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  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/30—Nitriles
  • C08F222/34—Vinylidene cyanide
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  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
  • C08F218/02—Esters of monocarboxylic acids
  • C08F218/04—Vinyl esters
  • C08F218/08—Vinyl acetate
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
  • C08F218/02—Esters of monocarboxylic acids
  • C08F218/04—Vinyl esters
  • C08F218/10—Vinyl esters of monocarboxylic acids containing three or more carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L35/04—Homopolymers or copolymers of nitriles
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  • 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
  • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D133/04—Homopolymers or copolymers of esters
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  • 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
  • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D133/04—Homopolymers or copolymers of esters
  • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C09D133/10—Homopolymers or copolymers of methacrylic acid esters
  • C09D133/12—Homopolymers or copolymers of methyl methacrylate
• • 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
  • C09D135/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D135/04—Homopolymers or copolymers of nitriles
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
  • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G4/00—Fixed capacitors; Processes of their manufacture
  • H01G4/002—Details
  • H01G4/018—Dielectrics
  • H01G4/06—Solid dielectrics
  • H01G4/14—Organic dielectrics
  • H01G4/18—Organic dielectrics of synthetic material, e.g. derivatives of cellulose
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G4/00—Fixed capacitors; Processes of their manufacture
  • H01G4/32—Wound capacitors
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G7/00—Capacitors in which the capacitance is varied by non-mechanical means; Processes of their manufacture
  • H01G7/02—Electrets, i.e. having a permanently-polarised dielectric
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
  • C08F2800/10—Copolymer characterised by the proportions of the comonomers expressed as molar percentages
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2331/00—Characterised by the use of copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, or carbonic acid, or of a haloformic acid
  • C08J2331/02—Characterised by the use of omopolymers or copolymers of esters of monocarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2331/00—Characterised by the use of copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, or carbonic acid, or of a haloformic acid
  • C08J2331/02—Characterised by the use of omopolymers or copolymers of esters of monocarboxylic acids
  • C08J2331/04—Homopolymers or copolymers of vinyl acetate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
  • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
  • C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
  • C08J2333/12—Homopolymers or copolymers of methyl methacrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2335/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Derivatives of such polymers
  • C08J2335/04—Homopolymers or copolymers of nitriles
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G4/00—Fixed capacitors; Processes of their manufacture
  • H01G4/002—Details
  • H01G4/018—Dielectrics
  • H01G4/06—Solid dielectrics
  • H01G4/14—Organic dielectrics
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G4/00—Fixed capacitors; Processes of their manufacture
  • H01G4/33—Thin- or thick-film capacitors (thin- or thick-film circuits; capacitors without a potential-jump or surface barrier specially adapted for integrated circuits, details thereof, multistep manufacturing processes therefor)

Definitions

• the present invention relates to a copolymer that contains structural units derived from 1,1-dicyanoethylene and structural units derived from a specific polymerizable monomer in a specific sequence, and a resin composition that contains the copolymer.
• Non-Patent Document 1 describes a method for analyzing copolymers of 1,1-dicyanoethylene and vinyl acetate.
• films made from copolymers obtained by radical polymerization of 1,1-dicyanoethylene and polymerizable monomers have excellent transparency, but there is a problem in that the copolymer becomes discolored when heated, impairing its appearance.
• the present invention has been made in consideration of the above-mentioned problems of the prior art, and aims to provide a copolymer that can suppress coloration even after heating.
• Another aim of the present invention is to provide a resin composition containing the copolymer, and a molded product and film using the copolymer.
• the inventors conducted research and discovered that radical polymerization of 1,1-dicyanoethylene and a specific polymerizable monomer at a relatively low temperature in a specific charge ratio results in the polymerization of structural units derived from 1,1-dicyanoethylene and structural units derived from the polymerizable monomer in a specific sequence. Based on this knowledge, the inventors conducted further research and discovered that by controlling the sequence of each monomer, a copolymer can be obtained in which coloring is suppressed even after heating, and thus completed the present invention.
• the copolymer contains the following four types of triad structures (U-1) to (U-4) composed of the structural unit (A) and the structural unit (B), (A)-(A)-(A) ... (U-1) (A)-(A)-(B) ... (U-2) (B) - (A) - (A) ... (U-3) (B) - (A) - (B) ...
• R 1 is at least one selected from a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, and a halogen atom
• R2 is at least one selected from an alkoxy group, a carboxy group, an ester group represented by -COOR3
• R3 is an alkyl group having 1 to 12 carbon atoms
• an acid anhydride group an acyl group represented by -COR4
• R4 is an alkyl group having 1 to 12 carbon atoms
• acyloxy group represented by -OCOR5 R5 is an alkyl group having 1 to 12 carbon atoms).
• [5] A resin composition comprising the copolymer according to any one of [1] to [4] above.
• [6] A molded product using the copolymer according to any one of [1] to [4] above or the resin composition according to [5] above.
• [7] A film using the copolymer according to any one of [1] to [4] above, or the resin composition according to [5] above, wherein the difference between the yellowness index before heating and the yellowness index after heating at 140° C. under normal pressure for 1 hour is 3.0% or less.
• [8] A conductive film obtained by laminating a conductive layer on the film according to [7] above.
• [9] A film capacitor comprising the film according to [7] or the conductive film according to [8].
• a polarizing material comprising the resin composition according to [5] above or the film according to [7] above.
• An electrostatic induction conversion element comprising the polarization material according to [10] above.
• a touch panel comprising the electrostatic induction conversion element according to [11] above.
• the present invention can provide a copolymer that can suppress coloration even after heating.
• the present invention can also provide a resin composition containing the copolymer, and a molded product and a film using the copolymer.
• the copolymer contains the following four types of triad structures (U-1) to (U-4) composed of the structural unit (A) and the structural unit (B), (A)-(A)-(A) ... (U-1) (A)-(A)-(B) ... (U-2) (B) - (A) - (A) ... (U-3) (B) - (A) - (B) ...
• R 1 is at least one selected from a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, and a halogen atom
• R2 is at least one selected from an alkoxy group, a carboxy group, an ester group represented by -COOR3
• R3 is an alkyl group having 1 to 12 carbon atoms
• an acid anhydride group an acyl group represented by -COR4
• R4 is an alkyl group having 1 to 12 carbon atoms
• acyloxy group represented by -OCOR5 R5 is an alkyl group having 1 to 12 carbon atoms).
• triad structure refers to a structure in which three structural units (A) derived from 1,1-dicyanoethylene and three structural units (B) derived from the compound represented by the general formula (I) are linked together.
• (A)-(A)-(A) which is one of the four types of triad structures, means a triad structure in which three structural units (A) derived from 1,1-dicyanoethylene are bonded in succession
• “(A)-(A)-(B)” means a triad structure in which two structural units (A) derived from 1,1-dicyanoethylene are bonded in succession and then a structural unit (B) derived from the compound represented by general formula (I) is bonded thereto, and the other triad structures have the same meaning.
• the amounts of four types of triad structures (U-1) to (U-4) are specified, and the amount of triad structure (U-1) means “the content (mol %) of (A) bonded between two (As) in the (A)-(A)-(A) structure constituting (U-1)".
• the content of triad structure (U-2) means “the content (mol %) of (A) bonded between (A) and (B) in the (A)-(A)-(B) structure constituting (U-2)", and the contents of other triad structures have the same meaning.
• the content of each of the triad structures (U-1) to (U-4) in the present invention can be measured by 13 C-NMR, specifically by the method described in the Examples.
• the present invention is characterized in that the total content of (U-2) and (U-3) in the total amount of the four types of triad structures is 9.0 mol % or less.
• the amount of sequences that cause coloring due to heat, specifically, sequences in which (A) are continuous can be kept low, so that coloring can be suppressed even after heating in molded products using the copolymer of the present invention.
• the total content of (U-2) and (U-3) in the total amount of the four types of triad structures is 9.0 mol% or less, preferably 8.5 mol% or less, preferably 8.0 mol% or less, preferably 7.5 mol% or less, preferably 7.0 mol% or less, preferably 6.0 mol% or less, and more preferably 5.0 mol% or less, and usually the lower limit is 0.5 mol% or more, but may be less than that.
• the total content of (U-2) and (U-3) can be adjusted by controlling the amount of monomers charged at a relatively low temperature of less than 50° C.
• the content of (U-1) in the total amount of the four types of triad structures is preferably 1.8 mol% or less.
• the content of (U-1) in the total amount of the four types of triad structures is preferably 1.4 mol% or less, more preferably 1.0 mol% or less, even more preferably 0.6 mol% or less, even more preferably 0.4 mol% or less, and particularly preferably 0.3 mol% or less.
• the copolymer of the present invention contains a structural unit (A) derived from 1,1-dicyanoethylene. Since 1,1-dicyanoethylene gives a copolymer having high transparency by radical polymerization, the copolymer of the present invention can be suitably used for molded products and the like that require transparency. 1,1-dicyanoethylene can be produced by the production method described in J. Am. Chem. Soc., 1989, 111, 9078-9081 and US Pat. No. 2,476,270.
• the copolymer of the present invention contains a structural unit (B) derived from a compound represented by the following general formula (I).
• CH2 CR1R2 ( I )
• R 1 is at least one selected from a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, and a halogen atom
• R2 is at least one selected from an alkoxy group, a carboxy group, an ester group represented by -COOR3 ( R3 is an alkyl group having 1 to 12 carbon atoms), an acid anhydride group, an acyl group represented by -COR4 ( R4 is an alkyl group having 1 to 12 carbon atoms), and an acyloxy group represented by -OCOR5 ( R5 is an alkyl group having 1 to 12 carbon atoms).
• R 1 is at least one selected from a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group and a halogen atom.
• the alkyl group for R1 is preferably an alkyl group having 1 to 12 carbon atoms, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, an n-hexyl group, a heptyl group, an octyl group, a decyl group, and a dodecyl group.
• the cycloalkyl group for R 1 is preferably a cycloalkyl group having 3 to 12 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.
• the aryl group for R 1 is preferably an aryl group having 6 to 20 carbon atoms, and examples thereof include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.
• the alkoxy group for R 1 is preferably an alkoxy group having 1 to 10 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group.
• the halogen atom for R 1 includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
• R 1 is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and further preferably a hydrogen atom or a methyl group.
• R2 is at least one selected from an alkoxy group, a carboxy group, an ester group represented by -COOR3 ( R3 is an alkyl group having 1 to 12 carbon atoms), an acid anhydride group, an acyl group represented by -COR4 ( R4 is an alkyl group having 1 to 12 carbon atoms), and an acyloxy group represented by -OCOR5 ( R5 is an alkyl group having 1 to 12 carbon atoms).
• the alkoxy group for R2 is preferably an alkoxy group having 1 to 12 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group.
• R2 may be an ester group represented by -COOR3 , where R3 represents an alkyl group having 1 to 12 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, an n-hexyl group, a heptyl group, an octyl group, a decyl group, and a dodecyl group.
• R3 represents an alkyl group having 1 to 12 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-but
• Examples of the acid anhydride group for R2 include acid anhydride groups derived from phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride, glutaric anhydride, dimethylglutaric anhydride, diethylglutaric anhydride, succinic anhydride, methylhexahydrophthalic anhydride, and methyltetrahydrophthalic anhydride.
• R2 may be an acyl group represented by -COR4 , where R4 represents an alkyl group having 1 to 12 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, and an n-hexyl group.
• R4 represents an alkyl group having 1 to 12 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group,
• R2 may be an acyloxy group represented by -OCOR5 , where R5 is an alkyl group having 1 to 12 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, and an n-hexyl group.
• R5 is an alkyl group having 1 to 12 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group,
• R 2 is preferably at least one selected from the group consisting of an ester group represented by -COOR 3 and an acyloxy group represented by -OCOR 5 , more preferably an ester group represented by -COOR 3 (in this case, R 3 is an alkyl group having 1 to 12 carbon atoms) or an acyloxy group represented by -OCOR 5 (in this case, R 5 is an alkyl group having 1 to 6 carbon atoms), and even more preferably an ester group represented by -COOR 3 (in this case, R 3 is an alkyl group having 1 to 12 carbon atoms) or an acyloxy group represented by -OCOR 5 (in this case, R 5 is an alkyl group having 1 to 4 carbon atoms).
• the compound represented by the general formula (I) is preferably one or more selected from the group consisting of vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, methyl methacrylate, methyl acrylate, ethyl acrylate, and butyl acrylate, and more preferably one or more selected from the group consisting of vinyl acetate, methyl methacrylate, methyl acrylate, and ethyl acrylate.
• the compound represented by the above general formula (I) is easily available as a commercial product, and can also be produced by known methods.
• the content of the structural unit (A) in the copolymer of the present invention is preferably from 30 to 55 mol %, more preferably from 40 to 53 mol %, and even more preferably from 45 to 53 mol %.
• the content of the structural unit (B) is preferably from 20 to 80 mol%, more preferably from 45 to 70 mol%, even more preferably from 47 to 60 mol%, and even more preferably from 47 to 55 mol%.
• a molded article using the copolymer of the present invention is less likely to be discolored even after heating.
• the content of each of the structural units can be measured by 1 H-NMR, specifically by the method described in the examples.
• the copolymer of the present invention may contain a constituent unit derived from a monomer other than the constituent unit (A) derived from 1,1-dicyanoethylene and the constituent unit (B) derived from the compound represented by the general formula (I).
• the other constituent units include aromatic vinyl compounds such as styrene, ⁇ -methylstyrene, and tert-butylstyrene.
• the content thereof in the copolymer is preferably 20 mol % or less, more preferably 10 mol % or less, and even more preferably 5 mol % or less.
• the method for producing the copolymer of the present invention is not particularly limited, but it is preferable to produce the copolymer at a polymerization temperature of less than 50° C. in the presence of a radical initiator.
• a polymerization temperature By setting the polymerization temperature to less than 50° C., it becomes easy to adjust the content of (U-2) and (U-3) to 9.0 mol % or less in the total amount of the four types of triad structures.
• the polymerization temperature is preferably 47° C. or less, more preferably 45° C. or less.
• the polymerization temperature is preferably 10°C or higher, more preferably 20°C or higher, and even more preferably 30°C or higher.
• the copolymer of the present invention is preferably produced in the presence of a radical polymerization initiator.
• a radical polymerization initiator By using the radical polymerization initiator, it becomes easier to adjust the total content of (U-2) and (U-3) in the total amount of the triad structure.
• radical polymerization initiator examples include azo compounds such as azobisisobutyronitrile, 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis[2-(2-imidazolin-2-yl)propane], and 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] hydrate; inorganic peroxides such as sodium persulfate, potassium persulfate, and hydrogen peroxide; organic peroxides such as t-butyl hydroperoxide, cumene hydroperoxide, and p-menthane hydroperoxide; and redox initiators that combine an oxidizing agent and a reducing agent, such as hydrogen peroxide and an iron(II) salt, or a persulfate and sodium hydrogen sulfite.
• azo compounds such as azobisisobutyronitrile, 2,2'-azobis(4-methoxy-2
• the copolymer of the present invention is easily adjusted in the total content of (U-2) and (U-3) in the total amount of the triad structure by performing radical polymerization at a low temperature. Therefore, among these radical polymerization initiators, azo compounds such as azobisisobutyronitrile and 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) and redox initiators, which are easy to use at low temperatures, are preferred.
• the amount of the radical polymerization initiator used is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and even more preferably 0.08 to 3 parts by mass, per 100 parts by mass of all the monomers that are the raw materials for the copolymer.
• the amount of the compound represented by the general formula (I) is preferably 1.5 equivalents or more relative to the amount of 1,1-dicyanoethylene, more preferably 1.8 equivalents or more, and even more preferably 2.2 equivalents or more, and usually, from the viewpoint of suppressing production costs, is preferably 5.0 equivalents or less.
• the water content of 1,1-dicyanoethylene is low from the viewpoint of suppressing ionic polymerization.
• the water content of 1,1-dicyanoethylene is preferably 10,000 ppm or less, more preferably 1,000 ppm or less, even more preferably 500 ppm or less, and even more preferably 300 ppm or less.
• the amount of water contained in 1,1-dicyanoethylene can be measured, for example, by a method in accordance with JIS K0068:2001.
• the resin composition of the present invention contains the copolymer, and can be suitably used as a raw material for molded products, etc. As described above, the copolymer of the present invention can suppress coloration even after heating, and is therefore particularly suitable as a material for films, etc.
• the resin composition of the present invention is not particularly limited as long as it contains the above-mentioned copolymer, but may contain a synthetic resin in addition to the above-mentioned copolymer.
• polyolefin resins such as polyethylene, polypropylene, copolymers of ethylene and one or more ⁇ -olefins having 3 to 20 carbon atoms (e.g., propylene, 1-butene, 1-pentene, 1-hexene, etc.), ethylene-propylene-diene copolymers (EPDM), ethylene-vinyl acetate copolymers, and ethylene-acrylic acid copolymers, polyurethane resins, polyamide resins, polyester resins, and polycarbonate resins.
• polyolefin resins such as polyethylene, polypropylene, copolymers of ethylene and one or more ⁇ -olefins having 3 to 20 carbon atoms (e.g., propylene, 1-butene, 1-pentene, 1-hexene, etc.), ethylene-propylene-diene copolymers (EPDM), ethylene-vinyl acetate copolymers, and ethylene-acrylic acid copo
• the resin composition of the present invention may contain other components, if necessary, in addition to the copolymer of the present invention and the synthetic resin.
• Other components may include solvents, fillers, thickeners, antioxidants, plasticizers, flame retardants, stabilizers, and antioxidants.
• the content of the copolymer in the resin composition of the present invention is preferably 0.1% by mass or more, more preferably 20% by mass or more, and even more preferably 50% by mass or more.
• the resin composition of the present invention contains optional components, i.e., the synthetic resin and other components, the total content thereof is preferably 99.9% by mass or less, more preferably 80% by mass or less, and even more preferably 50% by mass or less, and usually preferably 1% by mass or more, based on the total amount of the resin composition.
• the content of the other components is preferably 10% by mass or less, more preferably 3% by mass or less, and usually preferably 0.001% by mass or more.
• the method for producing the resin composition is not particularly limited, and the resin composition can be produced by a production method including a mixing step of mixing the copolymer of the present invention and the synthetic resin and other components used as necessary.
• the method for mixing the components is not particularly limited, and the components can be mixed by a known method.
• the molded article and film of the present invention are made using the copolymer or resin composition of the present invention.
• the shape of the molded article is not limited as long as it can be produced using the copolymer or resin composition of the present invention, and examples of the shape include films, pellets, sheets, plates, pipes, tubes, fibers, nonwoven fabrics, rods, granules, and various other shapes.
• There is no particular limitation on the method for producing the molded product and it can be molded by various conventionally known molding methods, such as injection molding, blow molding, press molding, extrusion molding, and calendar molding.
• Examples of molded products using the copolymer composition of the present invention include film capacitors, insulating layers for EL elements, electrostatic induction conversion elements, sensors (e.g., touch sensors, vibration sensors, biosensors, tire sensors (sensors installed on the inner surface of tires)), actuators, touch panels, haptic devices (devices with the function of providing tactile feedback to users), vibration power generation devices (e.g., vibration power generation floors, vibration power generation tires), speakers, microphones, etc.
• the molded product of the present invention is preferably a film.
• molded products using the copolymer of the present invention can suppress coloration even after heating, so by processing them into a film, a film with a better appearance can be obtained.
• the difference in yellowness between before heating and after heating at 140°C under normal pressure for 1 hour is preferably 3.0% or less, more preferably 2.0% or less, even more preferably 1.0% or less, and even more preferably 0.9% or less.
• the film of the present invention can keep the yellowness low even before heating, and the specific yellowness is preferably 1.5% or less, and more preferably 1.2% or less.
• the film of the present invention preferably has a low yellowness after heating, and the yellowness after heating at 140°C under normal pressure for 1 hour is preferably 3.0% or less, more preferably 2.5% or less, even more preferably 2.0% or less, and even more preferably 1.8% or less.
• the yellowness in the present invention is measured in accordance with JIS Z8722:2009, and specifically, can be measured by the method described in the Examples.
• the thickness of the film of the present invention is preferably 0.001 to 5.0 mm, more preferably 0.005 to 1.5 mm, even more preferably 0.01 to 1.0 mm, even more preferably 0.01 to 0.5 mm, and even more preferably 0.01 to 0.1 mm.
• the method for producing the film of the present invention is not particularly limited, and it can be formed by a conventionally known method.
• the forming method include a solution casting method, a melt extrusion method, a calendar method, a compression molding method, and an injection molding method.
• the conductive film of the present invention is obtained by laminating a conductive layer on the above-mentioned film, and the film capacitor of the present invention includes the above-mentioned film or the above-mentioned conductive film.
• the conductive film of the present invention exhibits excellent performance as a film capacitor since it uses the film of the present invention having an excellent relative dielectric constant.
• the conductive layer that constitutes the conductive film, but in general, it is preferred that the conductive layer be a layer made of a conductive metal such as aluminum, zinc, gold, platinum, or copper, and that the layer be a metal foil or a metal coating (e.g., a vapor-deposited metal coating), or both may be used in combination.
• a vapor-deposited metal coating is preferred from the viewpoints of making the conductive layer thinner and increasing the capacitance relative to the volume, improving adhesion with the dielectric, and further reducing thickness variation.
• a semiconductor aluminum oxide layer may be formed on top of the aluminum layer, making the coating multi-layered, as described in, for example, JP-A-2-250306.
• the thickness of the vapor-deposited metal coating is preferably 10 to 200 nm, and more preferably 20 to 100 nm. If the thickness of the vapor-deposited metal coating is within the above range, it is preferable because it is possible to achieve both the capacitance and strength of the capacitor.
• the method for forming the coating is not particularly limited, and for example, vacuum deposition, sputtering, ion plating, etc. can be used, with vacuum deposition being usually preferred.
• the conductive layer can be formed by a batch method, which is used for molded products, a semi-continuous method, which is used for long products, or a continuous (air to air) method, with the semi-continuous method being the most common.
• the semi-continuous metal deposition method involves depositing metal in a vacuum system, winding it up, and then returning the vacuum system to the atmospheric system, and removing the deposited film.
• the polarizing material of the present invention comprises the resin composition of the present invention or the film of the present invention.
• the polarizing material of the present invention can be obtained, for example, by subjecting the film of the present invention to a poling treatment.
• the poling treatment include a method in which a heat-treated molded product is heated to a predetermined temperature, and in that state, a high DC electric field or a high DC electric field combined with an AC electric field is applied from the front and back of the molded product for a certain period of time, and then the product is slowly cooled or rapidly cooled.
• Another example includes a method in which a high DC electric field or a high DC electric field combined with an AC electric field is applied from the front and back of the molded product for a certain period of time simultaneously with the heat treatment, and then the product is slowly cooled or rapidly cooled.
• the poling treatment is preferably performed at a temperature 30°C lower than the glass transition temperature (Tg) of the heat-treated molded product.
• the poling treatment is preferably performed using metal foil, metal plate, conductive paste, vacuum deposition, or chemically plated metal coating film attached to both sides of the molded product as electrodes.
• the applied voltage is generally 10 KV/cm or more, preferably at an electric field strength that does not cause dielectric breakdown, and more preferably 100 to 1500 KV/cm.
• There is no particular limit to the treatment time but it is preferably 1 minute to 5 hours, and more preferably 10 minutes to 2 hours, for the heat-treated molded product.
• the poling treatment can also be carried out by a corona discharge treatment.
• a corona discharge treatment Either a negative corona or a positive corona may be used for the corona discharge, but it is preferable to use a negative corona in view of the ease of polarization of a non-polarized film.
• the corona discharge treatment is not particularly limited, but examples thereof include a method of applying a corona discharge to a non-polarized film using a linear electrode as described in JP 2011-181748 A, a method of applying a corona discharge to a non-polarized film using a needle electrode, or a method of applying a corona discharge to a non-polarized film using a grid electrode.
• the conditions of the corona discharge treatment can be appropriately set based on common knowledge in the art. If the conditions of the corona discharge treatment are too weak, the piezoelectricity of the resulting film may be insufficient, whereas if the conditions of the corona discharge treatment are too strong, the resulting film may have point defects.
• the distance between each needle-like electrode and/or linear electrode and the film is constant, i.e., that there is no (or extremely small) in-plane variation in the distance between the electrodes and the film; specifically, the difference between the longest distance and the shortest distance is preferably within 6 mm, more preferably within 4 mm, and even more preferably within 3 mm.
• the DC electric field is preferably -10 to -25 kV
• the processing speed is preferably 10 to 1200 cm/min, although this varies depending on the distance between the linear electrode and the non-polarized film and the film thickness, etc.
• polarization treatment can also be performed by sandwiching a non-polarized film between flat electrodes on both sides.
• a DC electric field of 0 to 400 MV/m, more preferably 50 to 400 MV/m, for a time of 0.1 seconds to 60 minutes.
• the electrostatic induction conversion element of the present invention comprises the polarizable material of the present invention
• the touch panel of the present invention comprises the electrostatic induction conversion element of the present invention.
• the electrostatic induction conversion element may be incorporated in devices other than touch panels, such as vibration type power generators, actuators, sensors, etc.
• the electrostatic induction conversion element and touch panel of the present invention are derived from the resin composition or film of the present invention, and are useful in terms of durability, etc., particularly when used outdoors.
• Example 1 Into a 100 ml four-neck flask equipped with a stirrer, Dimroth, and thermometer, 2.0 g (0.026 mol, water content 390 ppm) of 1,1-dicyanoethylene synthesized by the method described in the aforementioned literature, 5.5 g (0.064 mol, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.), 25 ml of ethyl acetate (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.), and 18 mg of 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) were placed, and radical polymerization was carried out by heating and stirring under a nitrogen gas flow at 45°C for 6 hours.
• the obtained copolymer was dissolved in N,N-dimethylacetamide (manufactured by Tokyo Chemical Industry Co., Ltd.), and applied by solution casting using a film applicator (manufactured by Tester Sangyo Co., Ltd.) to a thickness of 50 ⁇ m.
• the coating was then vacuum dried at 40° C. and 1 kPa for 7 days to prepare a pre-heated film.
• the yellowness of the resulting film was measured by the method described below, and the results are shown in Table 1.
• the dielectric constant of the obtained film was measured by the method described later, and the results are shown in Table 1.
• Table 1 the film of the present invention can suppress the yellowness index to a low level and has a high relative dielectric constant.
• Such a material having a high relative dielectric constant is suitable for use in a film capacitor, as described in JP 2008-034189 A.
• the obtained film was subjected to a polarization treatment, and the piezoelectricity was evaluated by the method described below.
• the results are shown in Table 3.
• the film of the present invention can suppress the yellowness to a low level and further has excellent piezoelectricity, and is therefore suitable as a transparent piezoelectric film for applications requiring transparency, such as touch panel applications.
• Examples 2, 3, 5 to 7, Comparative Examples 1 and 2 A film was produced in the same manner as in Example 1, except that a copolymer was produced according to the ratio of the charged amounts and the polymerization temperature shown in Table 1. The resulting copolymer was subjected to NMR spectrum measurement, and the resulting film was subjected to yellowness measurement in the same manner as in Example 1. The results are shown in Tables 1 and 2.
• Example 4 Into a 100 ml four-neck flask equipped with a stirrer, Dimroth, and thermometer, 2.0 g (0.026 mol, water content 390 ppm) of 1,1-dicyanoethylene synthesized by the method described in the aforementioned literature, 6.4 g (0.064 mol, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.), 25 ml of toluene (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.), and 18 mg of 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) were placed, and radical polymerization was carried out by heating and stirring under a nitrogen gas flow at 40°C for 6 hours.
• the precipitated copolymer was filtered, washed with toluene and n-hexane (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) in that order, and then dried overnight at 80° C. under reduced pressure to obtain a product (copolymer powder).
• the obtained copolymer was subjected to NMR spectrum measurement by the method described below. Furthermore, a film was produced using the obtained copolymer in the same manner as in Example 1, and the yellowness index was measured. The results are shown in Table 1.
• Example 3 A film was produced in the same manner as in Example 4, except that the copolymer was produced according to the polymerization temperature and charge ratio shown in Table 1. The resulting copolymer was subjected to NMR spectrum measurement, and the resulting film was subjected to yellowness measurement in the same manner as in Example 1. The results are shown in Table 2.
• Example 4 A film was produced in the same manner as in Example 1, except that the water concentration in 1,1-dicyanoethylene, the polymerization temperature, the ratio of the charged amounts, etc. were changed as shown in Table 1. The resulting copolymer was subjected to NMR spectrum measurement, and the resulting film was subjected to yellowness measurement in the same manner as in Example 1. The results are shown in Table 2.
• the copolymer of the present invention can suppress coloration even after heating, making it suitable for use in molded products such as films.
• the film of the present invention has piezoelectric properties and can therefore be suitably used for touch panel applications, etc.

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• 2023
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