be combined. Further, the particles having a high dielectric constant can be oriented using a magnetic field and / or an electric field.

  The present invention also relates to an apparatus for producing an article having a negative pattern from the surface or surface of a solidifiable and fluid material to the inside, and (1) the surface or surface of the solidifiable and fluid material from the inside. A means for forming a positive pattern of a solid sublimable substance derived from a gas phase, (2) a means for solidifying the material, and (3) a surface of the material or an interior from the surface provided with a means for removing the sublimable substance. The present invention relates to an apparatus for manufacturing an article having a negative pattern.

  The means (1) can be performed by cooling the sublimable substance to a temperature below the sublimation point. The means (2) is a means for solidifying the material to form a negative pattern from the surface of the substance having fluidity or from the surface to the inside, and curing of the material by irradiation with energy rays or heating, cooling of the material, or in the material It can be carried out by solidification by evaporation of the solvent. The means of (3) is a means for removing a sublimable substance that forms a positive pattern from a cured fluid substance, by heating the sublimable substance by heating sublimation, vacuum sublimation, or dissolving a sublimable substance. It can be carried out.

  Further, when the sublimable substance is a substance having anisotropy in dielectric constant and / or magnetic susceptibility, the device further includes means for orienting the sublimable substance in an arbitrary direction with an electric field and / or a magnetic field. By providing, the positive pattern of the sublimable substance can be oriented.

  FIG. 7 schematically shows an apparatus for continuously forming a porous film on the surface of a film substrate, and is a type in which a magnet for magnetically orienting a sublimable substance is installed. The coater 19 is used to apply a UV curable resin of a fluid material to the surface of the film substrate 18 fed from the roll 17, and then the film substrate is cooled by the cooling stage 20, whereby the surface of the UV curable resin is applied. A positive pattern of frost which is a sublimable substance is formed (means (1)). In the meantime, the frost formed by continuing to apply the magnetic field with the magnet 21 is magnetically oriented, and in that state, UV is irradiated by the UV irradiator 22 to solidify the UV curable resin (means (2)), and then with the dryer 23. The attached frost is evaporated and removed (means (3)). Thus, the film 24 having a film-like negative pattern can be formed continuously. In addition, although this apparatus can be comprised as one body as mentioned above, it can also be comprised so that each means may be isolate | separated and performed with multiple bodies.

  Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. The amount added is in parts by weight unless otherwise noted.

  In Example 1, an article having a negative pattern was manufactured from the surface of the energy ray-curable resin or from the surface to the inside using a positive pattern of a sublimable substance.

Photo-curing acrylic resin manufactured by Kyoritsu Chemical Industry Co., Ltd. (Product name: World Lock No. XFL-06L; 1% or more of resin that cannot dissolve water) is applied to a glass plate with a thickness of 50 μm in a freezer. After cooling to −40 ° C. and then standing in an atmosphere of 25 ° C. and 80% humidity for 30 seconds, ultraviolet rays were irradiated at 3000 mJ / cm ² to obtain a film-like cured product (step (2)). The cured product was dried to remove frost (step (3)).

(Pattern observation)
FIG. 8 is a scanning electron micrograph, and it was confirmed that a large number of holes were opened inside the cured product as shown in (a). When the film-like cured product was peeled off from the glass plate and the back surface was similarly observed with a scanning electron microscope, it was confirmed that the negative pattern reached the back surface as shown in (b). When the cross section of the cured resin film was observed, it was confirmed that the negative pattern was a porous pattern as shown in (c). The porosity is about 30%.

  In Example 2, a magnetic field was further applied under the pattern production conditions of Example 1 to produce an article in which the negative pattern was oriented.

A photocurable acrylic resin (product name: World Rock No. XFL-06L) manufactured by Kyoritsu Chemical Sangyo Co., Ltd. coated on a glass plate with a thickness of 50 μm is cooled to −40 ° C. in a freezer, and then 14.09T (Tesla) While applying the magnetic field, the sample was allowed to stand in an atmosphere of 25 ° C. and 80% humidity for 60 seconds to orient the frost from the surface or from the surface to the inside. In this state, ultraviolet rays were irradiated at 3000 mJ / cm ² to obtain a cured product (step (2)). The cured product was dried to remove frost (step (3)).

(Pattern observation)
FIG. 9 shows a scanning electron microscope, and it was confirmed that a large number of holes were opened in the cured product as shown in (a). When the cured resin film was peeled off from the glass plate and the back surface was similarly observed with a scanning electron microscope, it was confirmed that the negative pattern reached the back surface as shown in (b). When the cross section of the cured resin film was observed, it was confirmed that the negative pattern was a porous pattern as shown in (c). The porosity is about 50%.

(Manufacture of Li-ion battery components)
In Example 3, a separator was manufactured on a Li ion battery electrode by using an electrode manufacturing method.

(Manufacture of electrodes)
Dainippon Ink & Chemicals, Inc. bisphenol A epoxy resin (product name: Epicron 850) 5 parts, Daicel Chemical Industries, Ltd. alicyclic epoxy resin (product name: Celoxide 2021P), Sanshin Chemical Industry Co., Ltd. 0.2 parts of photothermal cation initiator (product name: Sun-Aid SI-100L), 0.2 part of epoxy-modified silane coupling agent (product name: KBM-403) manufactured by Shin-Etsu Chemical Co., Ltd., manufactured by Denki Kagaku Kogyo Co., Ltd. Put 5 parts of carbon black (product name: Denka Black), 80 parts of lithium cobaltate powder and 500 parts of NMP into a planetary mixer with a cooling jacket, and stir until a uniform liquid is formed to prepare a coating liquid for forming the anode active material. did. This was applied to an aluminum current collector having a thickness of 30 μm and dried at 50 ° C. for 1 hour while applying a 2 T magnetic field from the surface normal direction of the aluminum current collector. Thereafter, the application of the magnetic field was stopped and 130 ° C. × 1 An anode was produced by heat curing for a period of time.
Dainippon Ink & Chemicals, Inc. bisphenol A epoxy resin (product name: Epicron 850) 5 parts, Daicel Chemical Industries, Ltd. alicyclic epoxy resin (product name: Celoxide 2021P), Sanshin Chemical Industry Co., Ltd. 0.2 parts of photothermal cation initiator (product name: Sun-Aid SI-100L), 0.2 part of epoxy-modified silane coupling agent (product name: KBM-403) manufactured by Shin-Etsu Chemical Co., Ltd., graphite manufactured by Nippon Graphite Co., Ltd. 10 parts of powder and 500 parts of NMP were put into a planetary mixer with a cooling jacket, and stirred until a uniform liquid was formed to prepare a coating liquid for forming an active material for the cathode. This is applied to a copper current collector with a thickness of 50 μm, and dried at 50 ° C. for 1 hour while applying a 2T rotating magnetic field so that the rotation axis of the magnetic field and the surface of the copper current collector are parallel to each other. Was removed and heated at 130 ° C. for 1 hour to produce a cathode.

(Formation of porous film)
50 parts of foamable material (product name: EXPANCEL 920DU40) manufactured by Nippon Philite Co., Ltd., 50 parts of photocurable adhesive (product name: World Rock No. XFL-06L) manufactured by Kyoritsu Chemical Industry Co., Ltd. and diethyl ether The liquid which mixed 100 parts was coated by thickness of 5 micrometers, and it cooled to -40 degreeC (process (1)). This was left to stand in an atmosphere of 25 ° C. and 80% humidity for 60 seconds while applying a magnetic field of 14.09 T from the surface normal direction of the electrode to orient the frost, and then cured by UV irradiation at 6000 mJ / cm ² as it was. (Step (2)). The application of the magnetic field was stopped, and the cured product was dried to remove frost (step (3)).

(Battery assembly)
A battery was assembled by impregnating a dimethyl carbonate solution containing 5% lithium hexafluorophosphate into an anode and a cathode coated with a cured product having a porous pattern, and then bonding the cathode and the anode together.

(Charge / discharge test)
As a result of the charge / discharge test, no short circuit occurred between the cathode and the anode, and charge / discharge could be performed through the produced porous film.

(High temperature overheating test)
Assuming thermal runaway of the battery, when the cell produced by the above method was heated at 150 ° C. for 1 minute, the foaming agent swelled and charging / discharging did not occur.

  As described above, a pattern can be easily formed by using the pattern forming method using the sublimable substance of the present invention. According to the present invention, a porous pattern penetrating a fluid material can also be formed, so that it can be used as a battery or capacitor separator. Furthermore, it can be used as a safety device against abnormal heat generation of the battery by blending a foaming substance.

(A) is a figure which shows the state which installed the board | substrate with which the coating film consisting of the material which can be solidified and fluidized was installed in the vaporized sublimable substance atmosphere, (b) is a solid sublimable substance. It is a figure which shows the state formed from the surface or the surface to the inside of the coating film which consists of a fluid material which can be solidified, and (c) after sublimating a substance is solidified after solidifying the fluid material It is a figure which shows the state from which the article | item in which the negative pattern was formed was obtained. (A) is a figure which shows the state which installed the board | substrate with which the coating film consisting of the material which can be solidified and fluidized in the vaporized sublimable substance atmosphere was installed, (b) is a solid sublimable substance. It is a figure which shows the state which formed from the surface or the surface to the inside of the coating film which consists of a fluid material which can be solidified, and reached the inside, and also the positive pattern reached the back surface of the coating film, (c) It is a figure which shows the state from which the sublimable substance which penetrated the coating film was removed after solidifying the material with the property, and the article which formed the negative pattern which penetrated the coating film was obtained. (A) is a figure which shows the state formed from the surface or surface to the inside of the coating film which consists of a solid material and the fluidity | liquidity which can solidify the positive pattern of a solid sublimable substance, (b) is an electric field and / or Or it is a figure which shows the state which orientated the positive pattern of the solid sublimable substance formed from the surface of the material which has fluidity by a magnetic field, or the inside from the surface to the inside, (c) is according to the positive pattern of the oriented sublimable substance It is a figure which shows the state which formed the negative pattern. (A) is a figure which shows the state which coated the electrode surface with the coating film which consists of a material which can be solidified and has fluidity, (b) is a solid sublimable substance on the surface of the coating film which covered the electrode surface. (C) is a figure which shows the state which coat | covered the electrode surface entirely with the porous material manufactured by this invention. (A) is a figure which shows the state which manufactured the separator containing a foamable material with the method of this invention, (b) shows the state which the distance between electrodes spread because foamable material foamed. FIG. (A) is a figure which shows the state which formed the coating film of the adhesive agent which is an active material and an electroconductive material, and is a solidified and fluid material on a collector, (b) is an electric field And / or shows a state in which the positive pattern 4 of the solid sublimation substance is oriented from the surface of the coating film containing the active material and the conductive material or the surface to the inside, which is oriented by a magnetic field, and (c) is an orientation It is a figure which shows the electrode in which the pattern of the active material and electroconductive material which were made and the hole was formed. It is the figure which showed typically the manufacturing apparatus of the articles | goods which have a negative pattern. (A) is a scanning electron micrograph of the surface of an article having a porous pattern manufactured by the method of the present invention, and (b) is a back surface of the article having a porous pattern manufactured by the method of the present invention. It is a scanning electron micrograph, (c) is a scanning electron micrograph of the cross section of the article | item which has the porous pattern manufactured with the method of this invention. (A) is a scanning electron micrograph of the surface of an article having a porous pattern manufactured by orienting a sublimable substance by applying a magnetic field, and (b) is a sublimation substance applied by applying a magnetic field. It is a scanning electron micrograph of the back surface of an article having a porous pattern produced by orientation, (c) is a cross-sectional view of an article having a porous pattern produced by orienting a sublimable substance by applying a magnetic field. It is a scanning electron micrograph.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Sublimable substance atmosphere 2 Solidifiable and fluid material 3 Substrate 4 Positive pattern of solid sublimable substance 5 Negative pattern 6 Direction of application of electric field and / or magnetic field 7 Sublimable substance oriented by electric field and / or magnetic field 8 Negative pattern oriented in the direction corresponding to the applied electric field and / or magnetic field 9 Electrode 10 Porous hole in porous pattern 11 Foamable material 12 Ion 13 Foamed material after foaming 14 Active material 15 Conductive filler 16 Adhesive 17 Roll 18 Film substrate 19 Coater 20 Cooling stage 21 Magnet 22 UV irradiator 23 Dryer 24 Film having negative pattern

Claims (8)

  (1) forming a positive pattern of a solid sublimable substance derived from a gas phase from the surface of the solidifiable and fluid material or from the surface to the inside; (2) solidifying the material; and (3) the sublimation. The method of manufacturing the articles | goods which have a negative pattern from the surface of the said material or the inside to the inside, performing the process of removing a sexual substance in this order.   The sublimable substance is a substance having anisotropy in dielectric constant and / or magnetic susceptibility, and at least before the material is solidified, the sublimable substance is further oriented in an arbitrary direction by an electric field and / or a magnetic field. The method of claim 1, comprising a step.   3. A method according to claim 1 or 2, characterized in that the material contains a foamable substance that foams at any temperature and the resulting article foams at any temperature.   The method according to claim 1, wherein the negative pattern is a pattern in which the volume fraction of the pores from the surface to the inside of the material is continuously changed.   (1) a step of forming a positive pattern of a solid sublimable substance derived from a gas phase from the surface of the solidifiable and fluid material applied to the electrode or from the surface to the inside; (2) a step of solidifying the material; (3) A method for producing an electrode in which an article having a negative pattern is formed on the surface of the material or from the surface to the inside, wherein the step of removing the sublimable substance is performed in this order.   (1) means for forming a positive pattern of a solid sublimable substance derived from a gas phase from the surface of the solidifiable and fluid material or from the surface to the inside thereof; (2) means for solidifying the material; and (3) the sublimation. Of an article having a negative pattern from the surface of the material or from the surface to the inside thereof, further comprising means for removing the active substance, and optionally further comprising means for orienting the sublimable substance in an arbitrary direction with an electric field and / or magnetic field. Manufacturing equipment.   The battery or capacitor using the articles | goods which have the pattern manufactured by the method of any one of Claims 1-4.   A battery or capacitor comprising an electrode produced by the method according to claim 5.