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
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  • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
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  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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  • C08F210/06—Propene
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  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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  • 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
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  • 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
  • C08F212/10—Styrene with nitriles
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  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
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  • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2250/00—Layers arrangement
  • B32B2250/02—2 layers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
  • B32B2307/202—Conductive
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2457/00—Electrical equipment
  • B32B2457/16—Capacitors
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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
  • 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
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  • 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
  • C08J2323/04—Homopolymers or copolymers of ethene
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  • 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
• • 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
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  • 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
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  • 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
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  • 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
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  • 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
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  • 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
  • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
  • C08J2423/02—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
  • C08J2423/04—Homopolymers or copolymers of ethene
• • 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)

Definitions

• the present invention relates to a copolymer containing structural units derived from 1,1-dicyanoethylene and structural units derived from a specific polymerizable monomer in a specific sequence, a method for producing said copolymer, and a resin composition containing said copolymer.
• Non-Patent Document 1 describes the analysis method for copolymers of 1,1-dicyanoethylene and styrene.
• 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 in the past, and aims to provide a copolymer that can suppress coloration even after heating, and a method for producing the copolymer.
• Another aim of the present invention is to provide a resin composition containing the copolymer, and a molded product and film that use 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) ...
• (U-4) A copolymer characterized in that the content of (U-2) and (U-3) is 5.5 mol % or less in the total amount of the four types of triad structures.
• 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 alkenyl group, a cycloalkyl group, an aryl group, a halogen atom, and a haloalkyl group.
• [5] A method for producing the copolymer according to any one of the above [1] to [4], wherein the polymerization temperature is 45° C. or lower, the amount of the compound represented by the general formula (I) is 0.80 to 3.5 equivalents relative to the amount of 1,1-dicyanoethylene, and the copolymer is produced in the presence of a radical polymerization initiator.
• [6] A resin composition comprising the copolymer according to any one of [1] to [4] above.
• [7] A molded article using the copolymer according to any one of [1] to [4] above or the resin composition according to [6] above.
• the present invention can provide a copolymer that can suppress coloration even after heating, and a method for producing the copolymer.
• 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) ...
• the copolymer is characterized in that the total content of (U-2) and (U-3) is 5.5 mol % or less based on the total amount of the four types of triad structures.
• 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 alkenyl group, a cycloalkyl group, an aryl group, a halogen atom, and a haloalkyl group.
• 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 5.5 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 5.5 mol% or less, preferably 5.2 mol% or less, preferably 5.0 mol% or less, preferably 4.8 mol% or less, and more preferably 4.6 mol% or less.
• the lower limit is 0.5 mol% or more, but may be lower than that, and is preferably 0.1 mol% or more.
• 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 50° C. or less.
• 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) is equal to or less than the upper limit, the number of consecutive sequences of (A) in the copolymer is reduced, and as a result, coloration of a molded product using the copolymer of the present invention after heating is further suppressed.
• 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, and even more preferably 0.5 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 a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, a halogen atom and a haloalkyl group.
• 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 a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, a halogen atom and a haloalkyl group.
• 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, and an n-hexyl group.
• the alkenyl group represented by R2 is preferably an alkenyl group having 2 to 12 carbon atoms, and examples thereof include a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, a pentenyl group, a prenyl group, a hexenyl group (such as a cis-3-hexenyl group), and a cyclohexenyl group.
• the cycloalkyl group for R2 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 R2 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 halogen atom of R2 includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• the haloalkyl group for R2 is preferably a haloalkyl group having 1 to 12 carbon atoms, and more preferably a haloalkyl group having 1 to 6 carbon atoms.
• Examples of the halogen atom constituting the haloalkyl group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• R2 is preferably one selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, and an aryl group, more preferably an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms, and even more preferably an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms.
• the compound represented by the general formula (I) is preferably at least one selected from the group consisting of styrene, ⁇ -methylstyrene, p-methylstyrene, isobutylene, 1-hexene, propylene, and ethylene.
• styrene ⁇ -methylstyrene
• p-methylstyrene isobutylene
• 1-hexene propylene
• ethylene ethylene
• 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 48 to 51 mol %.
• the content of the structural unit (B) is preferably 20 to 80 mol%, preferably 45 to 70 mol%, more preferably 47 to 60 mol%, even more preferably 49 to 52 mol%, and even more preferably 50 to 51 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 structural unit derived from a monomer other than the structural unit (A) derived from 1,1-dicyanoethylene and the structural unit (B) derived from the compound represented by the general formula (I).
• the other structural units include vinyl acetate, vinyl propionate, methyl acrylate, ethyl acrylate, and butyl acrylate.
• 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 by the method for producing the copolymer of the present invention, in which the polymerization temperature is 45° C. or less and the copolymer is produced in the presence of a radical initiator.
• the polymerization temperature is preferably 44° C. or less, more preferably 43° C. or less, and even more preferably 40° 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) to be charged is preferably 0.80 equivalents or more relative to the amount of 1,1-dicyanoethylene, more preferably 0.85 equivalents or more, and even more preferably 0.90 equivalents or more, and is usually preferably 3.5 equivalents or less from the viewpoint of suppressing production costs.
• the amount of the compound represented by the general formula (I) to the amount of 1,1-dicyanoethylene to be charged is equal to or more than the lower limit, it becomes easier to adjust the total content of (U-2) and (U-3) in the total amount of the triad structure, and as a result, discoloration of a molded product using the copolymer after heating can be suppressed.
• 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, even more preferably 200 ppm or less, and even more preferably 100 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 of these components is preferably 10 mass% or less, preferably 3 mass% or less, and preferably 0.001 mass% or more, 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 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 various shapes such as films, pellets, sheets, plates, pipes, tubes, rods, and granules.
• 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.
• 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 2.5% or less, more preferably 2.0% or less, even more preferably 1.0% or less, and even more preferably 0.9% or less.
• the yellowness in the present invention is a yellowness measured in accordance with JIS Z8722:2009, and specifically, can be measured by the method described in the examples.
• 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 2.5% or less, more preferably 1.5% or less, even more preferably 1.0% or less, and even more preferably 0.8% 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, 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.
• Example 1 Into a 100 ml four-neck flask equipped with a stirrer, a Dimroth device, and a thermometer, 2.0 g (0.026 mol, water content 390 ppm) of 1,1-dicyanoethylene synthesized by the method described in the aforementioned literature, 2.7 g (0.026 mol, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.), 17 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 4 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 below, 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.
• Example 2 Comparative Examples 1 to 4> A film was prepared in the same manner as in Example 1, except that the water concentration in 1,1-dicyanoethylene, the polymerization temperature, and the ratio of the charged amounts were changed as shown in Tables 1 and 2. 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 3 2.0 g (0.026 mol, water content 390 ppm) of 1,1-dicyanoethylene synthesized by the method described in the aforementioned literature, 3.6 g (0.064 mol, Tokyo Chemical Industry Co., Ltd.), 6.7 ml of ethyl acetate (Fuji Film Wako Pure Chemical Industries, Ltd.), and 18 mg of 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) were placed in a 300 ml autoclave equipped with a stirrer and a thermometer, and radical polymerization was carried out by heating and stirring under a nitrogen gas stream at 40°C for 6 hours.
• the precipitated copolymer was filtered, washed with ethyl acetate 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 resulting copolymer was subjected to NMR spectrum measurement by the method described below, and a film was produced using the resulting copolymer and the yellowness index was measured in the same manner as in Example 1. The results are shown in Table 1.
• Example 4 2.0 g (0.026 mol, water content 390 ppm) 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 Fuji Film Wako Pure Chemical Industries Co., Ltd.), and 18 mg of 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) were placed in a 300 ml autoclave equipped with a stirrer and a thermometer, and radical polymerization was carried out by heating and stirring under a nitrogen gas stream at 40°C for 6 hours.
• Examples 5 to 8 Comparative Examples 5 to 8> A film was prepared in the same manner as in Example 3 except that the water concentration in 1,1-dicyanoethylene, the polymerization temperature, and the ratio of the charged amounts were changed as shown in Tables 1 and 2. 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 3. The results are shown in Tables 1 and 2.
• Example 9 Comparative Examples 9 to 10> A film was prepared in the same manner as in Example 4, except that the water concentration in 1,1-dicyanoethylene, the polymerization temperature, and the ratio of the charged amounts were changed as shown in Tables 1 and 2. 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 4. The results are shown in Tables 1 and 2.
• the precipitated copolymer was filtered, washed with ethyl acetate 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 resulting copolymer was subjected to NMR spectrum measurement by the method described below, and a film was produced using the resulting copolymer and the yellowness index was measured in the same manner as in Example 1. The results are shown in Table 1.
• the copolymer of the present invention can be suppressed from discoloring even after heating, and therefore can be suitably used for molded products such as films.
• the experiments in Reference Examples 1 to 5 were conducted in accordance with the description in the specification of U.S. Patent Application Publication No. 2,615,868, but the copolymers obtained by the method described in the literature did not have a content of (U-2) and (U-3) of 5.5 mol % or less in the total amount of the four types of triad structures. Therefore, the films of Reference Examples 1 to 5 produced using the copolymers were discolored after heating.

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