Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
  • C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
  • C08L23/22—Copolymers of isobutene; Butyl rubber; Homopolymers or copolymers of other iso-olefins
• • 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
  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F210/04—Monomers containing three or four carbon atoms
  • C08F210/06—Propene
• • 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
  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F210/04—Monomers containing three or four carbon atoms
  • C08F210/08—Butenes
  • C08F210/10—Isobutene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/30—Nitriles
  • C08F222/34—Vinylidene cyanide
• • 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
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/18—Homopolymers or copolymers of nitriles
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D01F6/30—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising olefins as the major constituent
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D01F6/38—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising unsaturated nitriles as the major constituent
• • 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
• • 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
  • C08J2323/18—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
• • 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
  • C08J2323/18—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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
  • C08J2333/18—Homopolymers or copolymers of nitriles

Definitions

• the present invention relates to a copolymer composition containing a copolymer having structural units derived from 1,1-dicyanoethylene and structural units derived from a specific compound, a method for producing the same, and molded products and the like that use the same.
• Copolymer compositions containing copolymers obtained by radical polymerization of 1,1-dicyanoethylene and polymerizable monomers are known to be suitable for use as materials for films, filaments, etc. (see, for example, Patent Document 1).
• the copolymer compositions have excellent transparency, particularly when processed into films, and are therefore used as materials for optical components, lighting components, signboard components, decorative components, etc.
• Copolymers containing structural units derived from 1,1-dicyanoethylene have high cohesive strength and high melt viscosity, so they require high processing temperatures, but raising the temperature too high can lead to degradation due to crosslinking and thermal decomposition.
• the copolymer composition produced by the method described in Patent Document 1 contains a large amount of low-molecular-weight compounds with a molecular weight of less than 1,000, so when heated, gas is generated due to the low-molecular-weight compounds with a molecular weight of less than 1,000, which can lead to reduced moldability.
• the present invention has been made in consideration of the above-mentioned problems in the past, and aims to provide a copolymer composition that can give films and the like that have good moldability and excellent flex resistance, and a method for producing the same.
• Another aim of the present invention is to provide molded products, films, sheets, and fibers that use the copolymer composition.
• the inventors conducted research and discovered that in a copolymer composition obtained by copolymerizing 1,1-dicyanoethylene with a specific monomer, by reducing the amount of low molecular weight compounds with a molecular weight of less than 1,000 contained in the copolymer composition, the moldability is improved and deterioration of the copolymer composition can be suppressed, resulting in improved transparency and flex resistance of films and the like using the copolymer composition, leading to the completion of the present invention.
• a copolymer composition characterized in that the weight loss rate when held for 30 minutes at a temperature (T) at which a complex viscosity measured under conditions of a frequency of 1 Hz and a strain of 1% becomes 10,000 Pa s is 5.0 mass % or less.
• 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 present invention provides a copolymer composition that can produce films and the like that have good moldability and excellent flex resistance, and a method for producing the same.
• the present invention also provides molded products, films, sheets, and fibers that use the copolymer composition.
• the copolymer composition of the present invention is a copolymer composition containing a copolymer (A) having 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):
• the composition is characterized in that the weight loss rate when held for 30 minutes at a temperature (T) at which the complex viscosity, measured under conditions of a frequency of 1 Hz and a strain of 1%, is 10,000 Pa ⁇ s is 5% by mass or less.
• 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 composition of the present invention has a weight loss rate of 5.0% by mass or less when held for 30 minutes at a temperature (T) at which the complex viscosity measured under conditions of a frequency of 1 Hz and a strain of 1% is 10,000 Pa ⁇ s.
• T temperature
• the weight loss occurs when the low molecular weight compound contained in the copolymer composition is removed by volatilization by the temperature (T). This reduces the amount of low molecular weight compounds having a molecular weight of less than 1,000 in the copolymer composition, so that even if the copolymer composition is heated during processing, the amount of gas generated is small, and deterioration due to thermal decomposition can be suppressed, thereby improving moldability.
• the weight loss rate is preferably 4.0% by mass or less, more preferably 3.0% by mass or less, even more preferably 2.5% by mass or less, even more preferably 2.0% by mass or less, particularly preferably 1.5% by mass or less, particularly preferably 1.0% by mass or less, and particularly preferably 0.8% by mass or less.
• the weight loss rate can be measured using a thermogravimetric/differential thermal analyzer (TGA/DSC), specifically, by the method described in the examples.
• the temperature (T) at which the complex viscosity measured under conditions of a frequency of 1 Hz and a strain of 1% becomes 10,000 Pa s is preferably 120 to 300° C., more preferably 125 to 280° C., even more preferably 130 to 260° C., and even more preferably 140 to 240° C.
• the temperature (T) can be measured by a rheometer.
• the copolymer (A) used in the present invention has 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).
• the copolymer (A) used in the present invention has 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 has a structural unit (a2) derived from a compound represented by the following general formula (I).
• CH 2 CR 1 R 2 (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 of R1 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 aryl group in the present invention may have one or more substituents, and examples of the substituents include alkyl groups such as a methyl group and an ethyl group, an acetoxy group, an acetyl group, and a halogen atom selected from a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• substituents include alkyl groups such as a methyl group and an ethyl group, an acetoxy group, an acetyl group, and a halogen atom selected from a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• 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
• R2 is preferably one selected from the group consisting of a hydrogen atom, an alkyl group, an ester group represented by -COOR3 , and an acyloxy group represented by -OCOR5 , more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and even more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
• the compound represented by the general formula (I) is preferably one or more selected from the group consisting of vinyl esters, (meth)acrylic acid esters, styrene derivatives, ethylene, propylene, isobutylene, 1-pentene, 1-hexene, 3-methyl-1-butene, and 4-methyl-1-pentene, 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 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 a known method.
• (meth)acrylic acid ester means "acrylic acid ester or methacrylic acid ester”.
• the copolymer (A) may have two or more different structural units (a2), and from the viewpoint of reducing production costs, 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).
• each structural unit includes at least one 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 25 to 70 mol%, even more preferably from 30 to 55 mol%, and even more preferably from 35 to 55 mol%.
• the content of the structural unit (a2) is preferably from 20 to 80 mol%, preferably from 30 to 75 mol%, more preferably from 45 to 70 mol%, and even more preferably from 45 to 65 mol%.
• the copolymer composition has improved moldability and flex resistance.
• 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 (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 general formula (I).
• 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 5% thermal decomposition temperature of the copolymer (A) is preferably 200°C or higher, more preferably 230°C or higher, more preferably 240°C or higher, more preferably 250°C or higher, more preferably 270°C or higher, more preferably 280°C or higher, more preferably 290°C or higher, and even more preferably 300°C or higher.
• the thermal decomposition temperature is calculated by performing thermogravimetric analysis (TG) of the copolymer at a heating rate of 10°C/min in accordance with JIS K7120:1987 under a nitrogen atmosphere, and calculating the temperature at which the weight is reduced by 5% with the weight at 30°C as the origin.
• TG thermogravimetric analysis
• the complex viscosity of the copolymer (A) is not particularly limited and can be appropriately adjusted according to the processing method.
• the complex viscosity of the copolymer (A) is preferably 100,000 Pa.s or less at a frequency of 1 Hz and a strain of 1%, more preferably 50,000 Pa.s or less, more preferably 30,000 Pa.s or less, more preferably 20,000 Pa.s or less, and even more preferably 10,000 Pa.s or less.
• the complex viscosity can be adjusted by the molecular weight of the copolymer (A), and may be adjusted by using a copolymer (A) having a plurality of molecular weights.
• the complex viscosity can be measured, for example, by sandwiching the resin between parallel plates each having a diameter of 8 mm on both sides and using a DHR 2 manufactured by TA Instruments under conditions of a nitrogen atmosphere, a frequency of 1 Hz, a strain of 1%, and a heating rate of 3° C./min.
• the glass transition temperature of the copolymer (A) is not particularly limited, and may be appropriately selected depending on the application. From the viewpoint of increasing heat resistance, it is preferably 30°C or higher, more preferably 50°C or higher, even more preferably 70°C or higher, and even more preferably 75°C or higher.
• the glass transition temperature of the copolymer (A) is usually 200°C or lower, more preferably 190°C or lower, more preferably 180°C or lower, more preferably 170°C or lower, and even more preferably 160°C or lower.
• the glass transition temperature is below the lower limit, it becomes easier to set the molding temperature at a temperature lower than the thermal decomposition temperature, and it is easy to prevent the occurrence of defects such as foaming.
• the glass transition temperature can be measured by a method conforming to JIS K7121:2012 using a differential scanning calorimeter.
• the method for producing the copolymer (A) is not particularly limited, but for example, it is preferable to produce the copolymer at a polymerization temperature of 70° C. or less, and in the presence of a radical initiator. By producing the copolymer under the above conditions, deterioration of the copolymer composition can be suppressed. From this viewpoint, the polymerization temperature is preferably 65° C. or less, and more preferably 60° 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,
• radical polymerization initiators azo compounds such as azobisisobutyronitrile and 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) which 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) charged is preferably 0.9 equivalents or more relative to the amount of 1,1-dicyanoethylene charged, more preferably 1.0 equivalents or more, and usually, from the viewpoint of the transparency of the film or sheet, preferably 5.0 equivalents or less.
• the reaction can be carried out efficiently.
• the content of copolymer (A) in the copolymer 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 copolymer (A) in the copolymer composition is within the above range, so that gas generation during heating is suppressed and molding processability is improved. In addition, the bending resistance of molded products using the copolymer composition is improved.
• the weight average molecular weight (Mw) of the copolymer (A) is not particularly limited, but is preferably 30,000 to 3,000,000, more preferably 40,000 to 2,100,000, and even more preferably 50,000 to 1,700,000.
• Mw weight average molecular weight
• the weight average molecular weight (Mw) of the copolymer (A) is equal to or more than the lower limit, the bending resistance of a molded article using the copolymer composition is improved, and when it is equal to or less than the upper limit, the moldability is improved and the total light transmittance of a molded article using the copolymer composition is also improved.
• the number average molecular weight (Mn) of the copolymer (A) is not particularly limited, but is preferably 20,000 to 2,000,000, more preferably 30,000 to 1,500,000, and even more preferably 40,000 to 1,200,000.
• Mn number average molecular weight of the copolymer (A) is equal to or greater than the lower limit, the bending resistance of a molded product using the copolymer composition is improved, and when it is equal to or less than the upper limit, the moldability is improved and the total light transmittance of a molded product using the copolymer composition is also improved.
• the molecular weight distribution (Mw/Mn) of the copolymer (A) is preferably 1.0 to 10.0, more preferably 1.0 to 9.0, and even more preferably 1.0 to 8.0. When Mw/Mn is within the above range, the viscosity of the copolymer (A) varies little, making it easy to handle.
• the Mw and Mn of the copolymer (A) are the weight average molecular weight and number average molecular weight in terms of polystyrene determined by gel permeation chromatography (GPC), and specifically can be measured by the method described in the Examples.
• the copolymer composition of the present invention is not particularly limited as long as it contains the copolymer (A), but may also contain a synthetic resin.
• 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-pentene, 1-hexene,
• the amount of components other than the copolymer (A) is small. More specifically, in the copolymer composition of the present invention, the content of low-molecular-weight compounds having a molecular weight of less than 1,000 is preferably 10% by mass or less.
• the low molecular weight compound having a molecular weight of less than 1,000 is often a low molecular weight polymer produced as a by-product during the production of copolymer (A), and by reducing the amount of this low molecular weight polymer, the amount of gas generated is small even when the copolymer composition is heated during processing, and deterioration due to thermal decomposition can be suppressed, thereby improving moldability.
• the content of the low molecular weight compound having a molecular weight of less than 1,000 is more preferably 8% by mass or less, even more preferably 5% by mass or less, even more preferably 4% by mass or less, and particularly preferably 3% by mass or less.
• the content of low molecular weight compounds having a molecular weight of less than 1,000 can be determined by measuring the weight of components having a molecular weight of 1,000 or more separated by preparative chromatography and dried, and then calculating from the difference between the charged weight and the dried weight.
• the copolymer composition of the present invention may further contain other components as necessary.
• the other components may include solvents, fillers, thickeners, antioxidants, plasticizers, flame retardants, stabilizers, and antioxidants, but when these optional components are contained, the total content of these components is preferably 5 mass% or less of the total amount of the copolymer composition.
• the method for producing the copolymer composition of the present invention is not particularly limited.
• a product containing the copolymer (A) obtained by polymerization of the copolymer (A) may be used as the copolymer composition as it is.
• a method is preferred in which the product obtained by polymerization is washed with a solvent used in the polymerization, such as benzene, toluene, o-xylene, m-xylene, p-xylene, mesitylene, pseudocumene, ethylbenzene, propylbenzene, chlorobenzene, dichlorobenzene, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, n-pentane, n-hexane, n-heptane, or cyclohexane, and then washed with a solvent selected from nitrile solvents such as acetonitrile, propionitrile, or benzonitrile, alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, n-butan
• the copolymer composition contains the optional component
• it can be produced by a production method including a mixing step of mixing the optional component with the copolymer (A).
• a production method including a mixing step of mixing the optional component with the copolymer (A).
• the method for mixing each component and they can be mixed by a known method.
• the copolymer composition of the present invention can also be used as a coating material, and can also be used in the following applications: 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 users), vibration power generation devices (e.g., vibration power generation floors, vibration power generation tires), speakers, and microphones.
• 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, haptic devices (devices with the function of providing tactile feedback to users), vibration power generation devices (e.g., vibration power generation floors, vibration power generation tires), speakers, and microphones.
• the molded article of the present invention is a product made using the copolymer composition of the present invention.
• the shape of the molded article is not limited as long as it is made using the copolymer composition of the present invention, and may be, for example, a film, a sheet, a fiber, a pellet, a plate, a pipe, a tube, a rod-shaped body, a granular body, or the like.
• the method for producing the molded article is not particularly limited, and the molded article may be molded by various conventionally known molding methods, such as injection molding, blow molding, press molding, extrusion molding, and calendar molding.
• the molded article using the copolymer composition of the present invention can be processed into a film, in particular, to obtain a film having superior transparency.
• film refers to a membranous object having a thickness of less than 250 ⁇ m
• sheet refers to a thin plate-like object having a thickness of 250 ⁇ m or more.
• the film or sheet of the present invention preferably has a total light transmittance of 75% or more, more preferably 80% or more, and even more preferably 85% or more.
• the total light transmittance of the film or sheet in the present invention is a value measured in accordance with JIS K7361-1:1997, and specifically, it can be measured by the method described in the examples.
• the thickness of the film or sheet of the present invention is preferably 0.0001 to 10.0 mm, more 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 or sheet of the present invention can be molded by a conventionally known method.
• molding methods include solution casting, melt extrusion, calendaring, compression molding, and injection molding.
• Examples of molded products using the copolymer composition of the present invention include film capacitors, insulating layers for EL elements, electrostatic induction conversion elements, sensors (e.g., touch sensors, vibration sensors, biosensors, tire sensors (sensors installed on the inner surface of tires)), actuators, touch panels, haptic devices (devices with the function of providing tactile feedback to users), vibration power generation devices (e.g., vibration power generation floors, vibration power generation tires), speakers, microphones, etc.
• Example 1 In a 900 ml autoclave equipped with a stirrer and a thermometer, 8.0 g (0.104 mol) of 1,1-dicyanoethylene synthesized by the method described in J. Am. Chem.
• the mixture was washed in the order of toluene (the solvent used in the polymerization) and acetonitrile (a solvent other than the solvent used in the polymerization, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and then dried overnight at 40°C under reduced pressure to obtain a product (a powder of a resin composition containing a copolymer).
• toluene the solvent used in the polymerization
• acetonitrile a solvent other than the solvent used in the polymerization, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
• the copolymer composition thus obtained was placed in a mold (15 cm long x 15 cm wide x 0.50 mm high) placed between two stainless steel plates (35 cm long x 35 cm wide), and then set in a heat press (manufactured by Shinto Metal Industry Co., Ltd.), where the copolymer composition was heated at 175°C for 3 minutes without applying pressure. Next, the copolymer composition was hot pressed at a pressure of 90 kgf/cm 2 (about 8.8 MPa) for 180 seconds. Immediately after that, the stainless steel plate and the mold were set in a cooling press at 23° C. Pressure was applied to the copolymer composition sheet while cooling the sheet in the cooling press. Then, the sheet in the mold was cut out to obtain a sheet with a thickness of 0.5 mm. The following measurements were performed on the obtained copolymer composition and sheet. The results are shown in Table 1.
• Examples 2 to 14 Copolymer compositions and sheets were produced in the same manner as in Example 1, except that the production conditions were changed as shown in Tables 4 to 6. The physical properties of the obtained copolymer compositions and sheets were measured in the same manner as in Example 1. The results are shown in Tables 1 to 3.
• the reagents in the table used were the same as those described in Example 1, as well as propylene (manufactured by Takachiho Chemical Industry Co., Ltd.), styrene (manufactured by FUJIFILM Wako Pure Chemical Industries Co., Ltd.), ethyl acetate (manufactured by FUJIFILM Wako Pure Chemical Industries Co., Ltd.), dibenzyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.), benzene (manufactured by FUJIFILM Wako Pure Chemical Industries Co., Ltd.), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) (manufactured by FUJIFILM Wako Pure Chemical Industries Co., Ltd.), 2,2'-azobis(2,4-dimethylvaleronitrile) (manufactured by FUJIFILM Wako Pure Chemical Industries Co., Ltd.), pival
• the temperature (T) means “the temperature at which the complex viscosity measured under conditions of a frequency of 1 Hz and a strain of 1% becomes 10,000 Pa s”
• the weight loss rate means “the weight loss rate (%) when held for 30 minutes at the temperature (T).”
• Copolymer compositions and sheets were produced in the same manner as in Example 1, except that the production conditions were changed as shown in Tables 4 to 6 and washing was carried out using only the polymerization solvent.
• the physical properties of the obtained copolymer compositions and sheets were measured in the same manner as in Example 1. The results are shown in Tables 1 to 3.
• the weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw/Mn) were determined in terms of standard polystyrene by gel permeation chromatography (GPC) using the following measuring device and conditions: ⁇ Apparatus: Tosoh Corporation GPC device "HLC-8320" Separation column: "TSKgel Super HZM-M” manufactured by Tosoh Corporation Eluent: Tetrahydrofuran Eluent flow rate: 0.7 ml/min Sample concentration: 5 mg/10 ml Column temperature: 40° C.
• copolymer (A) having a polystyrene equivalent molecular weight of 1,000 or more was taken under the following conditions, the dry weight of copolymer (A) was measured, and the content of low molecular weight compounds was calculated from the difference between the charged weight and the dry weight of copolymer (A). Note that, for the copolymer compositions of the examples, the copolymer compositions were measured after washing with a solvent other than the solvent used in polymerization.
• the copolymer composition obtained was prepared as a sample before washing with a solvent (acetonitrile) other than the solvent used in the polymerization.
• the prepared sample was heated at the temperatures shown in Tables 1 to 3, and the volatile components generated were collected in a glass container cooled with liquid nitrogen.
• the amount of compounds (low molecular weight compounds) having a molecular weight of less than 1,000 in terms of standard polystyrene was measured for the collected components by GPC (gel permeation chromatography), and the amount was evaluated according to the following criteria.
• the results are shown in Tables 1 to 3.
• the measurement apparatus and conditions are as follows.
• ⁇ Melt moldability evaluation method> The obtained sheet was observed and the melt moldability was judged according to the following criteria. Rating [A]: There was no unmelted copolymer powder in the sheet, the copolymer was sufficiently melted, and a sheet was obtained having an area of 90 to 100% of the area of a mold frame measuring 15 cm long x 15 cm wide. Rating [B]: There was no unmelted copolymer powder in the sheet, the copolymer was melted, and a sheet was obtained with an area of 50 to 89% of the area of a mold frame of 15 cm length x 15 cm width.
• the copolymer composition of the present invention has good moldability and can give sheets and the like having excellent flex resistance. It is clear that the copolymer compositions of the comparative examples have poor moldability, since foaming occurred during melt molding.

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