Classifications

• • 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
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  • 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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  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • C—CHEMISTRY; METALLURGY
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  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/32—Phosphorus-containing compounds
• • C—CHEMISTRY; METALLURGY
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  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
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  • C08K5/00—Use of organic ingredients
  • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
  • C08K5/41—Compounds containing sulfur bound to oxygen
  • C08K5/42—Sulfonic acids; Derivatives thereof
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L31/00—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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
  • C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L31/00—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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
  • C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
  • C08L31/04—Homopolymers or copolymers of vinyl acetate
• • 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
• • 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
  • H01G4/186—Organic dielectrics of synthetic material, e.g. derivatives of cellulose halogenated
• • 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
  • 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)
• • 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
  • C08F212/00—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 aromatic carbocyclic ring
  • C08F212/02—Monomers containing only one unsaturated aliphatic radical
  • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
  • C08F212/06—Hydrocarbons
  • C08F212/08—Styrene
• • 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
  • 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
• • 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
  • 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
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
  • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
  • C08J2323/10—Homopolymers or copolymers of propene
  • C08J2323/14—Copolymers of propene
• • C—CHEMISTRY; METALLURGY
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  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
  • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
  • C08J2323/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
  • C08J2323/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
  • C08J2323/22—Copolymers of isobutene; butyl rubber
• • 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
  • C08J2325/00—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 an aromatic carbocyclic ring; Derivatives of such polymers
  • C08J2325/02—Homopolymers or copolymers of hydrocarbons
  • C08J2325/04—Homopolymers or copolymers of styrene
  • C08J2325/08—Copolymers of styrene
  • C08J2325/12—Copolymers of styrene with unsaturated nitriles
• • 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
  • 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
• • 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
  • C08J2335/06—Copolymers with vinyl aromatic monomers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/32—Phosphorus-containing compounds
  • C08K2003/329—Phosphorus containing acids

Definitions

• the present invention relates to a copolymer containing a structural unit derived from 1,1-dicyanoethylene and a structural unit derived from a specific polymerizable monomer, and a resin composition containing a Br ⁇ nsted acidic compound.
• Resin compositions containing copolymers obtained by radical polymerization of 1,1-dicyanoethylene and polymerizable monomers have excellent transparency when processed into films, and are therefore suitable for use as materials for optical components, lighting components, signboard components, decorative components, etc. (For example, see Patent Document 1).
• films made from resin compositions containing copolymers of 1,1-dicyanoethylene and polymerizable monomers have excellent transparency and dielectric properties, but have the problem of discoloration when heated, impairing their appearance.
• the present invention has been made in consideration of the above-mentioned problems of the prior art, and aims to provide a resin composition that can suppress coloration even after heating and can give films and the like with excellent dielectric properties.
• Another aim of the present invention is to provide molded products, films, conductive films, film capacitors, polarization materials, electrostatic induction conversion elements, and touch panels that use the resin composition.
• nitrile groups present in the side chains of the copolymer nitrile groups derived from 1,1-dicyanoethylene
• substituents on the side chains derived from other monomers constituting the copolymer resulting in a conjugated structure in which double bonds are partially connected, resulting in discoloration upon heating.
• 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 a hydrogen atom, an alkyl group, 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
• the structural unit (a2) is a structural unit (a21) derived from the compound represented by the general formula (I) and a structural unit (a22) derived from the compound represented by the general formula (I).
• [6] The resin composition according to any one of the above [1] to [5], wherein a composition ratio of sulfur atoms to nitrogen atoms [S/N] is 3.5 ⁇ 10 ⁇ 8 to 0.3.
• a composition ratio of phosphorus atoms to nitrogen atoms [P/N] is 1.4 ⁇ 10 ⁇ 8 to 0.3.
• a polarizing material comprising the film according to [9] or [10].
• the polarizing material according to [14] comprising a resin composition containing an acyloxy group represented by R 1 in the general formula (I) being H and R 2 being --OCOR 5 (R 5 being an alkyl group having 1 to 12 carbon atoms).
• the polarizing material according to [15] comprising a resin composition containing an acyloxy group represented by R 1 in the general formula (I) being H and R 2 being --OCOR 5 (R 5 being an alkyl group having 1 to 12 carbon atoms).
• An electrostatic induction conversion element comprising the polarization material according to [14] above.
• An electrostatic induction type conversion element comprising the polarization material according to [15] above.
• a touch panel comprising the electrostatic induction conversion element according to [18] above.
• a touch panel comprising the electrostatic induction conversion element according to [19] above.
• the present invention provides a resin composition that can suppress coloration even after heating and can produce films and the like that have excellent dielectric properties.
• the present invention also provides molded products, films, conductive films, film capacitors, polarization materials, electrostatic induction conversion elements, and touch panels that use the resin composition.
• the resin composition of the present invention is a resin composition containing a copolymer (A) including a structural unit (a1) derived from 1,1-dicyanoethylene and a structural unit (a2) derived from a compound represented by the following general formula (I), and a Br ⁇ nsted acidic compound (B), wherein the content of the Br ⁇ nsted acidic compound (B) in the resin composition is 0.1 to 95,000 ppm by mass: Since the resin composition of the present invention contains a specific amount of a Br ⁇ nsted acidic compound, the partial conjugated structure of the side chain of the copolymer (A), which causes coloring, can be stabilized, and as a result, coloring due to heating can be suppressed.
• a copolymer (A) including a structural unit (a1) derived from 1,1-dicyanoethylene and a structural unit (a2) derived from a compound represented by the following general formula (I), and a Br ⁇ nsted acidic compound (B), wherein the content of the Br ⁇ nsted acid
• 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 a hydrogen atom, an alkyl group, 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
• an acyloxy group represented by -OCOR5 R5 is an alkyl group having 1 to 12 carbon atoms).
• the copolymer (A) used in the present invention contains a structural unit (a1) derived from 1,1-dicyanoethylene and a structural unit (a2) derived from the compound represented by the general formula (I) above.
• the copolymer (A) used in the present invention contains a structural unit (a1) derived from 1,1-dicyanoethylene.
• 1,1-dicyanoethylene gives a highly transparent copolymer by radical polymerization, and therefore can be suitably used as a material for molded products and the like that require transparency.
• 1,1-Dicyanoethylene can be produced by the production methods described in J. Am. Chem. Soc., 1989, 111, 9078-9081 and US Pat. No. 2,476,270.
• the copolymer (A) used in the present invention contains a structural unit (a2) 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 a hydrogen atom, an alkyl group, 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
• 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, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 20 carbon atoms, more preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and further preferably a hydrogen atom, a methyl group, or a phenyl group.
• R2 is at least one selected from a hydrogen atom, an alkyl group, 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 alkyl group for R2 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 alkoxy group for R2 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.
• 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, an n-hexyl group, a heptyl group, an octyl group, a decyl group, and a dodecyl 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-
• 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, an n-hexyl group, a heptyl group, an octyl group, a decyl group, and a dodecyl 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
• R 2 is preferably one selected from the group consisting of a hydrogen atom, an alkyl group, an ester group represented by -COOR 3 , and an acyloxy group represented by -OCOR 5 , more preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an ester group represented by -COOR 3 (in this case, R 3 is an alkyl group having 1 to 6 carbon atoms), an acyloxy group represented by -OCOR 5 (in this case, R 5 is an alkyl group having 1 to 6 carbon atoms), more preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an ester group represented by -COOR 3 (in this case, R 3 is an alkyl group having 1 to 4 carbon atoms), an acyloxy group represented by -OCOR 5 (in this case, R 5 is an alkyl
• the compound represented by the general formula (I) is preferably one or more selected from the group consisting of vinyl esters, (meth)acrylic acid esters, styrene derivatives, isobutylene and propylene from the viewpoint of suppressing coloration, more specifically, it is more preferably one or more selected from the group consisting of vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, methyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, styrene, isobutylene and propylene, and even more preferably one or more selected from the group consisting of vinyl acetate, vinyl propionate, vinyl butyrate, methyl methacrylate, styrene, isobutylene and propylene.
• the compound represented by the above general formula (I) is easily available as a commercial product, and can also be produced by known methods.
• (meth)acrylic acid ester means "acrylic acid ester or methacrylic acid ester”.
• Copolymer (A) may have two or more different structural units (a2), and from the viewpoint of the balance between the effect of suppressing coloration and the manufacturing cost, it is preferable that the structural unit (a2) is composed of two different structural units, a structural unit (a21) derived from a compound represented by the general formula (I) and a structural unit (a22) derived from a compound represented by the general formula (I).
• the compounds represented by the general formula (I) constituting each structural unit are preferably two types selected from the group consisting of vinyl acetate, vinyl propionate, vinyl butyrate, methyl methacrylate, styrene, isobutylene, and propylene.
• the content of the structural unit (a1) in the copolymer (A) is preferably from 20 to 80 mol %, more preferably from 30 to 70 mol %, and even more preferably from 40 to 60 mol %.
• the content of the structural unit (a2) is preferably from 20 to 80 mol %, more preferably from 30 to 70 mol %, and even more preferably from 40 to 60 mol %.
• the copolymer (A) may contain a structural unit derived from a monomer other than the structural unit (a1) derived from 1,1-dicyanoethylene and the structural unit (a2) derived from the compound represented by the general formula (I).
• the other structural units include aromatic vinyl compounds such as ⁇ -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 copolymer (A) may contain the following four types of triad structures (U-1) to (U-4) composed of the structural unit (a1) and the structural unit (a2).
• the structural unit (a2) may be of two or more types. (a1)-(a1)-(a1) ... (U-1) (a1)-(a1)-(a2) ... (U-2) (a2)-(a1)-(a1) ... (U-3) (a2)-(a1)-(a2) ... (U-4)
• (a1)-(a1)-(a1)) which is one of the four types of triad structures, means a triad structure in which three consecutive structural units (a1) derived from 1,1-dicyanoethylene are bonded together, and "(a1)-(a1)-(a2)” means a triad structure in which two consecutive structural units (a1) derived from 1,1-dicyanoethylene are bonded together, followed by a structural unit (a2) derived from the compound represented by the general formula (I) above, and the other triad structures have the same meaning.
• the amount of the triad structure (U-1) means “the content (mol %) of (a1) bonded between two (a1) in the (a1)-(a1)-(a1) structure constituting (U-1)".
• the content of the triad structure (U-2) means “the content (mol %) of (a1) bonded between (a1) and (a2) in the (a1)-(a1)-(a2) 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 total content of (U-2) and (U-3) in the total amount of the four triad structures of the copolymer (A) is usually 25.0 mol% or less.
• the total content of (U-2) and (U-3) in the total amount of the four triad structures is more preferably 9.0 mol% or less, more preferably 8.5 mol% or less, more preferably 8.0 mol% or less, more preferably 7.5 mol% or less, more preferably 7.0 mol% or less, more preferably 6.0 mol% or less, more preferably 5.5 mol% or less, more preferably 5.3 mol% or less, more preferably 5.0 mol% or less, more preferably 4.8 mol% or less, and even more preferably 4.3 mol% or less.
• the lower limit is 0.1 mol% or more
• 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 1.7 mol% or less, more preferably 1.5 mol% or less, more preferably 1.0 mol% or less, more preferably 0.5 mol% or less, and even more preferably substantially 0 mol%.
• (U-4) is preferably 90 mol% or more, more preferably 94 mol% or more, and even more preferably 99 mol% or more.
• the glass transition temperature of the copolymer (A) is not particularly limited and may be appropriately selected depending on the application.
• Method for producing copolymer (A) Although there is no particular limitation on the method for producing the copolymer (A), it is preferable to produce the copolymer at a polymerization temperature of less than 50° C. in the presence of a radical initiator and a Bronsted acidic compound (B). By producing the copolymer under the above conditions, coloring of the film produced from the resin composition can be suppressed. From this viewpoint, the polymerization temperature is preferably 47° C. or less, more preferably 45° C. or less.
• 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 combining 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 (A) can be formed by subjecting the monomer units constituting the copolymer (A) to a sequence that is less colored by 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) that are easy to use at low temperatures, and redox initiators 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, relative to 100 parts by mass of all the monomers that are the raw materials for copolymer (A).
• the amount of the compound represented by formula (I) is preferably 0.9 equivalents or more relative to the amount of 1,1-dicyanoethylene, more preferably 1.0 equivalents or more, and usually, from the viewpoint of film transparency, preferably 5.0 equivalents or less.
• the amount of the compound represented by formula (I) relative to the amount of 1,1-dicyanoethylene is equal to or more than the lower limit, the reaction can be carried out efficiently.
• a Br ⁇ nsted Acidic compound (B) described below may be used during the production of the copolymer (A).
• the Br ⁇ nsted acidic compound (B) By allowing the Br ⁇ nsted acidic compound (B) to be present during the production of the copolymer (A), the partial conjugated structure of the side chain that causes coloration can be stabilized immediately after the formation of the copolymer (A).
• the amount of the compound 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, relative to 100 parts by mass of all the monomers that are the raw materials for the copolymer (A).
• the content of the copolymer (A) in the resin composition of the present invention is preferably 80% by mass or more, more preferably 85% by mass or more, and even more preferably 90% by mass or more.
• the content of the copolymer (A) in the resin composition is within the above range, it is possible to obtain a film that is less colored when heated.
• the resin composition of the present invention further contains a Br ⁇ nsted acidic compound.
• a Br ⁇ nsted acidic compound it is possible to stabilize the conjugated structure of the copolymer (A), and it is possible to suppress coloration of a film produced using the resin composition during heating.
• the content of the Bronsted acidic compound (B) in the resin composition of the present invention is 0.1 to 95,000 ppm by mass, preferably 0.5 to 90,000 ppm by mass, more preferably 0.8 to 85,000 ppm by mass, more preferably 0.8 to 50,000 ppm by mass, more preferably 1 to 30,000 ppm by mass, more preferably 5 to 10,000 ppm by mass, more preferably 5 to 9,000 ppm by mass, more preferably 10 to 5,000 ppm by mass, and even more preferably 20 to 2,000 ppm by mass.
• the content of the Bronsted acidic compound (B) is within the above range, it is possible to stabilize the conjugated structure of the copolymer (A), and coloring of a film produced using the resin composition during heating can be suppressed.
• the acid dissociation constant (pKa) of the Bronsted acidic compound (B) used in the present invention is preferably 4.8 or less, more preferably 3.0 or less, even more preferably 2.5 or less, and even more preferably 2.0 or less.
• the pKa value means the acid dissociation constant of a conjugate acid in water at 25° C., and can be calculated from the concentration of the substance in question and the hydrogen ion concentration measured using a pH meter.
• Bronsted acid compound that can be used in the present invention, and examples thereof include mineral acids such as sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, hydrobromic acid, and partially neutralized salts thereof, organic acids such as formic acid, acetic acid, trifluoroacetic acid, trichloroacetic acid, dichloroacetic acid, phenylphosphonic acid, ethylphosphinic acid, methanesulfonic acid, ethanesulfonic acid, 2-propanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, and p-toluenesulfonic acid, and combinations thereof.
• mineral acids such as sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, hydrobromic acid, and partially neutralized salts thereof
• organic acids such as formic acid, acetic acid, trifluoroacetic acid, trichloroacetic acid, dichlor
• Compounds that react with water to show Bronsted acidity may also be used.
• a compound having one or more selected from the group consisting of a phosphate group, a carboxy group, a sulfonic acid group, and a phosphite group is preferred.
• phosphoric acid, acetic acid, methanesulfonic acid, p-toluenesulfonic acid, and the like are preferred, with methanesulfonic acid and p-toluenesulfonic acid being more preferred.
• the resin composition of the present invention is not particularly limited as long as it contains the copolymer (A) and the Bronsted acidic compound (B), but may also contain other synthetic resins.
• Other synthetic resins include 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-penten
• the resin composition of the present invention may further contain other components as necessary, such as a solvent, a filler, a thickener, an antioxidant, a plasticizer, a flame retardant, a stabilizer, and an antioxidant.
• a solvent such as a solvent, a filler, a thickener, an antioxidant, a plasticizer, a flame retardant, a stabilizer, and an antioxidant.
• the resin composition of the present invention contains optional components, i.e., the synthetic resin and other components, the total content of these components is preferably 30 mass% or less, more preferably 20 mass% or less, and even more preferably 10 mass% or less, of the total amount of the resin composition.
• 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 (A), the Bronsted acidic compound (B), and the optional 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 composition ratio of sulfur atoms to nitrogen atoms [S/N] is preferably 3.5 ⁇ 10 -8 to 0.3, more preferably 0.5 ⁇ 10 -5 to 0.25, and even more preferably 0.5 ⁇ 10 -4 to 0.2.
• the composition ratio of sulfur atoms to nitrogen atoms [S/N] in the resin composition is within the above range, it is possible to maintain the transparency of the film even after heating for a long period of time.
• the composition ratio of phosphorus atoms to nitrogen atoms [P/N] is preferably 1.4 ⁇ 10 -8 to 0.3, more preferably 1.0 ⁇ 10 -5 to 0.05, and even more preferably 1.0 ⁇ 10 -4 to 0.01.
• the composition ratio of phosphorus atoms to nitrogen atoms [P/N] in the resin composition is within the above range, the transparency of the film can be maintained even after heating for a long period of time.
• the composition ratio can be measured by elemental analysis.
• the molded article and film of the present invention are made using the resin composition of the present invention.
• the shape of the molded article is not limited as long as it is made using the resin composition of the present invention, and examples of the molded article include various shapes such as films, pellets, sheets, plates, pipes, tubes, fibers, nonwoven fabrics, rods, and granules.
• the method for producing the molded product is not particularly limited, and the molded product can be molded by various conventionally known molding methods, such as solution casting, injection molding, blow molding, press molding, extrusion molding, calendar molding, etc.
• the molded product of the present invention may also be a laminate with other materials.
• Examples of molded products using the resin 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 inside surface of tires)), actuators, touch panels, haptic devices (devices with the function of providing tactile feedback to the user), vibration power generation devices (e.g., vibration power generation floors, vibration power generation tires), speakers, microphones, vibration-damping sheets, hollow fiber membranes for water purification, resist films, etc.
• sensors e.g., touch sensors, vibration sensors, biosensors, tire sensors (sensors installed on the inside surface of tires)
• actuators e.g., touch panels
• touch panels e.g., touch panels, touch panels, haptic devices (devices with the function of providing tactile feedback to the user), vibration power generation devices (e.g., vibration power generation floors, vibration power generation tires), speakers, microphones, vibration-damping sheets, hollow fiber membranes for water purification,
• the molded product of the present invention is preferably a film.
• molded products using the resin composition 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 the film before heating and the film after heating at 50° C. under normal pressure for 24 hours is preferably 1.5% or less, more preferably 1.0% or less, and even more preferably 0.8% or less.
• the "film before heating” refers to a film produced by applying the resin composition of the present invention in the case of a solution casting method, and then vacuum drying at 40° C. and 1 kPa for 7 days.
• the difference between the yellowness of the film before heating and the yellowness of the film after heating at 160°C under normal pressure for 1 hour is preferably 3.0% or less, more preferably 2.6% or less, more preferably 2.0% or less, more preferably 1.8% or less, more preferably 1.6% or less, more preferably 1.5% or less, and even more preferably 1.1% or less.
• the yellowness of the film in the present invention is a yellowness measured in accordance with JIS Z8722:2009, and specifically, it can be measured by the method described in the examples.
• the film of the present invention preferably has a low yellowness before heating, and after heating at 40°C and 1 kPa under normal pressure for 7 days, the yellowness is preferably 1.0% or less, more preferably 0.8% or less, even more preferably 0.5% or less, and even more preferably 0.4% or less.
• the film of the present invention preferably has a low yellowness after heating, and the yellowness after heating at 160°C under normal pressure for 1 hour is preferably 3.0% or less, more preferably 2.8% or less, more preferably 2.7% or less, more preferably 2.5% or less, more preferably 2.3% or less, more preferably 2.1% or less, more preferably 2.0% or less, more preferably 1.9% or less, and even more preferably 1.6% or less.
• 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, and even more preferably 0.01 to 1.0 mm.
• the method for producing the film of the present invention is not particularly limited, and it can be molded by a conventionally known method.
• molding methods include solution casting, melt extrusion, calendaring, compression molding, and injection molding.
• the molded product of the present invention may also be a laminate with other materials.
• 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 relative dielectric constant is high from the viewpoint of making it easier to increase the capacitance of the capacitor. Since the film containing the resin composition of the present invention has a high relative dielectric constant, it is suitable for use in a film capacitor.
• the relative dielectric constant of the film measured under conditions of 1 kHz and 25°C is preferably 3 or more, more preferably 3.5 or more, more preferably 3.6 or more, more preferably 3.7 or more, more preferably 3.8 or more, more preferably 4.0 or more, more preferably 4.2 or more, more preferably 4.4 or more, more preferably 4.5 or more, more preferably 4.6 or more, more preferably 4.8 or more, and even more preferably 5.0 or more.
• the dielectric constant of the film can be measured by forming a metal coating on both sides to make a film capacitor and using the method described below.
• the compound represented by the general formula (I) constituting the copolymer (A) is preferably vinyl ester, (meth)acrylic acid ester, styrene derivative, isobutylene, or propylene, more preferably vinyl ester, (meth)acrylic acid ester, styrene derivative, or isobutylene, more preferably vinyl acetate, vinyl propionate, vinyl butyrate, isopropenyl acetate, vinyl chloroacetate, methyl methacrylate, methyl acrylate, butyl acrylate, styrene, ⁇ -methylstyrene, or isobutylene, and even more preferably vinyl acetate, vinyl propionate, vinyl butyrate, methyl methacrylate, styrene, or isobutylene, from the viewpoint of being less susceptible to fluctuations in the relative dielectric constant.
• 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 refers to a material that exhibits piezoelectricity (d 33 ).
• d 33 In the case where d 33 cannot be measured directly, such as in the case of fibers, the piezoelectricity of the fibers may be confirmed by depositing the fibers and processing them into a film, or by producing a film using the same resin composition as that used in the fibers, and measuring d 33 of the film.
• the polarized material can be obtained, for example, by subjecting the film of the present invention to a poling treatment.
• Examples of 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.
• the compound represented by the general formula (I) constituting the copolymer (A) is preferably a vinyl ester or a (meth)acrylic acid ester, more preferably a vinyl ester, and even more preferably vinyl acetate, vinyl propionate, and vinyl butyrate, which have particularly excellent polarization performance.
• 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 -50 to -1 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, in which case a DC electric field of 0 to 400 MV/m, and more preferably 50 to 400 MV/m, is preferably applied for a time period 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) of 1,1-dicyanoethylene synthesized by the method described in the aforementioned literature, 5.5 g (0.064 mol, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), 25 ml of ethyl acetate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), 18 mg of 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), and 68 mg of p-toluenesulfonic acid monohydrate (manufactured by Tokyo Chemical Industry Co., Ltd.) were placed, and the mixture was heated and stirred at 40°C for 6 hours under a nitrogen gas stream to carry out radical polymerization.
• FUJIFILM Wako Pure Chemical Industries, Ltd. 25 ml of ethyl acetate
• the precipitated copolymer (A) was filtered, washed with ethyl acetate and n-hexane (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) in that order, and then dried overnight at 40° C. under reduced pressure to obtain a product (a powder of a resin composition containing copolymer (A)).
• the obtained resin composition containing the copolymer (A) was subjected to NMR spectrum measurement by the method described below. The results are shown in Table 1. Elemental analysis of the obtained resin composition containing copolymer (A) revealed that the resin composition contained 10 ppm by mass of p-toluenesulfonic acid. The remainder of the resin composition was copolymer (A).
• the obtained resin composition containing copolymer (A) was dissolved in a solvent (N,N-dimethylacetamide [manufactured by Tokyo Chemical Industry Co., Ltd.]), applied by a solution casting method using a film applicator (manufactured by Tester Sangyo Co., Ltd.) to a thickness of 50 ⁇ m, and vacuum dried at 40° C. and 1 kPa for 7 days to prepare film (1) [film before heating].
• the resulting film (1) was subjected to 1 H-NMR and elemental analysis, and as a result, the content of p-toluenesulfonic acid was found to be 10 ppm by mass.
• the yellowness of film (1) was measured in accordance with JIS Z8722:2009 using a haze meter SH7000 (manufactured by Nippon Denshoku Kogyo Co., Ltd.). The values were measured at three locations on film (1), and the average value was used as the yellowness. The results are shown in Table 1.
• film (1) was heated in a clean oven DE-41 (manufactured by Yamato Scientific Co., Ltd.) at 50° C. for 24 hours under atmospheric pressure to obtain film (2).
• the yellowness of film (2) was also measured in the same manner as film (1).
• the results are shown in Table 1.
• the film (2) was further heated at 160° C. for 1 hour under atmospheric pressure to obtain a film (3).
• the yellowness of the film (3) was measured in the same manner as for the film (1). The results are shown in Table 1.
• Example 2 The product obtained in Example 1 (powder of the resin composition containing copolymer (A)) was further repeatedly washed with ethyl acetate and n-hexane several times and dried, and then films (1) to (3) were produced in the same manner as in Example 1. The obtained films (1) to (3) were subjected to 1H -NMR, elemental analysis and yellowness measurement in the same manner as in Example 1, and the results are shown in Table 1.
• Example 3 The product obtained in Example 1 (powder of the resin composition containing copolymer (A)) and p-toluenesulfonic acid monohydrate were dissolved in a solvent (N,N-dimethylacetamide [manufactured by Tokyo Chemical Industry Co., Ltd.]) so that the content of p-toluenesulfonic acid in the film was 100 ppm by mass, and films (1) to (3) were produced in the same manner as in Example 1. The obtained films (1) to (3) were subjected to 1H -NMR, elemental analysis, and yellowness measurement in the same manner as in Example 1, and the results are shown in Table 1.
• a solvent N,N-dimethylacetamide [manufactured by Tokyo Chemical Industry Co., Ltd.]
• Examples 4 to 12 Using the materials shown in Tables 1 and 2, copolymer (A) was produced so as to have the composition and molar ratio shown in Tables 1 and 2, and films (1) to (3) were produced in the same manner as in Example 1, except that resin compositions having the compositions shown in Tables 1 and 2 were obtained. The obtained films (1) to (3) were subjected to 1H -NMR, elemental analysis, and yellowness measurement in the same manner as in Example 1. The results are shown in Tables 1 and 2.
• Example 13 Into a 100 ml four-neck flask equipped with a stirrer, a Dimroth stirrer, and a thermometer, 2.0 g (0.026 mol) of 1,1-dicyanoethylene synthesized by the method described in the aforementioned literature, 2.7 g (0.026 mol) of styrene (FUJIFILM Wako Pure Chemical Industries, Ltd.), 17 ml of toluene (FUJIFILM Wako Pure Chemical Industries, Ltd.), 18 mg of 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), and 34 mg of p-toluenesulfonic acid monohydrate (Tokyo Chemical Industry Co., Ltd.) were placed, and the mixture was heated and stirred at 40°C for 4 hours under a nitrogen gas stream to carry out radical polymerization.
• styrene FUJIFILM Wako Pure Chemical Industries, Ltd.
• the precipitated copolymer (A) was filtered, washed with toluene and n-hexane (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) in that order, and then dried overnight at 40° C. under reduced pressure to obtain a product (a powder of a resin composition containing copolymer (A)). Except for the above, films (1) to (3) were prepared in the same manner as in Example 1, and 1 H-NMR, elemental analysis and yellowness index were measured. The results are shown in Table 3.
• Example 14 Into a 300 ml autoclave equipped with a stirrer and a thermometer, 2.0 g (0.026 mol) of 1,1-dicyanoethylene synthesized by the method described in the aforementioned literature, 2.7 g (0.064 mol, manufactured by Takachiho Chemical Industry Co., Ltd.), 8.9 ml of ethyl acetate (manufactured by Fujifilm Wako Pure Chemical Industries Co., Ltd.), 18 mg of 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), and 34 mg of p-toluenesulfonic acid monohydrate (manufactured by Tokyo Chemical Industry Co., Ltd.) were placed, and radical polymerization was carried out by heating and stirring under a nitrogen gas stream at 40°C for 6 hours.
• Example 15 In a 300 ml autoclave equipped with a stirrer and a thermometer, 2.0 g (0.026 mol) of 1,1-dicyanoethylene synthesized by the method described in the aforementioned literature, 3.6 g (0.064 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), 6.7 ml of ethyl acetate (manufactured by Fujifilm Wako Pure Chemical Industries Co., Ltd.), 18 mg of 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), and 18 mg of p-toluenesulfonic acid monohydrate (manufactured by Tokyo Chemical Industry Co., Ltd.) were placed, and radical polymerization was carried out by heating and stirring under a nitrogen gas stream at 40°C for 6 hours.
• Example 16> In a 100 ml four-neck flask equipped with a stirrer, Dimroth, and thermometer, 2.0 g (0.026 mol) of 1,1-dicyanoethylene synthesized by the method described in the aforementioned literature, 2.8 g (0.032 mol, FUJIFILM Wako Pure Chemical Industries, Ltd.), 3.7 g (0.032 mol, FUJIFILM Wako Pure Chemical Industries, Ltd.), 25 ml of ethyl acetate (FUJIFILM Wako Pure Chemical Industries, Ltd.), 18 mg of 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), and 18 mg of p-toluenesulfonic acid monohydrate (Tokyo Chemical Industry Co., Ltd.) were placed, and radical polymerization was carried out by heating and stirring under a nitrogen gas stream at 40°C for 6 hours.
• radical polymerization was carried out by heating and stirring under a nitrogen gas stream at 40
• Example 17 Films (1) to (3) were prepared in the same manner as in Example 16, except that the amount of vinyl acetate used was changed to 3.6 g (0.039 mol, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) and 3.9 g (0.039 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of vinyl butyrate, and 1 H-NMR, elemental analysis and yellowness index measurements were performed. The results are shown in Table 3.
• Example 18 Films (1) to (3) were prepared in the same manner as in Example 17, except that 68 mg of p-toluenesulfonic acid monohydrate (Tokyo Chemical Industry Co., Ltd.) was added. The results of measuring 1H -NMR, elemental analysis and yellowness index of the obtained films (1) to (3) in the same manner as in Example 1 are shown in Table 3.
• Example 19 Into a 100 ml four-neck flask equipped with a stirrer, Dimroth and thermometer, 2.0 g (0.026 mol) of 1,1-dicyanoethylene synthesized by the method described in the aforementioned literature, 1.4 g (0.013 mol, Fujifilm Wako Pure Chemical Industries, Ltd.), 1.3 g (0.013 mol, Fujifilm Wako Pure Chemical Industries, Ltd.), 17 ml of toluene (Fujifilm Wako Pure Chemical Industries, Ltd.), 18 mg of 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), and 18 mg of p-toluenesulfonic acid monohydrate (Tokyo Chemical Industry Co., Ltd.) were placed, and radical polymerization was carried out by heating and stirring under a nitrogen gas stream at 40°C for 4 hours.
• radical polymerization was carried out by heating and stirring under a nitrogen gas stream at 40°C for 4 hours.
• Examples 20 to 24 Comparative Examples 1 to 4> Films (1) to (3) were produced in the same manner as in Example 1, except that the materials shown in Tables 4 to 5 were used, copolymer (A) was produced so as to have the composition and molar ratio shown in Tables 4 to 5, and resin compositions having the compositions shown in Tables 4 to 5 were obtained.
• Comparative Example 1 polymerization was performed without using p-toluenesulfonic acid monohydrate, and films (1) to (3) were produced. The obtained films were subjected to 1H -NMR, elemental analysis, and measurement of yellowness index. The results are shown in Tables 4 to 5.
• the dielectric constant of the obtained film was measured by the method described later, and the results are shown in Tables 1 to 5.
• 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 with 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 6.
• 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.
• Elemental analysis of the film was performed using a trace sulfur analyzer TS-2100H (manufactured by Nitto Seiko Analytech Co., Ltd.) for sulfur, an iCAP7400 Duo (manufactured by ThermoFisher) for phosphorus, and a FLASH2000 (manufactured by Thermoscientific) for carbon, hydrogen, oxygen, and nitrogen.
• TS-2100H manufactured by Nitto Seiko Analytech Co., Ltd.
• iCAP7400 Duo manufactured by ThermoFisher
• FLASH2000 manufactured by Thermoscientific
• film (1) refers to a film that was vacuum dried at 40 ° C. and 1 kPa for 7 days
• film (2) refers to a film obtained by heating film (1) at 50 ° C. for 24 hours under atmospheric pressure in a clean oven DE-41 (manufactured by Yamato Scientific Co., Ltd.)
• film (3) refers to a film obtained by heating film (2) at 160 ° C. for 1 hour under atmospheric pressure.
• films using the resin composition of the present invention are able to suppress coloration even after heating, and have excellent dielectric properties.
• the film of the present invention has piezoelectricity and can therefore be suitably used for touch panel applications and the like.

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• 2023
  • 2023-10-20 JP JP2024551871A patent/JPWO2024085249A1/ja active Pending
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