WO2015080155A1 - Photocurable inkjet ink - Google Patents
Photocurable inkjet ink Download PDFInfo
- Publication number
- WO2015080155A1 WO2015080155A1 PCT/JP2014/081252 JP2014081252W WO2015080155A1 WO 2015080155 A1 WO2015080155 A1 WO 2015080155A1 JP 2014081252 W JP2014081252 W JP 2014081252W WO 2015080155 A1 WO2015080155 A1 WO 2015080155A1
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- WIPO (PCT)
- Prior art keywords
- ink composition
- cured film
- compound
- meth
- weight
- Prior art date
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- 0 *C(C(N1C*N(C(C=C2*)=O)C2=O)=O)=CC1=O Chemical compound *C(C(N1C*N(C(C=C2*)=O)C2=O)=O)=CC1=O 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/42—Acrylic resins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
- H01B3/447—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from acrylic compounds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a photocurable inkjet ink (also simply referred to as “ink composition” in the present invention) that is suitably used for an insulating part of a secondary battery such as a lithium ion storage battery or an insulating part of an electronic component. More specifically, the present invention relates to the production of a secondary battery having a current collector coated with a positive electrode active material, a current collector coated with a negative electrode active material, and a separator, and an electromagnetic shielding case and an electromagnetic shielding material. It relates to a suitable ink composition.
- some secondary batteries have a structure in which a spiral wound electrode group is housed in a rectangular or cylindrical battery case, but there is a limit to reducing the thickness. Therefore, batteries using a folded structure or a laminated structure instead of a wound body are also manufactured.
- a battery having a structure in which a laminated electrode group is sealed with an aluminum laminate is very effective in terms of weight reduction.
- a gap or wrinkle occurs in the laminated body electrode group due to the pressure during lamination, there is a possibility of causing a short circuit or a function deterioration.
- Even for an exterior other than an aluminum laminate it is necessary to prevent the laminate electrode group from being displaced or uneven in thickness due to long-term use.
- an insulating resin film can be efficiently produced by applying and curing an ink composition on a metal substrate such as a metal current collector.
- a metal substrate such as a metal current collector.
- the conventional photo-curable composition that can be applied by the ink-jet printing method cannot achieve both electrolytic solution resistance and adhesion to a metal current collector.
- an object of the present invention is to provide an insulating resin film having resistance to an electrolytic solution and adhesion to a metal current collector by inkjet printing on a metal current collector of a secondary battery and photocuring.
- An ink composition that can form an ink, and ink-jet printing on a metal substrate of an electromagnetic shielding material and photocuring to form an insulating resin film having resistance to a cleaning agent and adhesion to a metal substrate.
- An object of the present invention is to provide an ink composition that can be used.
- the present inventors have (meth) acrylate monomer (A) having a phosphate ester and having 1 to 3 acryloyl groups in one molecule and — (CH 2 —CH 2 —O) n — (n> 3)
- An ink composition comprising a reactive compound (B) other than (A) having no structure, and at least one selected from a benzyl ketal compound and an ⁇ -hydroxyacetophenone compound as a photopolymerization initiator (C).
- a photocurable composition in which the addition amount of the (meth) acrylate monomer (A) having a phosphate ester group is 0.01 to 5.5 parts by weight with respect to 100 parts by weight of the total amount of the reactive compound (B).
- the material is highly resistant to the electrolyte used in the secondary battery, has high adhesion to a metal current collector such as aluminum, and is useful as an insulating resin for use in the secondary battery. It has high resistance to cleaning agents used when washing lubricants used in press molding and high adhesion to metal substrates, and is useful as an insulating resin that can be formed by printing on a metal base material for electromagnetic shielding materials. Based on this finding, the present invention has been completed. That is, the present invention includes the following items.
- (meth) acrylate monomer (A) which is at least one selected from compounds having a phosphate ester represented by general formulas (1-1) and (1-2), and 1 to 3 per molecule
- C) An (meth) acrylate monomer having a phosphate ester with respect to 100 parts by weight of the total amount of the reactive compound (B), the ink composition comprising at least one selected from benzyl ketal compounds and ⁇ -hydroxyacetophenone compounds
- each R 1 is independently hydrogen or methyl).
- the trifunctional (meth) acrylate compound is 0 to 80% by weight
- the bifunctional (meth) acrylate compound is 10 to 100
- the photocurable ink-jet ink according to [1] containing 1% by weight and 0 to 60% by weight of a monofunctional (meth) acrylate compound.
- the reactive compound (B) is trimethylolpropane triacrylate, pentaerythritol triacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, neopentyl glycol diacrylate, tricyclodecane dimethanol diacrylate, Dipropylene glycol diacrylate, tripropylene glycol diacrylate, propoxylated (2) neopentyl glycol diacrylate, bisphenol F EO-modified diacrylate, neopentyl glycol hydroxypivalate ester diacrylate, dioxane glycol diacrylate, 1,3- Butylene glycol diacrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate and benzyl meta It is at least one selected from the relations, the light-curable inkjet ink according to [1] or [2].
- the photopolymerization initiator (C) contains 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl- At least one selected from 1-phenyl-1-propanone and 2-hydroxy-1- ⁇ 4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl ⁇ -2-methyl-1-propanone
- the photocurable inkjet ink according to any one of [1] to [3].
- an insulating film having high adhesion to metal can be formed by a printing method, and particularly when a secondary battery is manufactured, an electrolyte-resistant material is formed on a metal current collector.
- a high insulating film can be formed.
- an insulating film having high resistance to the cleaning agent can be formed on the metal substrate of the electromagnetic wave shielding material.
- the photocurable inkjet ink of the present invention is a (meth) acrylate monomer (A) that is at least one selected from compounds having a phosphate ester represented by general formulas (1-1) and (1-2).
- the ink composition has an addition amount of the (meth) acrylate monomer (A) having a phosphate ester of 0.01 to 5.5 parts by weight with respect to 100 parts by weight of the total amount of B).
- each R 1 is independently hydrogen or methyl.
- the ink composition of the present invention may be colorless or colored.
- (meth) acrylate is used to indicate both or one of acrylate and methacrylate.
- the “(meth) acryloyl group” is used to indicate both or one of an acryloyl group and a methacryloyl group.
- the ink composition of the present invention may contain a polymerization inhibitor, a photopolymerizable compound other than the (meth) acrylate monomer (A) having a phosphate ester, a thermosetting compound, and the like.
- the (meth) acrylate monomer (A) having a phosphate ester of the present invention is at least one selected from compounds having a phosphate ester represented by formula (1-1) or (1-2).
- a compound having a phosphate ester represented by the general formulas (1-1) and (1-2) may be used in combination.
- each R 1 is independently hydrogen or methyl.
- the (meth) acrylate monomer (A) having a phosphate ester may be a synthetic product or a commercially available product.
- Examples of commercially available products include light ester P-1M, light ester P-2M, and light acrylate P-1A (all trade names: Kyoeisha) Chemical Co., Ltd.) and EBECRYL168 (trade name; Daicel Ornex Co., Ltd.).
- the content of the (meth) acrylate monomer (A) having a phosphate ester in the ink composition of the present invention is 0.01 to 5.5 parts by weight with respect to 100 parts by weight of the total amount of the reactive compound (B).
- the cured film formed from the ink composition of the present invention is preferable because it has high electrolytic solution resistance and high adhesion to a metal current collector, and high cleaning agent resistance and high adhesion to a metal substrate.
- the amount is from 01 to 3.5 parts by weight, more preferably from 0.01 to 2.5 parts by weight.
- the reactive compound (B) other than the (meth) acrylate monomer (A) having a phosphate ester according to the present invention includes a metal current collector and the like when the number of acryloyl groups in one molecule is 1 to 3 High adhesion to metal substrates, and resistance to battery electrolytes such as alkylene carbonates and cleaning agents such as hydrochlorofluorocarbons without the — (CH 2 —CH 2 —O) n — (n> 3) structure It is preferable because it is high.
- the reactive compound (B) of the present invention comprises a trifunctional (meth) acrylate compound 0 to 80% by weight, a bifunctional (meth) acrylate compound 10 to 100% by weight, a monofunctional (B)
- the meth) acrylate compound is contained in an amount of 0 to 60% by weight, it is preferable as an insulating film for an electromagnetic wave shielding material because the cured film has high cleaning agent resistance and high adhesion to a metal substrate.
- the cured film is preferable as an insulating film for a battery because it has high resistance to electrolyte and high adhesion to a metal current collector.
- reactive compound (B) of the present invention examples include trimethylolpropane triacrylate, pentaerythritol triacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, neopentyl glycol diacrylate, tricyclodecane dimethanol.
- the ink composition of the present invention contains a photopolymerization initiator (C).
- the photopolymerization initiator (C) is preferably a compound capable of generating radicals upon irradiation with ultraviolet rays or visible rays. Further, a benzyl ketal compound or an ⁇ -hydroxyacetophenone compound is photocured and cured. It is preferable from the viewpoint that the adhesion of the film to the metal substrate including the metal current collector, the electrolyte solution resistance, and the detergent resistance can be compatible.
- benzyl ketal compound examples include 2,2-dimethoxy-2-phenylacetophenone and 2,2-diethoxy-2-phenylacetophenone.
- ⁇ -hydroxyacetophenone compound examples include 1 -Hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2-hydroxy-1- ⁇ 4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl ⁇ -2-Methyl-1-propanone.
- the photopolymerization initiator (C) may be one type or a mixture of two or more types.
- the content of the photopolymerization initiator (C) is 3 to 20% by weight with respect to the total weight of the ink composition, the photocuring property against ultraviolet rays is excellent, and the metal foil of the resulting cured film is used. It is preferable because of its high adhesion to the metal substrate, more preferably 5 to 15% by weight, still more preferably 7 to 15% by weight.
- the ink composition of the present invention may contain a polymerization inhibitor in order to improve storage stability.
- a polymerization inhibitor include 4-methoxyphenol, hydroquinone, hindered amine, and phenothiazine.
- the polymerization inhibitor used in the ink composition of the present invention may be one type or a mixture of two or more types.
- the content of the polymerization inhibitor is 0.01 to 1% by weight based on the total weight of the ink composition because the increase in viscosity is small even during long-term storage, taking into account the balance with photocurability. Then, it is more preferably 0.01 to 0.5% by weight, and still more preferably 0.01 to 0.2% by weight.
- the ink composition of the present invention may contain a thermosetting compound.
- the thermosetting compound is not particularly limited as long as it is a compound having a functional group capable of thermosetting, and bismaleimide, a phenol resin, a resin containing a phenolic hydroxyl group, a melamine resin, an epoxy compound. Etc.
- the thermosetting compound used in the ink composition of the present invention may be one type or a mixture of two or more types.
- thermosetting compound Curing obtained when the content of the thermosetting compound is 2 to 50 parts by weight with respect to 100 parts by weight of the total amount of the reactive compound (B) other than the (meth) acrylate monomer (A) having a phosphate ester It is preferable because the heat resistance of the film is improved, more preferably 5 to 30 parts by weight, still more preferably 10 to 20 parts by weight.
- bismaleimide examples include compounds represented by the following general formula (1).
- the bismaleimide represented by the following general formula (1) is a compound obtained by reacting, for example, a diamine and maleic anhydride.
- R 10 and R 12 are each independently hydrogen or methyl, and R 11 is a divalent group represented by the following general formula (2).
- R 13 and R 14 each independently represents an alkylene having 1 to 18 carbon atoms in which arbitrary non-continuous methylene may be replaced by oxygen, or an aromatic ring that may have a substituent. It is a cycloalkylene which may have a valent group or a substituent. Examples of the substituent in the aromatic ring and cycloalkylene include carboxyl, hydroxyl, alkyl having 1 to 5 carbons, and alkoxy having 1 to 5 carbons. Because it has a high heat resistance resulting cured film, it is preferable R 13 and R 14 is a divalent group represented by independently following either equation.
- X is a divalent group represented by any of the following formulas.
- the bismaleimide may be one kind or a mixture of two or more kinds. [1.5.2 Phenol resin or resin containing a phenolic hydroxyl group]
- phenol resin a novolak resin obtained by a condensation reaction between an aromatic compound having a phenolic hydroxyl group and an aldehyde is preferably used.
- resin containing a phenolic hydroxyl group a vinylphenol homopolymer (hydrogenated product) is used.
- vinylphenol copolymers (including hydrogenated products) of vinylphenol and a compound copolymerizable therewith are preferably used.
- aromatic compounds having a phenolic hydroxyl group include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol.
- P-butylphenol o-xylenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3, 4,5-trimethylphenol, p-phenylphenol, resorcinol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, bisphenol A, bisphenol F, diphenol containing terpene skeleton, gallic acid, gallic ester, ⁇ -naphthol and ⁇ -naphth Thor.
- aldehydes include formaldehyde, paraformaldehyde, furfural, benzaldehyde, nitrobenzaldehyde and acetaldehyde.
- the compound copolymerizable with vinylphenol include (meth) acrylic acid or a derivative thereof, styrene or a derivative thereof, maleic anhydride, vinyl acetate, and acrylonitrile.
- phenolic resins include Resitop PSM-6200 (trade name; Gunei Chemical Co., Ltd.), Shonor BRG-555 (trade name; Showa Denko Co., Ltd.), and resins containing phenolic hydroxyl groups.
- Resitop PSM-6200 trade name; Gunei Chemical Co., Ltd.
- Shonor BRG-555 trade name; Showa Denko Co., Ltd.
- resins containing phenolic hydroxyl groups resins containing phenolic hydroxyl groups.
- Specific examples include Marca Linker M S-2G, Marca Linker CST70, and Marca Linker PHM-C (all trade names: Maruzen Petrochemical Co., Ltd.). *
- the phenol resin used in the ink composition of the present invention or the resin containing a phenolic hydroxyl group may be a single compound or a mixture of two or more compounds.
- the melamine resin is not particularly limited as long as it is a resin produced by polycondensation of melamine and formaldehyde, and examples thereof include methylol melamine, etherified methylol melamine, benzoguanamine, methylol benzoguanamine, etherified methylol benzoguanamine, and condensates thereof. It is done. Among these, etherified methylol melamine is preferable in that the resulting cured film has good chemical resistance.
- melamine resin examples include Nicalac MW-30, MW-30HM, MW-390, MW-100LM, and MX-750LM (all trade names: Sanwa Chemical Co., Ltd.).
- the melamine resin may be one type or a mixture of two or more types.
- the ink composition of the present invention may contain an epoxy compound in order to improve the strength of the obtained cured film or the like.
- the epoxy compound is not particularly limited as long as it has at least one structure represented by the following formula (3-1) or formula (3-2) in one molecule.
- the epoxy compound examples include novolak type (phenol novolak type and cresol novolak type), bisphenol A type, bisphenol F type, trisphenol methane type, hydrogenated bisphenol A type, hydrogenated bisphenol F type, bisphenol S type, and tetrapheny.
- an epoxy resin produced by a known method may be used, or a commercially available product may be used.
- Examples of commercially available products are jER828, 834, 1001, and 1004 (all trade names: manufactured by Mitsubishi Chemical Corporation), Epicron 840, 850, 1050, 1050, and 2055 (all trade names: DIC). Epototo YD-011, YD-013, YD-127, YD-128 (all trade names: Nippon Steel Chemical Co., Ltd.), D.E.R.
- the epoxy resin that can be used in the ink composition of the present invention may be a single compound or a mixture of two or more compounds.
- Viscosity of ink composition of the present invention When the ink composition of the present invention has a viscosity at 25 ° C. of 1 to 50 mPa ⁇ s measured with an E-type viscometer, the ink composition of the present invention has good ejection properties when applied by an ink jet method. .
- the viscosity of the ink of the present invention at 25 ° C. is more preferably 2 to 40 mPa ⁇ s, and further preferably 4 to 30 mPa ⁇ s.
- the ink composition of the present invention can be prepared by mixing each component as a raw material by a known method.
- the ink composition of the present invention includes the components (A) to (C) and, if necessary, a surfactant, an ultraviolet absorber, an antioxidant, a polymerization inhibitor, a thermally reactive compound, a thermal polymerization initiator, and the like. It is preferable to prepare by mixing and degassing the obtained solution using a membrane filter made of, for example, ultra high molecular weight polyethylene (UPE).
- UPE ultra high molecular weight polyethylene
- the ink composition of the present invention can be applied using a known ink jet method.
- the ink jet method include a piezo method in which mechanical energy is applied to ink to eject the ink from the ink jet head, and a thermal method in which thermal energy is applied to the ink to eject ink.
- a coating device used when coating with the ink composition of the present invention for example, energy corresponding to a coating signal is applied to an ink composition in an ink jet head having an ink storage portion in which the ink composition is stored. And an apparatus that performs coating (drawing) corresponding to the coating signal while generating ink droplets by the energy.
- the ink jet coating apparatus is not limited to one in which the ink jet head and the ink container are separated, and may be one in which they are inseparably integrated.
- the ink storage unit may be integrated with the ink jet head so as to be separable or non-separable and mounted on the carriage, or may be provided at a fixed portion of the apparatus.
- the ink composition may be supplied to the inkjet head via an ink supply member, for example, a tube.
- the ink jet head may be heated, and the heating temperature is preferably 80 ° C. or less, and more preferably 50 ° C. or less.
- the viscosity of the ink composition of the present invention at the heating temperature is preferably 1.0 to 30 mPa ⁇ s.
- the film obtained from the ink composition of the present invention (also simply referred to as “cured film” in the present invention) is obtained by applying the above-described ink composition of the present invention to the substrate surface by an inkjet method, and then applying ultraviolet rays, visible light, etc. It is obtained by irradiating and curing the light.
- the amount of light to be irradiated (exposure amount) when irradiating ultraviolet rays, visible rays, or the like depends on the ink composition, but the integrated light meter UIT-201 equipped with a photoreceiver UVD-365PD manufactured by USHIO INC. 100 to 5,000 mJ / cm 2 is preferable, 300 to 4,000 mJ / cm 2 is more preferable, and 500 to 3,000 mJ / cm 2 is more preferable. Further, the wavelength of ultraviolet rays or visible rays to be irradiated is preferably 200 to 500 nm, and more preferably 250 to 450 nm.
- the exposure amount described below is a value measured by an integrated light meter UIT-201 equipped with a photoreceiver UVD-365PD manufactured by USHIO INC.
- the exposure apparatus is not particularly limited as long as it is equipped with an electrodeless lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a halogen lamp, etc., and irradiates ultraviolet rays, visible rays, etc. in the range of 200 to 500 nm. . *
- the metal substrate including the metal current collector to which the ink composition of the present invention is applied is not particularly limited as long as it can be an object to which the ink composition is applied, and the shape is not limited to a flat plate shape. It may be curved.
- the material of the metal substrate including the metal current collector is not particularly limited, and examples thereof include aluminum, copper, nickel, and stainless steel. *
- the thickness of the metal substrate including the metal current collector is not particularly limited, but if it is 50 ⁇ m or less, printing can be performed while winding it with a roll, which is preferable because it is efficient. *
- the roll after winding is used for the purpose of completely winding the unreacted ink composition by winding it through an exposure process after printing. You may heat. *
- an insulating film can be produced on the current collector and electromagnetic wave shielding material used in the secondary battery using the cured film of the present invention.
- reaction raw materials used in Examples and Comparative Examples are indicated by abbreviations. This abbreviation is used in the following description.
- EB168 (EBECRYL168, trade name: manufactured by Daicel Ornex Co., Ltd.): Mixture of 2-methacryloxyethyl acid phosphate
- DPGDA Dipropylene glycol diacrylate
- NPDA Neopentyl glycol diacrylate
- HPNDA Neopentyl glycol hydroxypivalate ester
- Diacrylate SR9003 (trade name: manufactured by Sartomer): propoxylation (2) neopentyl glycol diacrylate
- TPGDA tripropylene glycol diacrylate 701A (NK ester 701A, trade name: manufactured by Shin-Nakamura Chemical Co., Ltd.): 2- Hydroxy-3-acryloyloxypropyl methacrylate 1,3-BGDA: 1,3-butylene glycol diacrylate FA-513AS (funcryl FA-51 AS, trade name: manufactured by Hitachi Chemical Co., Ltd.): dicyclopentanyl acrylate IBXA: isobornyl acryl
- Example 1 As the acrylate monomer (A), EB168, DPGDA as the compound (B), Irg1173 as the photopolymerization initiator (C), PF656 as the surfactant (D) are mixed in the following composition ratio, and manufactured by UPE The membrane filter (0.2 ⁇ m) was used to obtain a filtrate (ink composition 1).
- A EB168 0.25g
- B 4.75 g of DPGDA
- C Irg1173
- D PF656 0.001g
- an aluminum current collector (20 ⁇ m thick aluminum foil manufactured by Hosen Co., Ltd.) cut into a 6 cm square was prepared.
- Ink composition 1 is injected into an ink jet apparatus (ULVAC ID-225) equipped with KM512MH (14 pL) manufactured by Konica Minolta IJ Co., Ltd. as an ink jet head, and discharge voltage is 13 V, head temperature is 30 ° C., drive frequency is 5 kHz, and coating Under a discharge condition of once, the printing resolution was set to 841 dpi, and coating was performed in the range of 5 cm square on the prepared substrate.
- the ink composition is obtained.
- An aluminum foil on which a cured film of product 1 was formed was obtained. The following measurements and evaluations were performed using the aluminum foil on which the cured film was formed.
- Measurement of film thickness Measurement was performed using a Digimatic Micrometer (manufactured by Mitutoyo Corporation). It was 13 micrometers when the thickness of the aluminum foil in which the cured film similarly measured was not formed from the thickness of the aluminum foil in which the cured film of the ink composition 1 was formed was subtracted. The average value of three measurements was used as the film thickness value.
- Example 2 As shown below, an ink composition 2 was prepared in the same manner as in Example 1 except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
- the viscosity of the ink composition 2 was 10.0 mPa ⁇ s.
- a cured film was formed using the ink composition 2 under the same conditions as in Example 1, a cured film having a thickness of 12 ⁇ m was obtained. The cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
- Example 3 As shown below, an ink composition 3 was prepared in the same manner as in Example 1 except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
- the viscosity of the ink composition 3 was 9.7 mPa ⁇ s.
- a cured film was formed using this ink composition 3 under the same conditions as in Example 1, a cured film having a thickness of 12 ⁇ m was obtained.
- the cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
- Example 4 As shown below, an ink composition 4 was prepared in the same manner as in Example 1, except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
- the viscosity of the ink composition 4 was 9.4 mPa ⁇ s.
- a cured film was formed using this ink composition 4 under the same conditions as in Example 1, a cured film having a thickness of 12 ⁇ m was obtained. The cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
- Example 5 As shown below, an ink composition 5 was prepared in the same manner as in Example 1 except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
- the viscosity of the ink composition 5 was 12.2 mPa ⁇ s.
- a cured film was formed using this ink composition 5 under the same conditions as in Example 1, a cured film having a thickness of 12 ⁇ m was obtained. The cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
- Example 6 As shown below, an ink composition 6 was prepared in the same manner as in Example 1 except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
- the viscosity of the ink composition 6 was 15.5 mPa ⁇ s.
- a cured film was formed using this ink composition 6 under the same conditions as in Example 1 except that the head temperature was set to 35 ° C., a cured film having a thickness of 13 ⁇ m was obtained.
- the cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
- Example 7 As shown below, an ink composition 7 was prepared in the same manner as in Example 1 except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
- the viscosity of the ink composition 7 was 12.0 mPa ⁇ s.
- a cured film was formed using this ink composition 7 under the same conditions as in Example 1, a cured film having a thickness of 12 ⁇ m was obtained.
- the cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
- Example 8 As shown below, an ink composition 8 was prepared in the same manner as in Example 1 except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
- the viscosity of the ink composition 8 was 6.7 mPa ⁇ s.
- a cured film was formed under the same conditions as in Example 1 except that the discharge voltage was set to 11 V. As a result, a cured film having a thickness of 12 ⁇ m was obtained. The cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
- Example 9 As shown below, an ink composition 9 was prepared in the same manner as in Example 1 except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
- the viscosity of the ink composition 9 was 21.6 mPa ⁇ s.
- a cured film was formed using this ink composition 9 under the same conditions as in Example 1 except that the head temperature was set to 40 ° C., a cured film having a thickness of 15 ⁇ m was obtained.
- the cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
- Example 10 As shown below, an ink composition 10 was prepared in the same manner as in Example 1 except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
- the viscosity of the ink composition 10 was 16.6 mPa ⁇ s.
- a cured film was formed using this ink composition 10 under the same conditions as in Example 1 except that the head temperature was set to 35 ° C., a cured film having a thickness of 14 ⁇ m was obtained.
- the cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
- Example 11 As shown below, an ink composition 11 was prepared in the same manner as in Example 1 except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
- the viscosity of the ink composition 11 was 14.8 mPa ⁇ s.
- a cured film was formed using this ink composition 11 under the same conditions as in Example 1 except that the head temperature was set to 35 ° C., a cured film having a thickness of 13 ⁇ m was obtained.
- the cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
- Example 12 As shown below, an ink composition 12 was prepared in the same manner as in Example 1 except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
- the viscosity of the ink composition 12 was 42.1 mPa ⁇ s.
- a cured film was formed under the same conditions as in Example 1 except that the head temperature was set to 50 ° C., and a cured film having a thickness of 15 ⁇ m was obtained. The cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
- Example 13 As shown below, an ink composition 13 was prepared in the same manner as in Example 1 except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
- the viscosity of the ink composition 13 was 6.7 mPa ⁇ s.
- a cured film was formed under the same conditions as in Example 1 except that the discharge voltage was set to 11 V. As a result, a cured film having a thickness of 13 ⁇ m was obtained.
- the cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
- Example 14 As shown below, an ink composition 14 was prepared in the same manner as in Example 1 except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
- the viscosity of the ink composition 14 was 9.8 mPa ⁇ s.
- a cured film was formed using this ink composition 14 under the same conditions as in Example 1, a cured film having a thickness of 13 ⁇ m was obtained.
- the cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
- Example 15 As shown below, an ink composition 15 was prepared in the same manner as in Example 1 except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
- the viscosity of the ink composition 15 was 9.0 mPa ⁇ s.
- a cured film was formed using this ink composition 15 under the same conditions as in Example 1, a cured film having a thickness of 13 ⁇ m was obtained.
- the cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
- Example 16 As shown below, an ink composition 16 was prepared in the same manner as in Example 1 except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
- the viscosity of the ink composition 16 was 6.8 mPa ⁇ s.
- a cured film was formed using this ink composition 16 under the same conditions as in Example 1 except that the discharge voltage was set to 11 V, a cured film having a thickness of 14 ⁇ m was obtained.
- the cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
- Example 17 As shown below, an ink composition 17 was prepared in the same manner as in Example 1 except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
- the viscosity of the ink composition 17 was 21.9 mPa ⁇ s.
- a cured film was formed under the same conditions as in Example 1 except that the head temperature was set to 40 ° C., and a cured film having a thickness of 15 ⁇ m was obtained.
- the cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
- Example 18 As shown below, an ink composition 18 was prepared in the same manner as in Example 1, except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
- the viscosity of the ink composition 18 was 15.8 mPa ⁇ s.
- a cured film was formed using this ink composition 18 under the same conditions as in Example 1 except that the head temperature was set to 35 ° C., a cured film having a thickness of 14 ⁇ m was obtained.
- the cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
- Example 19 As shown below, an ink composition 19 was prepared in the same manner as in Example 1, except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
- the viscosity of the ink composition 19 was 16.4 mPa ⁇ s.
- a cured film was formed using this ink composition 19 under the same conditions as in Example 1 except that the head temperature was set to 35 ° C., a cured film having a thickness of 14 ⁇ m was obtained.
- the cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
- Example 20 As shown below, an ink composition 20 was prepared in the same manner as in Example 1 except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
- the viscosity of the ink composition 20 was 14.7 mPa ⁇ s.
- a cured film was formed using this ink composition 20 under the same conditions as in Example 1 except that the head temperature was set to 35 ° C., a cured film having a thickness of 14 ⁇ m was obtained.
- the cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
- Example 21 As shown below, an ink composition 21 was prepared in the same manner as in Example 1 except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
- the viscosity of the ink composition 21 was 34.8 mPa ⁇ s.
- a cured film was formed using this ink composition 21 under the same conditions as in Example 1 except that the head temperature was set to 50 ° C., a cured film having a thickness of 15 ⁇ m was obtained.
- the cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
- Example 22 As shown below, an ink composition 22 was prepared in the same manner as in Example 1 except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
- the viscosity of the ink composition 22 was 19.7 mPa ⁇ s.
- a cured film was formed under the same conditions as in Example 1 except that the head temperature was set to 40 ° C. As a result, a cured film having a thickness of 16 ⁇ m was obtained.
- the cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
- Example 23 As shown below, an ink composition 23 was prepared in the same manner as in Example 1 except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
- the viscosity of the ink composition 23 was 9.9 mPa ⁇ s.
- a cured film was formed using this ink composition 23 under the same conditions as in Example 1, a cured film having a thickness of 14 ⁇ m was obtained.
- the cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
- Example 24 As shown below, an ink composition 24 was prepared in the same manner as in Example 1 except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
- the viscosity of the ink composition 24 was 8.5 mPa ⁇ s.
- a cured film was formed using this ink composition 24 under the same conditions as in Example 1, a cured film having a thickness of 13 ⁇ m was obtained.
- the cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
- Example 25 As shown below, an ink composition 25 was prepared in the same manner as in Example 1, except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
- the viscosity of the ink composition 25 was 37.2 mPa ⁇ s.
- the SUS substrate coated with the ink composition 25 is irradiated with ultraviolet rays at a UV exposure amount of 2,000 mJ / cm 2 using a UV irradiation device (J-CURE 1500 manufactured by JATEC Co., Ltd.).
- substrate with which the cured film of the thing 25 was formed was obtained. The following measurement and evaluation were performed using the SUS substrate on which the cured film was formed.
- Measurement of film thickness Measurement was performed using a Digimatic Micrometer (manufactured by Mitutoyo Corporation). It was 15 micrometers when the thickness of the SUS board
- Example 26 As shown below, an ink composition 26 was prepared in the same manner as in Example 1 except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
- the viscosity of the ink composition 26 was 28.1 mPa ⁇ s.
- a cured film was formed under the same conditions as in Example 25 except that the head temperature was set to 45 ° C., and a cured film having a thickness of 15 ⁇ m was obtained. The cured film was evaluated for substrate adhesion and detergent resistance under the same conditions as in Example 25. The results are shown in Table 2.
- Example 27 As shown below, an ink composition 27 was prepared in the same manner as in Example 1 except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
- the viscosity of the ink composition 27 was 19.9 mPa ⁇ s.
- a cured film was formed under the same conditions as in Example 25 except that the head temperature was set to 40 ° C. As a result, a cured film having a thickness of 16 ⁇ m was obtained. The cured film was evaluated for substrate adhesion and detergent resistance under the same conditions as in Example 25. The results are shown in Table 2.
- Example 1 Comparative Example 1 As shown below, an ink composition 28 was prepared in the same manner as in Example 1, except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below. (B) DPGDA 5g (C) Irg1173 0.7g (D) PF656 0.001g The viscosity of the ink composition 28 was 9.4 mPa ⁇ s. When a cured film was formed using this ink composition 28 under the same conditions as in Example 1, a cured film having a thickness of 13 ⁇ m was obtained. The cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
- Example 2 As shown below, an ink composition 29 was prepared in the same manner as in Example 1 except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
- A EB168 0.5g
- B DPGDA 4.5g
- C Irg1173 0.7g
- D PF656 0.001g
- the viscosity of the ink composition 29 was 13.2 mPa ⁇ s.
- a cured film was formed under the same conditions as in Example 1 except that the head temperature was set to 35 ° C. A cured film having a thickness of 13 ⁇ m was obtained. The cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
- Example 3 Comparative Example 3
- an ink composition 30 was prepared in the same manner as in Example 1 except that the ratio of each compound was changed.
- the viscosity measured in the same manner as in Example 1 is shown below.
- the viscosity of the ink composition 30 was 18.0 mPa ⁇ s.
- a cured film was formed under the same conditions as in Example 1 except that the head temperature was set to 40 ° C.
- a cured film having a thickness of 14 ⁇ m was obtained.
- the cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
- Example 4 As shown below, an ink composition 31 was prepared in the same manner as in Example 1, except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
- the viscosity of the ink composition 31 was 8.7 mPa ⁇ s.
- a cured film was formed using this ink composition 31 under the same conditions as in Example 1, a cured film having a thickness of 13 ⁇ m was obtained. The cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
- Example 5 Comparative Example 5
- an ink composition 32 was prepared in the same manner as in Example 1 except that the ratio of each compound was changed.
- the viscosity measured in the same manner as in Example 1 is shown below.
- the viscosity of the ink composition 32 was 12.4 mPa ⁇ s.
- a cured film was formed under the same conditions as in Example 1 using this ink composition 32, a cured film having a thickness of 13 ⁇ m was obtained.
- the cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
- Example 6 Comparative Example 6
- an ink composition 33 was prepared in the same manner as in Example 1, except that the ratio of each compound was changed.
- the viscosity measured in the same manner as in Example 1 is shown below.
- the viscosity of the ink composition 33 was 14.3 mPa ⁇ s.
- a cured film was formed under the same conditions as in Example 1 except that the head temperature was set to 35 ° C.
- a cured film having a thickness of 13 ⁇ m was obtained.
- the cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
- Example 7 an ink composition 34 was prepared in the same manner as in Example 1, except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
- the viscosity of the ink composition 34 was 9.9 mPa ⁇ s.
- a cured film was formed using this ink composition 34 under the same conditions as in Example 1, a cured film having a thickness of 13 ⁇ m was obtained. The cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
- Example 8 As shown below, an ink composition 35 was prepared in the same manner as in Example 1, except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
- the viscosity of the ink composition 35 was 11.5 mPa ⁇ s.
- a cured film was formed using this ink composition 35 under the same conditions as in Example 1, a cured film having a thickness of 12 ⁇ m was obtained. The cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
- Example 9 an ink composition 36 was prepared in the same manner as in Example 1, except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
- the viscosity of the ink composition 36 was 25.8 mPa ⁇ s.
- a cured film was formed under the same conditions as in Example 1 except that the head temperature was set to 40 ° C. As a result, a cured film having a thickness of 15 ⁇ m was obtained. The cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
- Example 10 Comparative Example 10
- an ink composition 37 was prepared in the same manner as in Example 1 except that the ratio of each compound was changed.
- the viscosity measured in the same manner as in Example 1 is shown below.
- the viscosity of the ink composition 37 was 17.7 mPa ⁇ s.
- a cured film was formed under the same conditions as in Example 1 except that the head temperature was set to 35 ° C., and a cured film having a thickness of 14 ⁇ m was obtained.
- the cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
- Example 11 an ink composition 38 was prepared in the same manner as in Example 1 except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
- the viscosity of the ink composition 38 was 24.7 mPa ⁇ s.
- a cured film was formed under the same conditions as in Example 1 except that the head temperature was set to 40 ° C. As a result, a cured film having a thickness of 15 ⁇ m was obtained. The cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
- Example 12 Comparative Example 12
- an ink composition 39 was prepared in the same manner as in Example 1 except that the ratio of each compound was changed.
- the viscosity measured in the same manner as in Example 1 is shown below.
- the viscosity of the ink composition 39 was 24.8 mPa ⁇ s.
- a cured film was formed under the same conditions as in Example 1 except that the head temperature was set to 40 ° C.
- a cured film having a thickness of 15 ⁇ m was obtained.
- the cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
- Example 13 an ink composition 40 was prepared in the same manner as in Example 1 except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
- the viscosity of the ink composition 40 was 20.2 mPa ⁇ s.
- a cured film was formed under the same conditions as in Example 1 except that the head temperature was set to 40 ° C. As a result, a cured film having a thickness of 16 ⁇ m was obtained. The cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
- Example 14 an ink composition 41 was prepared in the same manner as in Example 1 except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
- B IB-XA 2.95 g
- B M-208 2.00g
- C Irg1173 0.7g
- D PF656 0.001g
- the viscosity of the ink composition 41 was 28.0 mPa ⁇ s.
- a cured film was formed under the same conditions as in Example 25 except that the head temperature was set at 45 ° C., and a cured film having a thickness of 15 ⁇ m was obtained. The cured film was evaluated for substrate adhesion and detergent resistance under the same conditions as in Example 25. The results are shown in Table 2.
- Example 15 an ink composition 42 was prepared in the same manner as in Example 1, except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
- the viscosity of the ink composition 42 was 9.6 mPa ⁇ s.
- a cured film was formed using this ink composition 42 under the same conditions as in Example 25 except that the head temperature was set to 30 ° C., a cured film having a thickness of 13 ⁇ m was obtained. The cured film was evaluated for substrate adhesion and detergent resistance under the same conditions as in Example 25. The results are shown in Table 2.
- the photocurable inkjet ink of the present invention is useful for producing an insulating cured film inside the secondary battery and on the electromagnetic shielding material.
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Abstract
Description
しかし、一般的な電磁波シールドケースや電磁波シールド材では電磁波遮蔽部のFPCとの間の電気絶縁性が確保できないため、電磁波シールド性と電気絶縁性を両立させることが困難である。
これまで、この問題を解決するために、銅などの金属基板に樹脂を熱融着させたり、金属基板に樹脂テープを貼り合わせることで対応されてきた(例えば特許文献5及び6を参照)。しかし、熱融着は高熱で樹脂を溶解させながら形成する必要があるため、操作が煩雑となる。また、樹脂テープの貼り合わせは手作業で行われるため、多くの手間がかかるのが問題であった。そのため、これらの工程を削減できるような金属基板上に印刷法で形成できる絶縁膜が必要とされている。 Further, for example, in order to shield electromagnetic waves generated from electronic components, there is a method of covering a complicated circuit such as a flexible printed wiring board (hereinafter referred to as FPC) with an electromagnetic shielding case or producing a circuit on an electromagnetic shielding material. Has been done.
However, in general electromagnetic shielding cases and electromagnetic shielding materials, it is difficult to achieve both electromagnetic shielding properties and electrical insulation properties because electrical insulation between the electromagnetic shielding portions and the FPC of the electromagnetic shielding portions cannot be ensured.
Until now, in order to solve this problem, it has been dealt with by thermally fusing a resin to a metal substrate such as copper, or bonding a resin tape to the metal substrate (see, for example, Patent Documents 5 and 6). However, since heat fusion needs to be formed while dissolving the resin at high heat, the operation becomes complicated. In addition, since the bonding of the resin tape is performed manually, there is a problem that much labor is required. Therefore, there is a need for an insulating film that can be formed by a printing method on a metal substrate that can reduce these steps.
インク組成物であって、反応性化合物(B)の総量100重量部に対し、リン酸エステル基を有する(メタ)アクリレートモノマー(A)の添加量が0.01~5.5重量部である光硬化性組成物が、二次電池に用いられる電解液に対する耐性が高く、アルミニウム等の金属集電体に対する密着性が高く、二次電池に用いる絶縁性樹脂として有用であり、更に、電磁波シールド材のプレス成形加工時に用いられる潤滑油を洗浄する際に使用される洗浄剤に対する耐性と金属基板に対する密着性が高く、電磁波シールド材の金属基材上に印刷で形成できるような絶縁性樹脂として有用であることを見出し、この知見に基づいて本発明を完成した。
すなわち本発明は、以下の項を含む。 The present inventors have (meth) acrylate monomer (A) having a phosphate ester and having 1 to 3 acryloyl groups in one molecule and — (CH 2 —CH 2 —O) n — (n> 3) An ink composition comprising a reactive compound (B) other than (A) having no structure, and at least one selected from a benzyl ketal compound and an α-hydroxyacetophenone compound as a photopolymerization initiator (C). A photocurable composition in which the addition amount of the (meth) acrylate monomer (A) having a phosphate ester group is 0.01 to 5.5 parts by weight with respect to 100 parts by weight of the total amount of the reactive compound (B). The material is highly resistant to the electrolyte used in the secondary battery, has high adhesion to a metal current collector such as aluminum, and is useful as an insulating resin for use in the secondary battery. It has high resistance to cleaning agents used when washing lubricants used in press molding and high adhesion to metal substrates, and is useful as an insulating resin that can be formed by printing on a metal base material for electromagnetic shielding materials. Based on this finding, the present invention has been completed.
That is, the present invention includes the following items.
(一般式(1-1)および(1-2)中、R1はそれぞれ独立して水素またはメチルである。)。 [1] (meth) acrylate monomer (A) which is at least one selected from compounds having a phosphate ester represented by general formulas (1-1) and (1-2), and 1 to 3 per molecule A reactive compound (B) other than (A) having a single acryloyl group and having no — (CH 2 —CH 2 —O) n — (n> 3) structure, as a photopolymerization initiator (C) An (meth) acrylate monomer having a phosphate ester with respect to 100 parts by weight of the total amount of the reactive compound (B), the ink composition comprising at least one selected from benzyl ketal compounds and α-hydroxyacetophenone compounds A photocurable inkjet ink in which the amount of addition of (A) is 0.01 to 5.5 parts by weight.
(In the general formulas (1-1) and (1-2), each R 1 is independently hydrogen or methyl).
By using the photo-curable ink-jet ink of the present invention, an insulating film having high adhesion to metal can be formed by a printing method, and particularly when a secondary battery is manufactured, an electrolyte-resistant material is formed on a metal current collector. A high insulating film can be formed. Also, an insulating film having high resistance to the cleaning agent can be formed on the metal substrate of the electromagnetic wave shielding material.
本発明の光硬化性インクジェットインクは、一般式(1-1)および(1-2)で表されるリン酸エステルを有する化合物から選ばれる少なくとも1つである(メタ)アクリレートモノマー(A)、1分子中に1~3個のアクリロイル基を有しかつ-(CH2-CH2-O)n-(n>3)構造を有さない(A)以外の反応性化合物(B)、光重合開始剤(C)としてベンジルケタール系化合物およびα-ヒドロキシアセトフェノン系化合物から選ばれる少なくとも1つを含む光硬化性インクジェットインク(以降、インク組成物ということがある)であって、反応性化合物(B)の総量100重量部に対し、リン酸エステルを有する(メタ)アクリレートモノマー(A)の添加量が0.01~5.5重量部であるインク組成物である。
(一般式(1-1)および(1-2)中、R1はそれぞれ独立して水素またはメチルである。)
また、本発明のインク組成物は無色であっても有色であってもよい。 [1. Photocurable inkjet ink of the present invention]
The photocurable inkjet ink of the present invention is a (meth) acrylate monomer (A) that is at least one selected from compounds having a phosphate ester represented by general formulas (1-1) and (1-2). 1 having 1-3 acryloyl groups in the molecule and - (CH 2 -CH 2 -O) n - (n> 3) no structure other than (a) of the reactive compound (B), light A photocurable inkjet ink (hereinafter sometimes referred to as an ink composition) containing at least one selected from a benzyl ketal compound and an α-hydroxyacetophenone compound as a polymerization initiator (C), and a reactive compound ( The ink composition has an addition amount of the (meth) acrylate monomer (A) having a phosphate ester of 0.01 to 5.5 parts by weight with respect to 100 parts by weight of the total amount of B).
(In the general formulas (1-1) and (1-2), each R 1 is independently hydrogen or methyl.)
The ink composition of the present invention may be colorless or colored.
本発明のリン酸エステルを有する(メタ)アクリレートモノマー(A)は、一般式(1-1)または(1-2)で表されるリン酸エステルを有する化合物から選ばれる少なくとも1つである。一般式(1-1)および(1-2)で示されるリン酸エステルを有する化合物を併用してもよい。
[1.1. (Meth) acrylate monomer (A) having phosphate ester]
The (meth) acrylate monomer (A) having a phosphate ester of the present invention is at least one selected from compounds having a phosphate ester represented by formula (1-1) or (1-2). A compound having a phosphate ester represented by the general formulas (1-1) and (1-2) may be used in combination.
本発明のリン酸エステルを有する(メタ)アクリレートモノマー(A)以外の反応性化合物(B)は、1分子中のアクリロイル基の数が1~3個であると金属集電体をはじめとする金属基板に対する密着性が高く、-(CH2-CH2-O)n-(n>3)構造を有さないとアルキレンカーボネートなどの電池用電解液やハイドロクロロフルオロカーボンなどの洗浄剤に対する耐性が高いため好ましい。 [1.2.1 Having a phosphate ester having 1 to 3 acryloyl groups in the molecule and having no — (CH 2 —CH 2 —O) n — (n> 3) structure (meth) Reactive compound (B) other than acrylate monomer (A)]
The reactive compound (B) other than the (meth) acrylate monomer (A) having a phosphate ester according to the present invention includes a metal current collector and the like when the number of acryloyl groups in one molecule is 1 to 3 High adhesion to metal substrates, and resistance to battery electrolytes such as alkylene carbonates and cleaning agents such as hydrochlorofluorocarbons without the — (CH 2 —CH 2 —O) n — (n> 3) structure It is preferable because it is high.
本発明のインク組成物は、光重合開始剤(C)を含む。光重合開始剤(C)は、紫外線あるいは可視光線の照射によりラジカルを発生することのできる化合物である事が好ましい、さらにベンジルケタール系化合物またはα-ヒドロキシアセトフェノン系化合物が光硬化性、得られる硬化膜の金属集電体をはじめとする金属基材に対する密着性および電解液耐性、洗浄剤耐性が両立できる観点から好ましい。 [1.3. Photopolymerization initiator (C)]
The ink composition of the present invention contains a photopolymerization initiator (C). The photopolymerization initiator (C) is preferably a compound capable of generating radicals upon irradiation with ultraviolet rays or visible rays. Further, a benzyl ketal compound or an α-hydroxyacetophenone compound is photocured and cured. It is preferable from the viewpoint that the adhesion of the film to the metal substrate including the metal current collector, the electrolyte solution resistance, and the detergent resistance can be compatible.
本発明のインク組成物は、保存安定性を向上させるために重合禁止剤を含有してもよい。重合禁止剤の具体例としては、4-メトキシフェノール、ヒドロキノン、ヒンダートアミンおよびフェノチアジンを挙げることができる。 [1.4. Polymerization inhibitor]
The ink composition of the present invention may contain a polymerization inhibitor in order to improve storage stability. Specific examples of the polymerization inhibitor include 4-methoxyphenol, hydroquinone, hindered amine, and phenothiazine.
本発明のインク組成物は、熱硬化性化合物を含んでもよい。本発明において、熱硬化性化合物とは熱硬化させることが可能な官能基を有する化合物であれば特に限定されず、ビスマレイミド、フェノール樹脂、またはフェノール性水酸基を含有する樹脂、メラミン樹脂、エポキシ化合物などが挙げられる。
本発明のインク組成物に用いられる熱硬化性化合物は、1種でも、2種以上の混合物でもよい。 [1.5. Thermosetting compound]
The ink composition of the present invention may contain a thermosetting compound. In the present invention, the thermosetting compound is not particularly limited as long as it is a compound having a functional group capable of thermosetting, and bismaleimide, a phenol resin, a resin containing a phenolic hydroxyl group, a melamine resin, an epoxy compound. Etc.
The thermosetting compound used in the ink composition of the present invention may be one type or a mixture of two or more types.
ビスマレイミドとしては、例えば、下記一般式(1)で表される化合物が挙げられる。下記一般式(1)で表されるビスマレイミドは、例えばジアミンとマレイン酸無水物とを反応させて得られる化合物である。 [1.5.1 Bismaleimide]
Examples of the bismaleimide include compounds represented by the following general formula (1). The bismaleimide represented by the following general formula (1) is a compound obtained by reacting, for example, a diamine and maleic anhydride.
In the formula (2), R 13 and R 14 each independently represents an alkylene having 1 to 18 carbon atoms in which arbitrary non-continuous methylene may be replaced by oxygen, or an aromatic ring that may have a substituent. It is a cycloalkylene which may have a valent group or a substituent. Examples of the substituent in the aromatic ring and cycloalkylene include carboxyl, hydroxyl, alkyl having 1 to 5 carbons, and alkoxy having 1 to 5 carbons. Because it has a high heat resistance resulting cured film, it is preferable R 13 and R 14 is a divalent group represented by independently following either equation.
[1.5.2 フェノール樹脂、またはフェノール性水酸基を含有する樹脂] The bismaleimide may be one kind or a mixture of two or more kinds.
[1.5.2 Phenol resin or resin containing a phenolic hydroxyl group]
メラミン樹脂は、メラミンとホルムアルデヒドとの重縮合により製造された樹脂であれば特に限定されず、メチロールメラミン、エーテル化メチロールメラミン、ベンゾグアナミン、メチロールベンゾグアナミン、エーテル化メチロールベンゾグアナミン、およびそれらの縮合物などが挙げられる。これらの中でも、得られる硬化膜の耐薬品性が良好である点で、エーテル化メチロールメラミンが好ましい。 [1.5.3 Melamine resin]
The melamine resin is not particularly limited as long as it is a resin produced by polycondensation of melamine and formaldehyde, and examples thereof include methylol melamine, etherified methylol melamine, benzoguanamine, methylol benzoguanamine, etherified methylol benzoguanamine, and condensates thereof. It is done. Among these, etherified methylol melamine is preferable in that the resulting cured film has good chemical resistance.
本発明のインク組成物は、得られる硬化膜等の強度を向上させるために、エポキシ化合物を含有してもよい。
前記エポキシ化合物は、1分子中に少なくとも1つの下記式(3-1)または式(3-2)で表される構造を有する化合物であれば、特に限定されない。 [1.5.4 Epoxy compound]
The ink composition of the present invention may contain an epoxy compound in order to improve the strength of the obtained cured film or the like.
The epoxy compound is not particularly limited as long as it has at least one structure represented by the following formula (3-1) or formula (3-2) in one molecule.
jER152、154(いずれも商品名:三菱化学(株))、D.E.R.431、同438(いずれも商品名:ダウ・ケミカル日本(株))、エピクロンN-730、同N-770、同N-865(いずれも商品名:DIC(株))、エポトートYDCN-701、同YDCN-704(いずれも商品名:新日鐵化学(株))、アラルダイトECN1235、同ECN1273、同ECN1299(いずれも商品名:ハンツマン・ジャパン(株))、XPY307、EPPN-201、EOCN-1025、EOCN-1020、EOCN-104S、RE-306(いずれも商品名:日本化薬(株))、スミ-エポキシESCN-195X、同ESCN-220(いずれも商品名:住友化学工業(株))、A.E.R.ECN-235、同ECN-299(いずれも商品名:旭化成イーマテリアルズ(株))等のノボラック型エポキシ樹脂;
エピクロン830(商品名:DIC(株))、jER807(商品名:三菱化学(株))、エポトートYDF-170(商品名:新日鐵化学(株))、YDF-175、YDF-2001、YDF-2004、アラルダイトXPY306(いずれも商品名:ハンツマン・ジャパン(株))等のビスフェノールF型エポキシ樹脂;
エポトートST-2004、同ST-2007、同ST-3000(いずれも商品名:新日鐵化学(株))等の水添ビスフェノールA型エポキシ樹脂;
セロキサイド2021P(商品名:(株)ダイセル)、アラルダイトCY175、同CY179(いずれも商品名:ハンツマン・ジャパン(株))等の脂環式エポキシ樹脂;
YL-6056、YX-4000、YL-6121(いずれも商品名:三菱化学(株)製)等のビキシレノール型もしくはビフェノール型エポキシ樹脂またはそれらの混合物;
EBPS-200(商品名:日本化薬(株))、EPX-30(商品名:(株)ADEKA)、EXA-1514(商品名:DIC(株))等のビスフェノールS型エポキシ樹脂;
jER157S(商品名:三菱化学(株))等のビスフェノールAノボラック型エポキシ樹脂;
YL-931(商品名:三菱化学(株))、アラルダイト163(商品名:ハンツマン・ジャパン(株))等のテトラフェニロールエタン型エポキシ樹脂;
アラルダイトPT810(商品名:ハンツマン・ジャパン(株))、TEPIC(商品名:日産化学工業(株))等の複素環式エポキシ樹脂;
HP-4032、EXA-4750、EXA-4700(いずれも商品名:DIC(株))等のナフタレン基含有エポキシ樹脂;
HP-7200、HP-7200H、HP-7200HH(いずれも商品名:DIC(株))等のジシクロペンタジエン骨格を有するエポキシ樹脂;
テクモアVG3101L(商品名:三井化学(株))、YL-933(商品名:三菱化学(株))、EPPN-501、EPPN-502(いずれも商品名:日本化薬(株))等のトリスフェノールメタン型エポキシ樹脂が挙げられる。 Examples of commercially available products are jER828, 834, 1001, and 1004 (all trade names: manufactured by Mitsubishi Chemical Corporation), Epicron 840, 850, 1050, 1050, and 2055 (all trade names: DIC). Epototo YD-011, YD-013, YD-127, YD-128 (all trade names: Nippon Steel Chemical Co., Ltd.), D.E.R. 317, 331, 661, 664 (both trade names: Dow Chemical Japan Co., Ltd.), Araldite 6071, 6084, GY250, GY260 (both trade names: Huntsman Japan Co., Ltd.), Sumi-Epoxy ESA- 011, ESA-014, ELA-115, ELA-115, ELA-128 (all trade names: Sumitomo Chemical Co., Ltd.), AER 330, 331, 661, 664 Trade name Re: Asahi Kasei E-materials Corp.) Bisphenol A type epoxy resins and the like;
jER152, 154 (all trade names: Mitsubishi Chemical Corporation), D.E.R.431, 438 (all trade names: Dow Chemical Japan Co., Ltd.), Epicron N-730, N-770 N-865 (all trade names: DIC Corporation), Epototo YDCN-701, YDCN-704 (all trade names: Nippon Steel Chemical Co., Ltd.), Araldite ECN1235, ECN1273, ECN1299 ( All are trade names: Huntsman Japan Co., Ltd.), XPY307, EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306 (all trade names: Nippon Kayaku Co., Ltd.), Sumi- Epoxy ESCN-195X, ESCN-220 (both trade names: Sumitomo Chemical Co., Ltd.), AER ECN-235, ECN 299 (trade name: Asahi Kasei E-Materials Co., Ltd.) novolak epoxy resins and the like;
Epicron 830 (trade name: DIC Corporation), jER807 (trade name: Mitsubishi Chemical Corporation), Epototo YDF-170 (trade name: Nippon Steel Chemical Co., Ltd.), YDF-175, YDF-2001, YDF -Bisphenol F type epoxy resins such as 2004 and Araldite XPY306 (both trade names: Huntsman Japan Co., Ltd.);
Hydrogenated bisphenol A type epoxy resins such as Epototo ST-2004, ST-2007, ST-3000 (all trade names: Nippon Steel Chemical Co., Ltd.);
An alicyclic epoxy resin such as Celoxide 2021P (trade name: Daicel Corporation), Araldite CY175, CY179 (both trade names: Huntsman Japan Co., Ltd.);
Bixylenol-type or biphenol-type epoxy resins such as YL-6056, YX-4000, YL-6121 (all trade names: manufactured by Mitsubishi Chemical Corporation) or mixtures thereof;
Bisphenol S type epoxy resins such as EBPS-200 (trade name: Nippon Kayaku Co., Ltd.), EPX-30 (trade name: ADEKA Corp.), EXA-1514 (trade name: DIC Corp.);
bisphenol A novolac epoxy resin such as jER157S (trade name: Mitsubishi Chemical Corporation);
Tetraphenylolethane type epoxy resins such as YL-931 (trade name: Mitsubishi Chemical Corporation), Araldite 163 (trade name: Huntsman Japan Co., Ltd.);
Heterocyclic epoxy resins such as Araldite PT810 (trade name: Huntsman Japan Co., Ltd.), TEPIC (trade name: Nissan Chemical Industries, Ltd.);
Naphthalene group-containing epoxy resins such as HP-4032, EXA-4750, EXA-4700 (all trade names: DIC Corporation);
Epoxy resins having a dicyclopentadiene skeleton such as HP-7200, HP-7200H, HP-7200HH (all trade names: DIC Corporation);
Tris such as Techmore VG3101L (trade name: Mitsui Chemicals), YL-933 (trade name: Mitsubishi Chemical), EPPN-501, EPPN-502 (all trade names: Nippon Kayaku Co., Ltd.) A phenol methane type epoxy resin is mentioned.
本発明のインク組成物に用いられうるエポキシ樹脂は、1種の化合物であっても、2種以上の化合物の混合物であってもよい。 Among these, jER828, 834, 1001, and 1004 (all trade names: Mitsubishi Chemical Corporation), TECHMORE VG3101L (trade name: Printec Co., Ltd.), EPPN-501, EPPN-502 (all Use of Nippon Kayaku Co., Ltd.) is preferable because a cured film having high adhesion can be obtained.
The epoxy resin that can be used in the ink composition of the present invention may be a single compound or a mixture of two or more compounds.
本発明のインク組成物の、E型粘度計で測定した25℃における粘度は1~50mPa・sであると、本発明のインク組成物をインクジェット法で塗布する場合に、吐出性が良好となる。25℃における本発明のインクの粘度は、より好ましくは2~40mPa・sであり、さらに好ましくは4~30mPa・sである。 [2.1. Viscosity of ink composition of the present invention]
When the ink composition of the present invention has a viscosity at 25 ° C. of 1 to 50 mPa · s measured with an E-type viscometer, the ink composition of the present invention has good ejection properties when applied by an ink jet method. . The viscosity of the ink of the present invention at 25 ° C. is more preferably 2 to 40 mPa · s, and further preferably 4 to 30 mPa · s.
本発明のインク組成物は、原料となる各成分を公知の方法により混合することで調製することができる。
特に、本発明のインク組成物は、前記(A)~(C)成分ならびに必要に応じて界面活性剤、紫外線吸収剤、酸化防止剤、重合禁止剤、熱反応性化合物および熱重合開始剤等を混合し、得られた溶液を例えば超高分子量ポリエチレン(UPE)製のメンブレンフィルターを用いてろ過して脱気することにより調製されることが好ましい。このようにして調製されたインク組成物は、インクジェット法による塗布時の吐出性に優れる。 [2.2. Method for preparing ink composition of the present invention]
The ink composition of the present invention can be prepared by mixing each component as a raw material by a known method.
In particular, the ink composition of the present invention includes the components (A) to (C) and, if necessary, a surfactant, an ultraviolet absorber, an antioxidant, a polymerization inhibitor, a thermally reactive compound, a thermal polymerization initiator, and the like. It is preferable to prepare by mixing and degassing the obtained solution using a membrane filter made of, for example, ultra high molecular weight polyethylene (UPE). The ink composition thus prepared is excellent in dischargeability at the time of application by the ink jet method.
本発明のインク組成物は、5~30℃で保存すると保存中の粘度増加が小さく、保存安定性が良好となる。 [2.3. Storage of Ink Composition of the Present Invention]
When the ink composition of the present invention is stored at 5 to 30 ° C., the increase in viscosity during storage is small and the storage stability is good.
本発明のインク組成物は、公知のインクジェット法を用いて塗布することができる。インクジェット法としては、例えば、インクに力学的エネルギーを作用させてインクをインクジェットヘッドから吐出させるピエゾ方式、およびインクに熱エネルギーを作用させてインクを吐出させるサーマル方式が挙げられる。 [2.4. Application of ink composition by inkjet method]
The ink composition of the present invention can be applied using a known ink jet method. Examples of the ink jet method include a piezo method in which mechanical energy is applied to ink to eject the ink from the ink jet head, and a thermal method in which thermal energy is applied to the ink to eject ink.
インクジェットヘッドは加熱してもよく、加熱温度としては80℃以下が好ましく、50℃以下であることがより好ましい。その加熱温度における本発明のインク組成物の粘度は、1.0~30mPa・sであることが好ましい。 The ink jet coating apparatus is not limited to one in which the ink jet head and the ink container are separated, and may be one in which they are inseparably integrated. Further, the ink storage unit may be integrated with the ink jet head so as to be separable or non-separable and mounted on the carriage, or may be provided at a fixed portion of the apparatus. In the latter case, the ink composition may be supplied to the inkjet head via an ink supply member, for example, a tube.
The ink jet head may be heated, and the heating temperature is preferably 80 ° C. or less, and more preferably 50 ° C. or less. The viscosity of the ink composition of the present invention at the heating temperature is preferably 1.0 to 30 mPa · s.
本発明のインク組成物より得られる膜(本発明において、単に「硬化膜」ともいう。)は、上述した本発明のインク組成物をインクジェット法により基板表面に塗布した後に、紫外線や可視光線等の光を照射して硬化させることで得られる。 [3. Formation of cured film]
The film obtained from the ink composition of the present invention (also simply referred to as “cured film” in the present invention) is obtained by applying the above-described ink composition of the present invention to the substrate surface by an inkjet method, and then applying ultraviolet rays, visible light, etc. It is obtained by irradiating and curing the light.
なお、以下に記載する露光量はウシオ電機(株)製の受光器UVD-365PDを取り付けた積算光量計UIT-201で測定した値である。 The amount of light to be irradiated (exposure amount) when irradiating ultraviolet rays, visible rays, or the like depends on the ink composition, but the integrated light meter UIT-201 equipped with a photoreceiver UVD-365PD manufactured by USHIO INC. 100 to 5,000 mJ / cm 2 is preferable, 300 to 4,000 mJ / cm 2 is more preferable, and 500 to 3,000 mJ / cm 2 is more preferable. Further, the wavelength of ultraviolet rays or visible rays to be irradiated is preferably 200 to 500 nm, and more preferably 250 to 450 nm.
The exposure amount described below is a value measured by an integrated light meter UIT-201 equipped with a photoreceiver UVD-365PD manufactured by USHIO INC.
DPGDA:ジプロピレングリコールジアクリレート
NPDA:ネオペンチルグリコールジアクリレート
HPNDA:ネオペンチルグリコール・ヒドロキシピバリン酸エステルジアクリレート
SR9003(商品名:サートマー社 製):プロポキシ化(2)ネオペンチルグリコールジアクリレート
TPGDA:トリプロピレングリコールジアクリレート
701A(NKエステル701A、商品名:新中村化学工業(株)製):2-ヒドロキシ-3-アクリロイロキシプロピルメタアクリレート
1,3-BGDA:1,3-ブチレングリコールジアクリレート
FA-513AS(ファンクリルFA-513AS、商品名:日立化成(株)製):ジシクロペンタニルアクリレート
IBXA:イソボルニルアクリレート
BzMA:ベンジルメタクリレート
M-208(アロニックスM-208、商品名:東亞合成(株)製):ビスフェノールF EO変性ジアクリレート
IRR214-K(IRR214-K、商品名:ダイセル・オルネクス(株)製):トリシクロデカンジメタノールジアクリレート
DOGDA:ジオキサングリコールジアクリレート
TMPTA:トリメチロールプロパントリアクリレート
M-305(アロニックスM-305、商品名:東亞合成(株)製):ペンタエリスリトールトリアクリレートとペンタエリスリトールテトラアクリレートの混合物
3EG(ライトエステル3EG、商品名:共栄社化学(株)製):トリエチレングリコールジアクリレート
4EG(ライトエステル4EG、商品名:共栄社化学(株)製):ポリエチレングリコール#200ジアクリレート
A-BPE-10(NKエステルA-BPE-10、商品名:新中村化学工業(株)製):エトキシ化ビスフェノールAジアクリレート
A-GLY-9E(NKエステルA-GLY-9E、商品名:新中村化学工業(株)製):エトキシ化グリセリントリアクリレート
A-9550(NKエステルA-9550、商品名:新中村化学工業(株)製):ジペンタエリスリトールポリアクリレート
DPCA-20(KAYARAD DPCA-20、商品名:日本化薬(株)製):カプロラクトン変性ジペンタエリスリトールヘキサアクリレート
CN2302(商品名:サートマー社 製):ハイパーブランチオリゴマー
Irg1173(Irgacure1173、商品名:BASF製):2-ヒドロキシ-2-メチル-1-フェニル-プロパン-1-オン
Irg651(Irgacure651、商品名:BASF製):2,2-ジメトキシ-2-フェニルアセトフェノン
Irg127(Irgacure127、商品名:BASF製):2-ヒドロキシ-1-{4-[4-(2-ヒドロキシ-2-メチル-プロピオニル)-ベンジル]フェニル}-2-メチル-1-プロパノン
Irg184(Irgacure184、商品名:BASF製):1-ヒドロキシ-シクロヘキシル-フェニル-ケトン
IrgMBF(IrgacureMBF、商品名:BASF製):フェニルグリオキシリックアシッドメチルエステル
Irg754(Irgacure754、商品名:BASF製):オキシ-フェニル-酢酸2-[2-オキソ-2-フェニル-アセトキシ-エトキシ]-エチルエステルとオキシ-フェニル-酢酸2-[2-ヒドロキシ-エトキシ]-エチルエステルとの混合物
IrgTPO(IrgacureTPO、商品名:BASF製):2,4,6-トリメチルベンゾイルジフェニルフォスフィンオキサイド
PF656(PolyFox PF-656、商品名:OMNOVA(株)製):フッ素基含有界面活性剤 EB168 (EBECRYL168, trade name: manufactured by Daicel Ornex Co., Ltd.): Mixture of 2-methacryloxyethyl acid phosphate DPGDA: Dipropylene glycol diacrylate NPDA: Neopentyl glycol diacrylate HPNDA: Neopentyl glycol hydroxypivalate ester Diacrylate SR9003 (trade name: manufactured by Sartomer): propoxylation (2) neopentyl glycol diacrylate TPGDA: tripropylene glycol diacrylate 701A (NK ester 701A, trade name: manufactured by Shin-Nakamura Chemical Co., Ltd.): 2- Hydroxy-3-acryloyloxypropyl methacrylate 1,3-BGDA: 1,3-butylene glycol diacrylate FA-513AS (funcryl FA-51 AS, trade name: manufactured by Hitachi Chemical Co., Ltd.): dicyclopentanyl acrylate IBXA: isobornyl acrylate BzMA: benzyl methacrylate M-208 (Aronix M-208, trade name: manufactured by Toagosei Co., Ltd.): bisphenol F EO-modified diacrylate IRR214-K (IRR214-K, trade name: manufactured by Daicel Ornex Co., Ltd.): tricyclodecane dimethanol diacrylate DOGDA: dioxane glycol diacrylate TMPTA: trimethylolpropane triacrylate M-305 (Aronix M) -305, trade name: manufactured by Toagosei Co., Ltd.): mixture 3EG of pentaerythritol triacrylate and pentaerythritol tetraacrylate (light ester 3EG, trade name: manufactured by Kyoeisha Chemical Co., Ltd.): triethyle Glycol diacrylate 4EG (light ester 4EG, trade name: manufactured by Kyoeisha Chemical Co., Ltd.): polyethylene glycol # 200 diacrylate A-BPE-10 (NK ester A-BPE-10, trade name: Shin-Nakamura Chemical Co., Ltd.) Manufactured): ethoxylated bisphenol A diacrylate A-GLY-9E (NK ester A-GLY-9E, trade name: manufactured by Shin-Nakamura Chemical Co., Ltd.): ethoxylated glycerin triacrylate A-9550 (NK ester A-9550) Product name: Shin-Nakamura Chemical Co., Ltd.): Dipentaerythritol polyacrylate DPCA-20 (KAYARAD DPCA-20, product name: Nippon Kayaku Co., Ltd.): Caprolactone-modified dipentaerythritol hexaacrylate CN2302 (Product) Name: Made by Sartomer) Hyper Blanc Oligomer Irg 1173 (Irgacure 1173, trade name: manufactured by BASF): 2-hydroxy-2-methyl-1-phenyl-propan-1-one Irg651 (Irgacure 651, trade name: manufactured by BASF): 2,2-dimethoxy-2-phenylacetophenone Irg127 (Irgacure 127, trade name: manufactured by BASF): 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-1-propanone Irg184 (Irgacure 184) , Trade name: manufactured by BASF): 1-hydroxy-cyclohexyl-phenyl-ketone IrgMBF (Irgacure MBF, trade name: manufactured by BASF): phenylglyoxylic acid methyl ester Irg754 (Irgac) re754, trade name: manufactured by BASF): oxy-phenyl-acetic acid 2- [2-oxo-2-phenyl-acetoxy-ethoxy] -ethyl ester and oxy-phenyl-acetic acid 2- [2-hydroxy-ethoxy] -ethyl ester IrgTPO (IrgacureTPO, trade name: manufactured by BASF): 2,4,6-trimethylbenzoyldiphenylphosphine oxide PF656 (PolyFox PF-656, trade name: manufactured by OMNOVA): Fluorine group-containing surfactant
アクリレートモノマー(A)として、EB168と、化合物(B)として、DPGDAと、光重合開始剤(C)として、Irg1173、界面活性剤(D)として、PF656を下記組成割合にて混合し、UPE製のメンブレンフィルター(0.2μm)でろ過し、ろ液(インク組成物1)を得た。
(A)EB168 0.25g
(B)DPGDA 4.75g
(C)Irg1173 0.7g
(D)PF656 0.001g Example 1
As the acrylate monomer (A), EB168, DPGDA as the compound (B), Irg1173 as the photopolymerization initiator (C), PF656 as the surfactant (D) are mixed in the following composition ratio, and manufactured by UPE The membrane filter (0.2 μm) was used to obtain a filtrate (ink composition 1).
(A) EB168 0.25g
(B) 4.75 g of DPGDA
(C) Irg1173 0.7g
(D) PF656 0.001g
硬化膜を形成する基材として、6cm角に裁断したアルミ集電体(宝泉(株)製の20μm厚のアルミ箔)を用意した。コニカミノルタIJ(株)製のKM512MH(14pL)をインクジェットヘッドとして搭載したインクジェット装置(アルバック製ID-225)にインク組成物1を注入し、吐出電圧13V、ヘッド温度30℃、駆動周波数5kHz、塗布回数1回の吐出条件で、印刷解像度を841dpiに設定して、用意した基板上に5cm角の範囲で塗布した。このインク組成物1が塗布されたアルミ箔に、UV照射装置((株)ジャテック製のJ-CURE1500)を用いて紫外線を2,000mJ/cm2のUV露光量で照射することで、インク組成物1の硬化膜が形成されたアルミ箔を得た。この硬化膜が形成されたアルミ箔を用いて、以下の測定および評価を行った。 (Formation of cured film)
As a base material for forming a cured film, an aluminum current collector (20 μm thick aluminum foil manufactured by Hosen Co., Ltd.) cut into a 6 cm square was prepared. Ink composition 1 is injected into an ink jet apparatus (ULVAC ID-225) equipped with KM512MH (14 pL) manufactured by Konica Minolta IJ Co., Ltd. as an ink jet head, and discharge voltage is 13 V, head temperature is 30 ° C., drive frequency is 5 kHz, and coating Under a discharge condition of once, the printing resolution was set to 841 dpi, and coating was performed in the range of 5 cm square on the prepared substrate. By irradiating the aluminum foil coated with this ink composition 1 with UV light at a UV exposure amount of 2,000 mJ / cm 2 using a UV irradiation device (J-CURE 1500 manufactured by JATEC Corporation), the ink composition is obtained. An aluminum foil on which a cured film of product 1 was formed was obtained. The following measurements and evaluations were performed using the aluminum foil on which the cured film was formed.
デジマチックマイクロメーター((株)ミツトヨ製)を使用して測定した。インク組成物1の硬化膜が形成されたアルミ箔の厚さから、同様に測定した硬化膜を形成していないアルミ箔の厚さを差し引いたところ、13μmであった。膜厚の値には、3箇所の測定の平均値を用いた。 (Measurement of film thickness)
Measurement was performed using a Digimatic Micrometer (manufactured by Mitutoyo Corporation). It was 13 micrometers when the thickness of the aluminum foil in which the cured film similarly measured was not formed from the thickness of the aluminum foil in which the cured film of the ink composition 1 was formed was subtracted. The average value of three measurements was used as the film thickness value.
JIS D0202-1988に準拠して、碁盤目剥離試験を行った。セロハンテープ(商品名:CT24、ニチバン(株)製)を用い、指の腹でインク組成物1の硬化膜に付着させた後、2分後にテープ端を塗膜面に直角に保ち瞬間的に引き剥がした。評価は100マスの内、剥離しないマス目の数で表し、剥離がない場合を100/100、完全に剥離する場合を0/100とした。 (Evaluation of substrate adhesion)
A cross-cut peel test was performed in accordance with JIS D0202-1988. After using cellophane tape (trade name: CT24, manufactured by Nichiban Co., Ltd.) and attaching it to the cured film of ink composition 1 with the belly of the finger, 2 minutes later, the end of the tape is kept at right angles to the coating surface and instantaneously I peeled it off. The evaluation is represented by the number of squares that do not peel out of 100 squares. The case where there is no peeling is defined as 100/100, and the case where peeling completely occurs is defined as 0/100.
インク組成物1の硬化膜が形成されたアルミ箔を、温水を張った恒温槽で60℃に加熱した電解液(重量比でエチレンカーボネート:ジエチレンカーボネート=1:1)の入ったガラス容器に7日間浸漬した後に取り出し、硬化膜の剥離や膜自体に変化がないかを硬化膜の膜厚変化および膜外観を光学顕微鏡で確認した。評価は、硬化膜に剥離および膜自体に変化がない場合を「○」、部分的な剥離や膜自体に変化が見られる場合を「△」、硬化膜が完全に剥離する場合を「×」とした。 (Evaluation of electrolyte resistance)
The aluminum foil on which the cured film of the ink composition 1 was formed was placed in a glass container containing an electrolytic solution (ethylene carbonate: diethylene carbonate = 1: 1 by weight) heated to 60 ° C. in a thermostatic bath filled with warm water. It was taken out after being immersed for days, and the thickness change of the cured film and the appearance of the film were confirmed with an optical microscope to determine whether the cured film was peeled off or the film itself was changed. Evaluation is “◯” when the cured film has no peeling and no change in the film itself, “△” when a partial peeling or a change in the film itself is observed, and “×” when the cured film is completely peeled off It was.
以下に示すようにそれぞれの化合物をそれぞれの割合とした以外は実施例1と同様にしてインク組成物2を調製した。実施例1と同様に測定した粘度を以下に示す。
(A)EB168 0.1g
(B)DPGDA 4.9g
(C)Irg1173 0.7g
(D)PF656 0.001g
インク組成物2の粘度は、10.0mPa・sであった。このインク組成物2を用いて実施例1と同様の条件で硬化膜の形成したところ、膜厚12μmの硬化膜が得られた。その硬化膜について実施例1と同様の条件にて基材密着性の評価および電解液耐性の評価を行なった。結果を表1に示す。 (Example 2)
As shown below, an ink composition 2 was prepared in the same manner as in Example 1 except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
(A) EB168 0.1 g
(B) DPGDA 4.9 g
(C) Irg1173 0.7g
(D) PF656 0.001g
The viscosity of the ink composition 2 was 10.0 mPa · s. When a cured film was formed using the ink composition 2 under the same conditions as in Example 1, a cured film having a thickness of 12 μm was obtained. The cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
以下に示すようにそれぞれの化合物をそれぞれの割合とした以外は実施例1と同様にしてインク組成物3を調製した。実施例1と同様に測定した粘度を以下に示す。
(A)EB168 0.05g
(B)DPGDA 4.95g
(C)Irg1173 0.7g
(D)PF656 0.001g
インク組成物3の粘度は、9.7mPa・sであった。このインク組成物3を用いて実施例1と同様の条件で硬化膜の形成したところ、膜厚12μmの硬化膜が得られた。その硬化膜について実施例1と同様の条件にて基材密着性の評価および電解液耐性の評価を行なった。結果を表1に示す。 Example 3
As shown below, an ink composition 3 was prepared in the same manner as in Example 1 except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
(A) EB168 0.05g
(B) DPGDA 4.95 g
(C) Irg1173 0.7g
(D) PF656 0.001g
The viscosity of the ink composition 3 was 9.7 mPa · s. When a cured film was formed using this ink composition 3 under the same conditions as in Example 1, a cured film having a thickness of 12 μm was obtained. The cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
以下に示すようにそれぞれの化合物をそれぞれの割合とした以外は実施例1と同様にしてインク組成物4を調製した。実施例1と同様に測定した粘度を以下に示す。
(A)EB168 0.0005g
(B)DPGDA 4.9995g
(C)Irg1173 0.7g
(D)PF656 0.001g
インク組成物4の粘度は、9.4mPa・sであった。このインク組成物4を用いて実施例1と同様の条件で硬化膜の形成したところ、膜厚12μmの硬化膜が得られた。その硬化膜について実施例1と同様の条件にて基材密着性の評価および電解液耐性の評価を行なった。結果を表1に示す。 Example 4
As shown below, an ink composition 4 was prepared in the same manner as in Example 1, except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
(A) EB168 0.0005g
(B) DPGDA 4.9995 g
(C) Irg1173 0.7g
(D) PF656 0.001g
The viscosity of the ink composition 4 was 9.4 mPa · s. When a cured film was formed using this ink composition 4 under the same conditions as in Example 1, a cured film having a thickness of 12 μm was obtained. The cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
以下に示すようにそれぞれの化合物をそれぞれの割合とした以外は実施例1と同様にしてインク組成物5を調製した。実施例1と同様に測定した粘度を以下に示す。
(A)EB168 0.1g
(B)DPGDA 4.9g
(C)Irg651 0.7g
(D)PF656 0.001g
インク組成物5の粘度は、12.2mPa・sであった。このインク組成物5を用いて実施例1と同様の条件で硬化膜の形成したところ、膜厚12μmの硬化膜が得られた。その硬化膜について実施例1と同様の条件にて基材密着性の評価および電解液耐性の評価を行なった。結果を表1に示す。 (Example 5)
As shown below, an ink composition 5 was prepared in the same manner as in Example 1 except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
(A) EB168 0.1 g
(B) DPGDA 4.9 g
(C) Irg651 0.7g
(D) PF656 0.001g
The viscosity of the ink composition 5 was 12.2 mPa · s. When a cured film was formed using this ink composition 5 under the same conditions as in Example 1, a cured film having a thickness of 12 μm was obtained. The cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
以下に示すようにそれぞれの化合物をそれぞれの割合とした以外は実施例1と同様にしてインク組成物6を調製した。実施例1と同様に測定した粘度を以下に示す。
(A)EB168 0.1g
(B)DPGDA 4.9g
(C)Irg127 0.7g
(D)PF656 0.001g
インク組成物6の粘度は、15.5mPa・sであった。このインク組成物6を用いて、ヘッド温度を35℃に設定した以外は実施例1と同様の条件で硬化膜の形成したところ、膜厚13μmの硬化膜が得られた。その硬化膜について実施例1と同様の条件にて基材密着性の評価および電解液耐性の評価を行なった。結果を表1に示す。 (Example 6)
As shown below, an ink composition 6 was prepared in the same manner as in Example 1 except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
(A) EB168 0.1 g
(B) DPGDA 4.9 g
(C) Irg127 0.7g
(D) PF656 0.001g
The viscosity of the ink composition 6 was 15.5 mPa · s. When a cured film was formed using this ink composition 6 under the same conditions as in Example 1 except that the head temperature was set to 35 ° C., a cured film having a thickness of 13 μm was obtained. The cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
以下に示すようにそれぞれの化合物をそれぞれの割合とした以外は実施例1と同様にしてインク組成物7を調製した。実施例1と同様に測定した粘度を以下に示す。
(A)EB168 0.1g
(B)DPGDA 4.9g
(C)Irg184 0.7g
(D)PF656 0.001g
インク組成物7の粘度は、12.0mPa・sであった。このインク組成物7を用いて実施例1と同様の条件で硬化膜の形成したところ、膜厚12μmの硬化膜が得られた。その硬化膜について実施例1と同様の条件にて基材密着性の評価および電解液耐性の評価を行なった。結果を表1に示す。 (Example 7)
As shown below, an ink composition 7 was prepared in the same manner as in Example 1 except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
(A) EB168 0.1 g
(B) DPGDA 4.9 g
(C) Irg184 0.7g
(D) PF656 0.001g
The viscosity of the ink composition 7 was 12.0 mPa · s. When a cured film was formed using this ink composition 7 under the same conditions as in Example 1, a cured film having a thickness of 12 μm was obtained. The cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
以下に示すようにそれぞれの化合物をそれぞれの割合とした以外は実施例1と同様にしてインク組成物8を調製した。実施例1と同様に測定した粘度を以下に示す。
(A)EB168 0.1g
(B)NPDA 4.9g
(C)Irg1173 0.7g
(D)PF656 0.001g
インク組成物8の粘度は、6.7mPa・sであった。このインク組成物8を用いて、吐出電圧を11Vに設定した以外は実施例1と同様の条件で硬化膜の形成したところ、膜厚12μmの硬化膜が得られた。その硬化膜について実施例1と同様の条件にて基材密着性の評価および電解液耐性の評価を行なった。結果を表1に示す。 (Example 8)
As shown below, an ink composition 8 was prepared in the same manner as in Example 1 except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
(A) EB168 0.1 g
(B) NPDA 4.9 g
(C) Irg1173 0.7g
(D) PF656 0.001g
The viscosity of the ink composition 8 was 6.7 mPa · s. Using this ink composition 8, a cured film was formed under the same conditions as in Example 1 except that the discharge voltage was set to 11 V. As a result, a cured film having a thickness of 12 μm was obtained. The cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
以下に示すようにそれぞれの化合物をそれぞれの割合とした以外は実施例1と同様にしてインク組成物9を調製した。実施例1と同様に測定した粘度を以下に示す。
(A)EB168 0.1g
(B)HPNDA 4.9g
(C)Irg1173 0.7g
(D)PF656 0.001g
インク組成物9の粘度は、21.6mPa・sであった。このインク組成物9を用いて、ヘッド温度を40℃に設定した以外は実施例1と同様の条件で硬化膜の形成したところ、膜厚15μmの硬化膜が得られた。その硬化膜について実施例1と同様の条件にて基材密着性の評価および電解液耐性の評価を行なった。結果を表1に示す。 Example 9
As shown below, an ink composition 9 was prepared in the same manner as in Example 1 except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
(A) EB168 0.1 g
(B) HPNDA 4.9 g
(C) Irg1173 0.7g
(D) PF656 0.001g
The viscosity of the ink composition 9 was 21.6 mPa · s. When a cured film was formed using this ink composition 9 under the same conditions as in Example 1 except that the head temperature was set to 40 ° C., a cured film having a thickness of 15 μm was obtained. The cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
以下に示すようにそれぞれの化合物をそれぞれの割合とした以外は実施例1と同様にしてインク組成物10を調製した。実施例1と同様に測定した粘度を以下に示す。
(A)EB168 0.1g
(B)SR9003 4.9g
(C)Irg1173 0.7g
(D)PF656 0.001g
インク組成物10の粘度は、16.6mPa・sであった。このインク組成物10を用いて、ヘッド温度を35℃に設定した以外は実施例1と同様の条件で硬化膜の形成したところ、膜厚14μmの硬化膜が得られた。その硬化膜について実施例1と同様の条件にて基材密着性の評価および電解液耐性の評価を行なった。結果を表1に示す。 (Example 10)
As shown below, an ink composition 10 was prepared in the same manner as in Example 1 except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
(A) EB168 0.1 g
(B) SR9003 4.9 g
(C) Irg1173 0.7g
(D) PF656 0.001g
The viscosity of the ink composition 10 was 16.6 mPa · s. When a cured film was formed using this ink composition 10 under the same conditions as in Example 1 except that the head temperature was set to 35 ° C., a cured film having a thickness of 14 μm was obtained. The cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
以下に示すようにそれぞれの化合物をそれぞれの割合とした以外は実施例1と同様にしてインク組成物11を調製した。実施例1と同様に測定した粘度を以下に示す。
(A)EB168 0.1g
(B)TPGDA 4.9g
(C)Irg1173 0.7g
(D)PF656 0.001g
インク組成物11の粘度は、14.8mPa・sであった。このインク組成物11を用いて、ヘッド温度を35℃に設定した以外は実施例1と同様の条件で硬化膜の形成したところ、膜厚13μmの硬化膜が得られた。その硬化膜について実施例1と同様の条件にて基材密着性の評価および電解液耐性の評価を行なった。結果を表1に示す。 (Example 11)
As shown below, an ink composition 11 was prepared in the same manner as in Example 1 except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
(A) EB168 0.1 g
(B) TPGDA 4.9g
(C) Irg1173 0.7g
(D) PF656 0.001g
The viscosity of the ink composition 11 was 14.8 mPa · s. When a cured film was formed using this ink composition 11 under the same conditions as in Example 1 except that the head temperature was set to 35 ° C., a cured film having a thickness of 13 μm was obtained. The cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
以下に示すようにそれぞれの化合物をそれぞれの割合とした以外は実施例1と同様にしてインク組成物12を調製した。実施例1と同様に測定した粘度を以下に示す。
(A)EB168 0.1g
(B)701A 4.9g
(C)Irg1173 0.7g
(D)PF656 0.001g
インク組成物12の粘度は、42.1mPa・sであった。このインク組成物12を用いて、ヘッド温度を50℃に設定した以外は実施例1と同様の条件で硬化膜の形成したところ、膜厚15μmの硬化膜が得られた。その硬化膜について実施例1と同様の条件にて基材密着性の評価および電解液耐性の評価を行なった。結果を表1に示す。 Example 12
As shown below, an ink composition 12 was prepared in the same manner as in Example 1 except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
(A) EB168 0.1 g
(B) 701A 4.9 g
(C) Irg1173 0.7g
(D) PF656 0.001g
The viscosity of the ink composition 12 was 42.1 mPa · s. Using this ink composition 12, a cured film was formed under the same conditions as in Example 1 except that the head temperature was set to 50 ° C., and a cured film having a thickness of 15 μm was obtained. The cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
以下に示すようにそれぞれの化合物をそれぞれの割合とした以外は実施例1と同様にしてインク組成物13を調製した。実施例1と同様に測定した粘度を以下に示す。
(A)EB168 0.1g
(B)1,3-BGDA 4.9g
(C)Irg1173 0.7g
(D)PF656 0.001g
インク組成物13の粘度は、6.7mPa・sであった。このインク組成物13を用いて、吐出電圧を11Vに設定した以外は実施例1と同様の条件で硬化膜の形成したところ、膜厚13μmの硬化膜が得られた。その硬化膜について実施例1と同様の条件にて基材密着性の評価および電解液耐性の評価を行なった。結果を表1に示す。 (Example 13)
As shown below, an ink composition 13 was prepared in the same manner as in Example 1 except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
(A) EB168 0.1 g
(B) 1,3-BGDA 4.9 g
(C) Irg1173 0.7g
(D) PF656 0.001g
The viscosity of the ink composition 13 was 6.7 mPa · s. Using this ink composition 13, a cured film was formed under the same conditions as in Example 1 except that the discharge voltage was set to 11 V. As a result, a cured film having a thickness of 13 μm was obtained. The cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
以下に示すようにそれぞれの化合物をそれぞれの割合とした以外は実施例1と同様にしてインク組成物14を調製した。実施例1と同様に測定した粘度を以下に示す。
(A)EB168 0.1g
(B)DPGDA 3.92g
(B)FA-513AS 1.47g
(C)Irg1173 0.7g
(D)PF656 0.001g
インク組成物14の粘度は、9.8mPa・sであった。このインク組成物14を用いて実施例1と同様の条件で硬化膜の形成したところ、膜厚13μmの硬化膜が得られた。その硬化膜について実施例1と同様の条件にて基材密着性の評価および電解液耐性の評価を行なった。結果を表1に示す。 (Example 14)
As shown below, an ink composition 14 was prepared in the same manner as in Example 1 except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
(A) EB168 0.1 g
(B) DPGDA 3.92g
(B) FA-513AS 1.47 g
(C) Irg1173 0.7g
(D) PF656 0.001g
The viscosity of the ink composition 14 was 9.8 mPa · s. When a cured film was formed using this ink composition 14 under the same conditions as in Example 1, a cured film having a thickness of 13 μm was obtained. The cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
以下に示すようにそれぞれの化合物をそれぞれの割合とした以外は実施例1と同様にしてインク組成物15を調製した。実施例1と同様に測定した粘度を以下に示す。
(A)EB168 0.1g
(B)DPGDA 3.92g
(B)IBXA 1.47g
(C)Irg1173 0.7g
(D)PF656 0.001g
インク組成物15の粘度は、9.0mPa・sであった。このインク組成物15を用いて実施例1と同様の条件で硬化膜の形成したところ、膜厚13μmの硬化膜が得られた。その硬化膜について実施例1と同様の条件にて基材密着性の評価および電解液耐性の評価を行なった。結果を表1に示す。 (Example 15)
As shown below, an ink composition 15 was prepared in the same manner as in Example 1 except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
(A) EB168 0.1 g
(B) DPGDA 3.92g
(B) 1.47 g of IBXA
(C) Irg1173 0.7g
(D) PF656 0.001g
The viscosity of the ink composition 15 was 9.0 mPa · s. When a cured film was formed using this ink composition 15 under the same conditions as in Example 1, a cured film having a thickness of 13 μm was obtained. The cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
以下に示すようにそれぞれの化合物をそれぞれの割合とした以外は実施例1と同様にしてインク組成物16を調製した。実施例1と同様に測定した粘度を以下に示す。
(A)EB168 0.1g
(B)DPGDA 3.92g
(B)BzMA 1.47g
(C)Irg1173 0.7g
(D)PF656 0.001g
インク組成物16の粘度は、6.8mPa・sであった。このインク組成物16を用いて、吐出電圧を11Vに設定した以外は実施例1と同様の条件で硬化膜の形成したところ、膜厚14μmの硬化膜が得られた。その硬化膜について実施例1と同様の条件にて基材密着性の評価および電解液耐性の評価を行なった。結果を表1に示す。 (Example 16)
As shown below, an ink composition 16 was prepared in the same manner as in Example 1 except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
(A) EB168 0.1 g
(B) DPGDA 3.92g
(B) 1.47 g of BzMA
(C) Irg1173 0.7g
(D) PF656 0.001g
The viscosity of the ink composition 16 was 6.8 mPa · s. When a cured film was formed using this ink composition 16 under the same conditions as in Example 1 except that the discharge voltage was set to 11 V, a cured film having a thickness of 14 μm was obtained. The cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
以下に示すようにそれぞれの化合物をそれぞれの割合とした以外は実施例1と同様にしてインク組成物17を調製した。実施例1と同様に測定した粘度を以下に示す。
(A)EB168 0.1g
(B)DPGDA 3.92g
(B)M-208 1.47g
(C)Irg1173 0.7g
(D)PF656 0.001g
インク組成物17の粘度は、21.9mPa・sであった。このインク組成物17を用いて、ヘッド温度を40℃に設定した以外は実施例1と同様の条件で硬化膜の形成したところ、膜厚15μmの硬化膜が得られた。その硬化膜について実施例1と同様の条件にて基材密着性の評価および電解液耐性の評価を行なった。結果を表1に示す。 (Example 17)
As shown below, an ink composition 17 was prepared in the same manner as in Example 1 except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
(A) EB168 0.1 g
(B) DPGDA 3.92g
(B) M-208 1.47g
(C) Irg1173 0.7g
(D) PF656 0.001g
The viscosity of the ink composition 17 was 21.9 mPa · s. Using this ink composition 17, a cured film was formed under the same conditions as in Example 1 except that the head temperature was set to 40 ° C., and a cured film having a thickness of 15 μm was obtained. The cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
以下に示すようにそれぞれの化合物をそれぞれの割合とした以外は実施例1と同様にしてインク組成物18を調製した。実施例1と同様に測定した粘度を以下に示す。
(A)EB168 0.1g
(B)DPGDA 3.92g
(B)IRR214-K 1.47g
(C)Irg1173 0.7g
(D)PF656 0.001g
インク組成物18の粘度は、15.8mPa・sであった。このインク組成物18を用いて、ヘッド温度を35℃に設定した以外は実施例1と同様の条件で硬化膜の形成したところ、膜厚14μmの硬化膜が得られた。その硬化膜について実施例1と同様の条件にて基材密着性の評価および電解液耐性の評価を行なった。結果を表1に示す。 (Example 18)
As shown below, an ink composition 18 was prepared in the same manner as in Example 1, except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
(A) EB168 0.1 g
(B) DPGDA 3.92g
(B) IRR214-K 1.47 g
(C) Irg1173 0.7g
(D) PF656 0.001g
The viscosity of the ink composition 18 was 15.8 mPa · s. When a cured film was formed using this ink composition 18 under the same conditions as in Example 1 except that the head temperature was set to 35 ° C., a cured film having a thickness of 14 μm was obtained. The cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
以下に示すようにそれぞれの化合物をそれぞれの割合とした以外は実施例1と同様にしてインク組成物19を調製した。実施例1と同様に測定した粘度を以下に示す。
(A)EB168 0.1g
(B)DPGDA 3.92g
(B)DOGDA 1.47g
(C)Irg1173 0.7g
(D)PF656 0.001g
インク組成物19の粘度は、16.4mPa・sであった。このインク組成物19を用いて、ヘッド温度を35℃に設定した以外は実施例1と同様の条件で硬化膜の形成したところ、膜厚14μmの硬化膜が得られた。その硬化膜について実施例1と同様の条件にて基材密着性の評価および電解液耐性の評価を行なった。結果を表1に示す。 (Example 19)
As shown below, an ink composition 19 was prepared in the same manner as in Example 1, except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
(A) EB168 0.1 g
(B) DPGDA 3.92g
(B) DOGDA 1.47g
(C) Irg1173 0.7g
(D) PF656 0.001g
The viscosity of the ink composition 19 was 16.4 mPa · s. When a cured film was formed using this ink composition 19 under the same conditions as in Example 1 except that the head temperature was set to 35 ° C., a cured film having a thickness of 14 μm was obtained. The cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
以下に示すようにそれぞれの化合物をそれぞれの割合とした以外は実施例1と同様にしてインク組成物20を調製した。実施例1と同様に測定した粘度を以下に示す。
(A)EB168 0.1g
(B)DPGDA 3.92g
(B)TMPTA 1.47g
(C)Irg1173 0.7g
(D)PF656 0.001g
インク組成物20の粘度は、14.7mPa・sであった。このインク組成物20を用いて、ヘッド温度を35℃に設定した以外は実施例1と同様の条件で硬化膜の形成したところ、膜厚14μmの硬化膜が得られた。その硬化膜について実施例1と同様の条件にて基材密着性の評価および電解液耐性の評価を行なった。結果を表1に示す。 (Example 20)
As shown below, an ink composition 20 was prepared in the same manner as in Example 1 except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
(A) EB168 0.1 g
(B) DPGDA 3.92g
(B) 1.47 g of TMPTA
(C) Irg1173 0.7g
(D) PF656 0.001g
The viscosity of the ink composition 20 was 14.7 mPa · s. When a cured film was formed using this ink composition 20 under the same conditions as in Example 1 except that the head temperature was set to 35 ° C., a cured film having a thickness of 14 μm was obtained. The cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
以下に示すようにそれぞれの化合物をそれぞれの割合とした以外は実施例1と同様にしてインク組成物21を調製した。実施例1と同様に測定した粘度を以下に示す。
(A)EB168 0.1g
(B)DPGDA 1.47g
(B)TMPTA 3.92g
(C)Irg1173 0.7g
(D)PF656 0.001g
インク組成物21の粘度は、34.8mPa・sであった。このインク組成物21を用いて、ヘッド温度を50℃に設定した以外は実施例1と同様の条件で硬化膜の形成したところ、膜厚15μmの硬化膜が得られた。その硬化膜について実施例1と同様の条件にて基材密着性の評価および電解液耐性の評価を行なった。結果を表1に示す。 (Example 21)
As shown below, an ink composition 21 was prepared in the same manner as in Example 1 except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
(A) EB168 0.1 g
(B) DPGDA 1.47g
(B) 3.92 g of TMPTA
(C) Irg1173 0.7g
(D) PF656 0.001g
The viscosity of the ink composition 21 was 34.8 mPa · s. When a cured film was formed using this ink composition 21 under the same conditions as in Example 1 except that the head temperature was set to 50 ° C., a cured film having a thickness of 15 μm was obtained. The cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
以下に示すようにそれぞれの化合物をそれぞれの割合とした以外は実施例1と同様にしてインク組成物22を調製した。実施例1と同様に測定した粘度を以下に示す。
(A)EB168 0.1g
(B)DPGDA 3.92g
(B)M-305 1.47g
(C)Irg1173 0.7g
(D)PF656 0.001g
インク組成物22の粘度は、19.7mPa・sであった。このインク組成物22を用いて、ヘッド温度を40℃に設定した以外は実施例1と同様の条件で硬化膜の形成したところ、膜厚16μmの硬化膜が得られた。その硬化膜について実施例1と同様の条件にて基材密着性の評価および電解液耐性の評価を行なった。結果を表1に示す。 (Example 22)
As shown below, an ink composition 22 was prepared in the same manner as in Example 1 except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
(A) EB168 0.1 g
(B) DPGDA 3.92g
(B) M-305 1.47g
(C) Irg1173 0.7g
(D) PF656 0.001g
The viscosity of the ink composition 22 was 19.7 mPa · s. Using this ink composition 22, a cured film was formed under the same conditions as in Example 1 except that the head temperature was set to 40 ° C. As a result, a cured film having a thickness of 16 μm was obtained. The cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
以下に示すようにそれぞれの化合物をそれぞれの割合とした以外は実施例1と同様にしてインク組成物23を調製した。実施例1と同様に測定した粘度を以下に示す。
(A)EB168 0.1g
(B)DPGDA 2.94g
(B)FA-513AS 1.96g
(C)Irg1173 0.7g
(D)PF656 0.001g
インク組成物23の粘度は、9.9mPa・sであった。このインク組成物23を用いて実施例1と同様の条件で硬化膜の形成したところ、膜厚14μmの硬化膜が得られた。その硬化膜について実施例1と同様の条件にて基材密着性の評価および電解液耐性の評価を行なった。結果を表1に示す。 (Example 23)
As shown below, an ink composition 23 was prepared in the same manner as in Example 1 except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
(A) EB168 0.1 g
(B) DPGDA 2.94 g
(B) FA-513AS 1.96 g
(C) Irg1173 0.7g
(D) PF656 0.001g
The viscosity of the ink composition 23 was 9.9 mPa · s. When a cured film was formed using this ink composition 23 under the same conditions as in Example 1, a cured film having a thickness of 14 μm was obtained. The cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
以下に示すようにそれぞれの化合物をそれぞれの割合とした以外は実施例1と同様にしてインク組成物24を調製した。実施例1と同様に測定した粘度を以下に示す。
(A)EB168 0.1g
(B)DPGDA 2.94g
(B)IBXA 1.96g
(C)Irg1173 0.7g
(D)PF656 0.001g
インク組成物24の粘度は、8.5mPa・sであった。このインク組成物24を用いて実施例1と同様の条件で硬化膜の形成したところ、膜厚13μmの硬化膜が得られた。その硬化膜について実施例1と同様の条件にて基材密着性の評価および電解液耐性の評価を行なった。結果を表1に示す。 (Example 24)
As shown below, an ink composition 24 was prepared in the same manner as in Example 1 except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
(A) EB168 0.1 g
(B) DPGDA 2.94 g
(B) IBXA 1.96 g
(C) Irg1173 0.7g
(D) PF656 0.001g
The viscosity of the ink composition 24 was 8.5 mPa · s. When a cured film was formed using this ink composition 24 under the same conditions as in Example 1, a cured film having a thickness of 13 μm was obtained. The cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
以下に示すようにそれぞれの化合物をそれぞれの割合とした以外は実施例1と同様にしてインク組成物25を調製した。実施例1と同様に測定した粘度を以下に示す。
(A)EB168 0.1g
(B)FA-513AS 2.95g
(B)M-208 2.00g
(C)Irg1173 0.7g
(D)PF656 0.001g
インク組成物25の粘度は、37.2mPa・sであった。 (Example 25)
As shown below, an ink composition 25 was prepared in the same manner as in Example 1, except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
(A) EB168 0.1 g
(B) FA-513AS 2.95 g
(B) M-208 2.00g
(C) Irg1173 0.7g
(D) PF656 0.001g
The viscosity of the ink composition 25 was 37.2 mPa · s.
硬化膜を形成する基材として、6cm角に裁断したSUS304(日本テストパネル(株)製、150μm厚)を用意した。コニカミノルタIJ(株)製のKM512MH(14pL)をインクジェットヘッドとして搭載したインクジェット装置(アルバック製ID-225)にインク組成物25を注入し、吐出電圧13V、ヘッド温度50℃、駆動周波数5kHz、塗布回数1回の吐出条件で、印刷解像度を841dpiに設定して、用意した基板上に5cm角の範囲で塗布した。このインク組成物25が塗布されたSUS基板に、UV照射装置((株)ジャテック製のJ-CURE1500)を用いて紫外線を2,000mJ/cm2のUV露光量で照射することで、インク組成物25の硬化膜が形成されたSUS基板を得た。この硬化膜が形成されたSUS基板を用いて、以下の測定および評価を行った。 (Formation of cured film)
As a base material for forming a cured film, SUS304 (manufactured by Nippon Test Panel Co., Ltd., 150 μm thick) cut into a 6 cm square was prepared. Ink composition 25 is injected into an ink jet apparatus (ULVAC ID-225) equipped with KM512MH (14 pL) manufactured by Konica Minolta IJ Co., Ltd. as an ink jet head, discharge voltage 13 V, head temperature 50 ° C., drive frequency 5 kHz, coating Under a discharge condition of once, the printing resolution was set to 841 dpi, and coating was performed in the range of 5 cm square on the prepared substrate. The SUS substrate coated with the ink composition 25 is irradiated with ultraviolet rays at a UV exposure amount of 2,000 mJ / cm 2 using a UV irradiation device (J-CURE 1500 manufactured by JATEC Co., Ltd.). The SUS board | substrate with which the cured film of the thing 25 was formed was obtained. The following measurement and evaluation were performed using the SUS substrate on which the cured film was formed.
デジマチックマイクロメーター((株)ミツトヨ製)を使用して測定した。インク組成物25の硬化膜が形成されたSUS基板の厚さから、同様に測定した硬化膜を形成していないSUS基板の厚さを差し引いたところ、15μmであった。膜厚の値には、3箇所の測定の平均値を用いた。 (Measurement of film thickness)
Measurement was performed using a Digimatic Micrometer (manufactured by Mitutoyo Corporation). It was 15 micrometers when the thickness of the SUS board | substrate which has not formed the cured film measured similarly was subtracted from the thickness of the SUS board | substrate with which the cured film of the ink composition 25 was formed. The average value of three measurements was used as the film thickness value.
JIS D0202-1988に準拠して、碁盤目剥離試験を行った。セロハンテープ(商品名:CT24、ニチバン(株)製)を用い、指の腹でインク組成物25の硬化膜に付着させた後、2分後にテープ端を塗膜面に直角に保ち瞬間的に引き剥がした。評価は100マスの内、剥離しないマス目の数で表し、剥離がない場合を100/100、完全に剥離する場合を0/100とした。 (Evaluation of substrate adhesion)
A cross-cut peel test was performed in accordance with JIS D0202-1988. After using cellophane tape (trade name: CT24, manufactured by Nichiban Co., Ltd.) and attaching it to the cured film of the ink composition 25 with the belly of the finger, 2 minutes later, the tape edge is kept at right angles to the coating film surface and instantaneously I peeled it off. The evaluation is represented by the number of squares that do not peel out of 100 squares. The case where there is no peeling is defined as 100/100, and the case where peeling completely occurs is defined as 0/100.
インク組成物25の硬化膜が形成されたSUS基板を、温水を張った恒温槽で40℃に調整した洗浄剤であるジクロロペンタンフルオロカーボン(HCFC-225)の入ったガラス容器に30分浸漬した後に取り出し、硬化膜の剥離や膜自体に変化がないかを硬化膜の膜厚変化および膜外観を光学顕微鏡で確認した。評価は、硬化膜に剥離および膜自体に変化がない場合を「○」、部分的な剥離や膜自体に変化が見られる場合を「△」、硬化膜が完全に剥離する場合を「×」とした。 (Evaluation of detergent resistance)
After immersing a SUS substrate on which a cured film of the ink composition 25 is formed in a glass container containing dichloropentanefluorocarbon (HCFC-225), which is a cleaning agent adjusted to 40 ° C. in a thermostatic bath filled with warm water, for 30 minutes. The film was taken out, and the change in the thickness of the cured film and the appearance of the film were confirmed with an optical microscope to determine whether the cured film was peeled off or the film itself was changed. Evaluation is “◯” when the cured film has no peeling and no change in the film itself, “△” when a partial peeling or a change in the film itself is observed, and “×” when the cured film is completely peeled off It was.
以下に示すようにそれぞれの化合物をそれぞれの割合とした以外は実施例1と同様にしてインク組成物26を調製した。実施例1と同様に測定した粘度を以下に示す。
(A)EB168 0.1g
(B)IB-XA 2.95g
(B)M-208 2.00g
(C)Irg1173 0.7g
(D)PF656 0.001g
インク組成物26の粘度は、28.1mPa・sであった。
このインク組成物26を用いて、ヘッド温度を45℃に設定した以外は実施例25と同様の条件で硬化膜の形成したところ、膜厚15μmの硬化膜が得られた。その硬化膜について実施例25と同様の条件にて基材密着性の評価および洗浄剤耐性の評価を行なった。結果を表2に示す。 (Example 26)
As shown below, an ink composition 26 was prepared in the same manner as in Example 1 except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
(A) EB168 0.1 g
(B) IB-XA 2.95 g
(B) M-208 2.00g
(C) Irg1173 0.7g
(D) PF656 0.001g
The viscosity of the ink composition 26 was 28.1 mPa · s.
Using this ink composition 26, a cured film was formed under the same conditions as in Example 25 except that the head temperature was set to 45 ° C., and a cured film having a thickness of 15 μm was obtained. The cured film was evaluated for substrate adhesion and detergent resistance under the same conditions as in Example 25. The results are shown in Table 2.
以下に示すようにそれぞれの化合物をそれぞれの割合とした以外は実施例1と同様にしてインク組成物27を調製した。実施例1と同様に測定した粘度を以下に示す。
(A)EB168 0.1g
(B)IBXA 3.45g
(B)M-208 1.50g
(C)Irg1173 0.7g
(D)PF656 0.001g
インク組成物27の粘度は、19.9mPa・sであった。
このインク組成物27を用いて、ヘッド温度を40℃に設定した以外は実施例25と同様の条件で硬化膜の形成したところ、膜厚16μmの硬化膜が得られた。その硬化膜について実施例25と同様の条件にて基材密着性の評価および洗浄剤耐性の評価を行なった。結果を表2に示す。 (Example 27)
As shown below, an ink composition 27 was prepared in the same manner as in Example 1 except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
(A) EB168 0.1 g
(B) 3.45 g of IBXA
(B) M-208 1.50 g
(C) Irg1173 0.7g
(D) PF656 0.001g
The viscosity of the ink composition 27 was 19.9 mPa · s.
Using this ink composition 27, a cured film was formed under the same conditions as in Example 25 except that the head temperature was set to 40 ° C. As a result, a cured film having a thickness of 16 μm was obtained. The cured film was evaluated for substrate adhesion and detergent resistance under the same conditions as in Example 25. The results are shown in Table 2.
以下に示すようにそれぞれの化合物をそれぞれの割合とした以外は実施例1と同様にしてインク組成物28を調製した。実施例1と同様に測定した粘度を以下に示す。
(B)DPGDA 5g
(C)Irg1173 0.7g
(D)PF656 0.001g
インク組成物28の粘度は、9.4mPa・sであった。このインク組成物28を用いて実施例1と同様の条件で硬化膜の形成したところ、膜厚13μmの硬化膜が得られた。その硬化膜について実施例1と同様の条件にて基材密着性の評価および電解液耐性の評価を行なった。結果を表1に示す。 (Comparative Example 1)
As shown below, an ink composition 28 was prepared in the same manner as in Example 1, except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
(B) DPGDA 5g
(C) Irg1173 0.7g
(D) PF656 0.001g
The viscosity of the ink composition 28 was 9.4 mPa · s. When a cured film was formed using this ink composition 28 under the same conditions as in Example 1, a cured film having a thickness of 13 μm was obtained. The cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
以下に示すようにそれぞれの化合物をそれぞれの割合とした以外は実施例1と同様にしてインク組成物29を調製した。実施例1と同様に測定した粘度を以下に示す。
(A)EB168 0.5g
(B)DPGDA 4.5g
(C)Irg1173 0.7g
(D)PF656 0.001g
インク組成物29の粘度は、13.2mPa・sであった。このインク組成物29を用いて、ヘッド温度を35℃に設定した以外は実施例1と同様の条件で硬化膜の形成したところ、膜厚13μmの硬化膜が得られた。その硬化膜について実施例1と同様の条件にて基材密着性の評価および電解液耐性の評価を行なった。結果を表1に示す。 (Comparative Example 2)
As shown below, an ink composition 29 was prepared in the same manner as in Example 1 except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
(A) EB168 0.5g
(B) DPGDA 4.5g
(C) Irg1173 0.7g
(D) PF656 0.001g
The viscosity of the ink composition 29 was 13.2 mPa · s. Using this ink composition 29, a cured film was formed under the same conditions as in Example 1 except that the head temperature was set to 35 ° C. A cured film having a thickness of 13 μm was obtained. The cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
以下に示すようにそれぞれの化合物をそれぞれの割合とした以外は実施例1と同様にしてインク組成物30を調製した。実施例1と同様に測定した粘度を以下に示す。
(A)EB168 1g
(B)DPGDA 4g
(C)Irg1173 0.7g
(D)PF656 0.001g
インク組成物30の粘度は、18.0mPa・sであった。このインク組成物30を用いて、ヘッド温度を40℃に設定した以外は実施例1と同様の条件で硬化膜の形成したところ、膜厚14μmの硬化膜が得られた。その硬化膜について実施例1と同様の条件にて基材密着性の評価および電解液耐性の評価を行なった。結果を表1に示す。 (Comparative Example 3)
As shown below, an ink composition 30 was prepared in the same manner as in Example 1 except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
(A) EB168 1g
(B) DPGDA 4g
(C) Irg1173 0.7g
(D) PF656 0.001g
The viscosity of the ink composition 30 was 18.0 mPa · s. Using this ink composition 30, a cured film was formed under the same conditions as in Example 1 except that the head temperature was set to 40 ° C. As a result, a cured film having a thickness of 14 μm was obtained. The cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
以下に示すようにそれぞれの化合物をそれぞれの割合とした以外は実施例1と同様にしてインク組成物31を調製した。実施例1と同様に測定した粘度を以下に示す。
(A)EB168 0.1g
(B)DPGDA 4.9g
IrgMBF 0.7g
(D)PF656 0.001g
インク組成物31の粘度は、8.7mPa・sであった。このインク組成物31を用いて実施例1と同様の条件で硬化膜の形成したところ、膜厚13μmの硬化膜が得られた。その硬化膜について実施例1と同様の条件にて基材密着性の評価および電解液耐性の評価を行なった。結果を表1に示す。 (Comparative Example 4)
As shown below, an ink composition 31 was prepared in the same manner as in Example 1, except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
(A) EB168 0.1 g
(B) DPGDA 4.9 g
IrgMBF 0.7g
(D) PF656 0.001g
The viscosity of the ink composition 31 was 8.7 mPa · s. When a cured film was formed using this ink composition 31 under the same conditions as in Example 1, a cured film having a thickness of 13 μm was obtained. The cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
以下に示すようにそれぞれの化合物をそれぞれの割合とした以外は実施例1と同様にしてインク組成物32を調製した。実施例1と同様に測定した粘度を以下に示す。
(A)EB168 0.1g
(B)DPGDA 4.9g
Irg754 0.7g
(D)PF656 0.001g
インク組成物32の粘度は、12.4mPa・sであった。このインク組成物32を用いて実施例1と同様の条件で硬化膜の形成したところ、膜厚13μmの硬化膜が得られた。その硬化膜について実施例1と同様の条件にて基材密着性の評価および電解液耐性の評価を行なった。結果を表1に示す。 (Comparative Example 5)
As shown below, an ink composition 32 was prepared in the same manner as in Example 1 except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
(A) EB168 0.1 g
(B) DPGDA 4.9 g
Irg754 0.7g
(D) PF656 0.001g
The viscosity of the ink composition 32 was 12.4 mPa · s. When a cured film was formed under the same conditions as in Example 1 using this ink composition 32, a cured film having a thickness of 13 μm was obtained. The cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
以下に示すようにそれぞれの化合物をそれぞれの割合とした以外は実施例1と同様にしてインク組成物33を調製した。実施例1と同様に測定した粘度を以下に示す。
(A)EB168 0.1g
(B)DPGDA 4.9g
IrgTPO 0.7g
(D)PF656 0.001g
インク組成物33の粘度は、14.3mPa・sであった。このインク組成物33を用いて、ヘッド温度を35℃に設定した以外は実施例1と同様の条件で硬化膜の形成したところ、膜厚13μmの硬化膜が得られた。その硬化膜について実施例1と同様の条件にて基材密着性の評価および電解液耐性の評価を行なった。結果を表1に示す。 (Comparative Example 6)
As shown below, an ink composition 33 was prepared in the same manner as in Example 1, except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
(A) EB168 0.1 g
(B) DPGDA 4.9 g
IrgTPO 0.7g
(D) PF656 0.001g
The viscosity of the ink composition 33 was 14.3 mPa · s. Using this ink composition 33, a cured film was formed under the same conditions as in Example 1 except that the head temperature was set to 35 ° C. A cured film having a thickness of 13 μm was obtained. The cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
以下に示すようにそれぞれの化合物をそれぞれの割合とした以外は実施例1と同様にしてインク組成物34を調製した。実施例1と同様に測定した粘度を以下に示す。
(A)EB168 0.1g
3EG 5.39g
(C)Irg1173 0.7g
(D)PF656 0.001g
インク組成物34の粘度は、9.9mPa・sであった。このインク組成物34を用いて実施例1と同様の条件で硬化膜の形成したところ、膜厚13μmの硬化膜が得られた。その硬化膜について実施例1と同様の条件にて基材密着性の評価および電解液耐性の評価を行なった。結果を表1に示す。 (Comparative Example 7)
As shown below, an ink composition 34 was prepared in the same manner as in Example 1, except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
(A) EB168 0.1 g
3EG 5.39g
(C) Irg1173 0.7g
(D) PF656 0.001g
The viscosity of the ink composition 34 was 9.9 mPa · s. When a cured film was formed using this ink composition 34 under the same conditions as in Example 1, a cured film having a thickness of 13 μm was obtained. The cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
以下に示すようにそれぞれの化合物をそれぞれの割合とした以外は実施例1と同様にしてインク組成物35を調製した。実施例1と同様に測定した粘度を以下に示す。
(A)EB168 0.1g
3EG 3.92g
4EG 1.47g
(C)Irg1173 0.7g
(D)PF656 0.001g
インク組成物35の粘度は、11.5mPa・sであった。このインク組成物35を用いて実施例1と同様の条件で硬化膜の形成したところ、膜厚12μmの硬化膜が得られた。その硬化膜について実施例1と同様の条件にて基材密着性の評価および電解液耐性の評価を行なった。結果を表1に示す。 (Comparative Example 8)
As shown below, an ink composition 35 was prepared in the same manner as in Example 1, except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
(A) EB168 0.1 g
3EG 3.92g
4EG 1.47g
(C) Irg1173 0.7g
(D) PF656 0.001g
The viscosity of the ink composition 35 was 11.5 mPa · s. When a cured film was formed using this ink composition 35 under the same conditions as in Example 1, a cured film having a thickness of 12 μm was obtained. The cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
以下に示すようにそれぞれの化合物をそれぞれの割合とした以外は実施例1と同様にしてインク組成物36を調製した。実施例1と同様に測定した粘度を以下に示す。
(A)EB168 0.1g
3EG 3.92g
A-BPE-10 1.47g
(C)Irg1173 0.7g
(D)PF656 0.001g
インク組成物36の粘度は、25.8mPa・sであった。このインク組成物36を用いて、ヘッド温度を40℃に設定した以外は実施例1と同様の条件で硬化膜の形成したところ、膜厚15μmの硬化膜が得られた。その硬化膜について実施例1と同様の条件にて基材密着性の評価および電解液耐性の評価を行なった。結果を表1に示す。 (Comparative Example 9)
As shown below, an ink composition 36 was prepared in the same manner as in Example 1, except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
(A) EB168 0.1 g
3EG 3.92g
A-BPE-10 1.47g
(C) Irg1173 0.7g
(D) PF656 0.001g
The viscosity of the ink composition 36 was 25.8 mPa · s. Using this ink composition 36, a cured film was formed under the same conditions as in Example 1 except that the head temperature was set to 40 ° C. As a result, a cured film having a thickness of 15 μm was obtained. The cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
以下に示すようにそれぞれの化合物をそれぞれの割合とした以外は実施例1と同様にしてインク組成物37を調製した。実施例1と同様に測定した粘度を以下に示す。
(A)EB168 0.1g
3EG 3.92g
A-GLY-9E 1.47g
(C)Irg1173 0.7g
(D)PF656 0.001g
インク組成物37の粘度は、17.7mPa・sであった。このインク組成物37を用いて、ヘッド温度を35℃に設定した以外は実施例1と同様の条件で硬化膜の形成したところ、膜厚14μmの硬化膜が得られた。その硬化膜について実施例1と同様の条件にて基材密着性の評価および電解液耐性の評価を行なった。結果を表1に示す。 (Comparative Example 10)
As shown below, an ink composition 37 was prepared in the same manner as in Example 1 except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
(A) EB168 0.1 g
3EG 3.92g
A-GLY-9E 1.47g
(C) Irg1173 0.7g
(D) PF656 0.001g
The viscosity of the ink composition 37 was 17.7 mPa · s. Using this ink composition 37, a cured film was formed under the same conditions as in Example 1 except that the head temperature was set to 35 ° C., and a cured film having a thickness of 14 μm was obtained. The cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
以下に示すようにそれぞれの化合物をそれぞれの割合とした以外は実施例1と同様にしてインク組成物38を調製した。実施例1と同様に測定した粘度を以下に示す。
(A)EB168 0.1g
3EG 3.92g
A-9550 1.47g
(C)Irg1173 0.7g
(D)PF656 0.001g
インク組成物38の粘度は、24.7mPa・sであった。このインク組成物38を用いて、ヘッド温度を40℃に設定した以外は実施例1と同様の条件で硬化膜の形成したところ、膜厚15μmの硬化膜が得られた。その硬化膜について実施例1と同様の条件にて基材密着性の評価および電解液耐性の評価を行なった。結果を表1に示す。 (Comparative Example 11)
As shown below, an ink composition 38 was prepared in the same manner as in Example 1 except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
(A) EB168 0.1 g
3EG 3.92g
A-9550 1.47g
(C) Irg1173 0.7g
(D) PF656 0.001g
The viscosity of the ink composition 38 was 24.7 mPa · s. Using this ink composition 38, a cured film was formed under the same conditions as in Example 1 except that the head temperature was set to 40 ° C. As a result, a cured film having a thickness of 15 μm was obtained. The cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
以下に示すようにそれぞれの化合物をそれぞれの割合とした以外は実施例1と同様にしてインク組成物39を調製した。実施例1と同様に測定した粘度を以下に示す。
(A)EB168 0.1g
3EG 3.92g
DPCA-20 1.47g
(C)Irg1173 0.7g
(D)PF656 0.001g
インク組成物39の粘度は、24.8mPa・sであった。このインク組成物39を用いて、ヘッド温度を40℃に設定した以外は実施例1と同様の条件で硬化膜の形成したところ、膜厚15μmの硬化膜が得られた。その硬化膜について実施例1と同様の条件にて基材密着性の評価および電解液耐性の評価を行なった。結果を表1に示す。 (Comparative Example 12)
As shown below, an ink composition 39 was prepared in the same manner as in Example 1 except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
(A) EB168 0.1 g
3EG 3.92g
DPCA-20 1.47g
(C) Irg1173 0.7g
(D) PF656 0.001g
The viscosity of the ink composition 39 was 24.8 mPa · s. Using this ink composition 39, a cured film was formed under the same conditions as in Example 1 except that the head temperature was set to 40 ° C. As a result, a cured film having a thickness of 15 μm was obtained. The cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
以下に示すようにそれぞれの化合物をそれぞれの割合とした以外は実施例1と同様にしてインク組成物40を調製した。実施例1と同様に測定した粘度を以下に示す。
(A)EB168 0.1g
3EG 3.92g
CN2302 1.47g
(C)Irg1173 0.7g
(D)PF656 0.001g
インク組成物40の粘度は、20.2mPa・sであった。このインク組成物40を用いて、ヘッド温度を40℃に設定した以外は実施例1と同様の条件で硬化膜の形成したところ、膜厚16μmの硬化膜が得られた。その硬化膜について実施例1と同様の条件にて基材密着性の評価および電解液耐性の評価を行なった。結果を表1に示す。 (Comparative Example 13)
As shown below, an ink composition 40 was prepared in the same manner as in Example 1 except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
(A) EB168 0.1 g
3EG 3.92g
CN2302 1.47g
(C) Irg1173 0.7g
(D) PF656 0.001g
The viscosity of the ink composition 40 was 20.2 mPa · s. Using this ink composition 40, a cured film was formed under the same conditions as in Example 1 except that the head temperature was set to 40 ° C. As a result, a cured film having a thickness of 16 μm was obtained. The cured film was evaluated for substrate adhesion and electrolyte resistance under the same conditions as in Example 1. The results are shown in Table 1.
以下に示すようにそれぞれの化合物をそれぞれの割合とした以外は実施例1と同様にしてインク組成物41を調製した。実施例1と同様に測定した粘度を以下に示す。
(B)IB-XA 2.95g
(B)M-208 2.00g
(C)Irg1173 0.7g
(D)PF656 0.001g
インク組成物41の粘度は、28.0mPa・sであった。このインク組成物41を用いて、ヘッド温度を45℃に設定した以外は実施例25と同様の条件で硬化膜の形成したところ、膜厚15μmの硬化膜が得られた。その硬化膜について実施例25と同様の条件にて基材密着性の評価および洗浄剤耐性の評価を行なった。結果を表2に示す。 (Comparative Example 14)
As shown below, an ink composition 41 was prepared in the same manner as in Example 1 except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
(B) IB-XA 2.95 g
(B) M-208 2.00g
(C) Irg1173 0.7g
(D) PF656 0.001g
The viscosity of the ink composition 41 was 28.0 mPa · s. Using this ink composition 41, a cured film was formed under the same conditions as in Example 25 except that the head temperature was set at 45 ° C., and a cured film having a thickness of 15 μm was obtained. The cured film was evaluated for substrate adhesion and detergent resistance under the same conditions as in Example 25. The results are shown in Table 2.
以下に示すようにそれぞれの化合物をそれぞれの割合とした以外は実施例1と同様にしてインク組成物42を調製した。実施例1と同様に測定した粘度を以下に示す。
(A)EB168 0.1g
3EG 4.9g
(C)Irg1173 0.7g
(D)PF656 0.001g
インク組成物42の粘度は、9.6mPa・sであった。このインク組成物42を用いて、ヘッド温度を30℃に設定した以外は実施例25と同様の条件で硬化膜の形成したところ、膜厚13μmの硬化膜が得られた。その硬化膜について実施例25と同様の条件にて基材密着性の評価および洗浄剤耐性の評価を行なった。結果を表2に示す。 (Comparative Example 15)
As shown below, an ink composition 42 was prepared in the same manner as in Example 1, except that the ratio of each compound was changed. The viscosity measured in the same manner as in Example 1 is shown below.
(A) EB168 0.1 g
3EG 4.9g
(C) Irg1173 0.7g
(D) PF656 0.001g
The viscosity of the ink composition 42 was 9.6 mPa · s. When a cured film was formed using this ink composition 42 under the same conditions as in Example 25 except that the head temperature was set to 30 ° C., a cured film having a thickness of 13 μm was obtained. The cured film was evaluated for substrate adhesion and detergent resistance under the same conditions as in Example 25. The results are shown in Table 2.
Claims (13)
- 一般式(1-1)および(1-2)で表されるリン酸エステルを有する(メタ)アクリレートモノマー(A)、(A)以外の1分子中に1~3個のアクリロイル基を有しかつ-(CH2-CH2-O)n-(n>3)構造を有さない反応性化合物(B)、光重合開始剤(C)としてベンジルケタール系化合物およびα-ヒドロキシアセトフェノン系化合物から選ばれる少なくとも1つを含むインク組成物であって、反応性化合物(B)の総量100重量部に対し、リン酸エステルを有する(メタ)アクリレートモノマー(A)の添加量が0.01~5.5重量部である光硬化性インクジェットインク。
(一般式(1-1)および(1-2)中、R1はそれぞれ独立して水素またはメチルである。)
(Meth) acrylate monomer having phosphoric acid ester represented by general formula (1-1) and (1-2) (A), having 1 to 3 acryloyl groups in one molecule other than (A) And a reactive compound (B) having no — (CH 2 —CH 2 —O) n — (n> 3) structure, a benzyl ketal compound and an α-hydroxyacetophenone compound as a photopolymerization initiator (C). An ink composition containing at least one selected from the above, wherein the addition amount of the (meth) acrylate monomer (A) having a phosphate ester is 0.01 to 5 with respect to 100 parts by weight of the total amount of the reactive compound (B). A photocurable inkjet ink that is 5 parts by weight.
(In the general formulas (1-1) and (1-2), each R 1 is independently hydrogen or methyl.)
- 反応性化合物(B)が、反応性化合物(B)の総量を100重量%としたとき、3官能(メタ)アクリレート化合物0~80重量%、2官能(メタ)アクリレート化合物10~100重量%、および単官能(メタ)アクリレート化合物0~60重量%である、請求項1に記載の光硬化インクジェットインク。 When the total amount of the reactive compound (B) is 100% by weight, the reactive compound (B) is 0 to 80% by weight of the trifunctional (meth) acrylate compound, 10 to 100% by weight of the bifunctional (meth) acrylate compound, The photocurable inkjet ink according to claim 1, wherein the content of the monofunctional (meth) acrylate compound is 0 to 60 wt%.
- 反応性化合物(B)が、トリメチロールプロパントリアクリレート、ペンタエリスリトールトリアクリレート、2-ヒドロキシ-3-アクリロイロキシプロピルメタアクリレート、ネオペンチルグリコールジアクリレート、トリシクロデカンジメタノールジアクリレート、ジプロピレングリコールジアクリレート、トリプロピレングリコールジアクリレート、プロポキシ化(2)ネオペンチルグリコールジアクリレート、ビスフェノールF EO変性ジアクリレート、ネオペンチルグリコール・ヒドロキシピバリン酸エステルジアクリレート、ジオキサングリコールジアクリレート、1,3-ブチレングリコールジアクリレート、イソボルニル(メタ)アクリレート、ジシクロペンタニル(メタ)アクリレートおよびベンジルメタクリレートから選ばれる少なくとも1つである、請求項1または請求項2に記載の光硬化性インクジェットインク。 The reactive compound (B) is trimethylolpropane triacrylate, pentaerythritol triacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, neopentyl glycol diacrylate, tricyclodecane dimethanol diacrylate, dipropylene glycol diacrylate. Acrylate, tripropylene glycol diacrylate, propoxylated (2) neopentyl glycol diacrylate, bisphenol F EO-modified diacrylate, neopentyl glycol hydroxypivalate ester diacrylate, dioxane glycol diacrylate, 1,3-butylene glycol diacrylate , Isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate and benzyl methacrylate At least one is, the light-curable inkjet ink according to claim 1 or claim 2 selected from.
- 光重合開始剤(C)が、2,2-ジメトキシ-2-フェニルアセトフェノン、2,2-ジエトキシ-2-フェニルアセトフェノン、1-ヒドロキシシクロヘキシルフェニルケトン、2-ヒドロキシ-2-メチル-1-フェニル-1-プロパノン、および2-ヒドロキシ-1-{4-[4-(2-ヒドロキシ-2-メチル-プロピオニル)-ベンジル]フェニル}-2-メチル-1-プロパノンから選ばれる少なくとも1つである、請求項1~3のいずれか1項に記載の光硬化性インクジェットインク。 The photopolymerization initiator (C) is 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl- 1-propanone, and 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-1-propanone, The photocurable inkjet ink according to any one of claims 1 to 3.
- 反応性化合物(B)が、反応性化合物(B)の総量を100重量%としたとき、3官能(メタ)アクリレート化合物0~80重量%、2官能(メタ)アクリレート化合物10~100重量%、および単官能(メタ)アクリレート化合物0~40重量%である、請求項1~3のいずれか1項に記載の光硬化インクジェットインク。 When the total amount of the reactive compound (B) is 100% by weight, the reactive compound (B) is 0 to 80% by weight of the trifunctional (meth) acrylate compound, 10 to 100% by weight of the bifunctional (meth) acrylate compound, The photocurable inkjet ink according to any one of claims 1 to 3, wherein the content of the monofunctional (meth) acrylate compound is 0 to 40% by weight.
- 請求項1~5のいずれか1項に記載の光硬化性インクジェットインクを硬化させて得られる硬化膜。 A cured film obtained by curing the photocurable inkjet ink according to any one of claims 1 to 5.
- 請求項6に記載の硬化膜を用いた電子部品用の絶縁膜。 The insulating film for electronic components using the cured film of Claim 6.
- 請求項6に記載の硬化膜を用いた金属基材上に形成される電子部品用の絶縁膜。 The insulating film for electronic components formed on the metal base material using the cured film of Claim 6.
- 請求項6に記載の絶縁膜を用いた電磁波シールド材用の絶縁膜。 An insulating film for an electromagnetic wave shielding material using the insulating film according to claim 6.
- 請求項9に記載の絶縁膜を用いた電磁波シールド材。 An electromagnetic wave shielding material using the insulating film according to claim 9.
- 請求項6に記載の硬化膜を用いた電池用の絶縁膜。 An insulating film for a battery using the cured film according to claim 6.
- 請求項11に記載の絶縁膜を用いた電池用部材。 A battery member using the insulating film according to claim 11.
- 請求項12に記載の電池用部材を有する二次電池。 A secondary battery comprising the battery member according to claim 12.
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