WO2023191062A1 - Chlorine-containing polymer modifier, resin composition, and molded body - Google Patents

Chlorine-containing polymer modifier, resin composition, and molded body Download PDF

Info

Publication number
WO2023191062A1
WO2023191062A1 PCT/JP2023/013573 JP2023013573W WO2023191062A1 WO 2023191062 A1 WO2023191062 A1 WO 2023191062A1 JP 2023013573 W JP2023013573 W JP 2023013573W WO 2023191062 A1 WO2023191062 A1 WO 2023191062A1
Authority
WO
WIPO (PCT)
Prior art keywords
mass
chlorine
resin composition
containing polymer
copolymer
Prior art date
Application number
PCT/JP2023/013573
Other languages
French (fr)
Japanese (ja)
Inventor
和希 西川
達宏 松原
Original Assignee
デンカ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by デンカ株式会社 filed Critical デンカ株式会社
Publication of WO2023191062A1 publication Critical patent/WO2023191062A1/en

Links

Classifications

    • 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
    • C08F212/10—Styrene with nitriles
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C08L101/04—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—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 halogen; Compositions of derivatives of such polymers
    • C08L27/02—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 halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—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 halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride

Definitions

  • the present invention relates to a modifier for chlorine-containing polymers, a resin composition containing the modifier for chlorine-containing polymers and a chlorine-containing polymer, and a molded article using the resin composition.
  • the present invention also relates to a resin composition and a molded article.
  • Chlorine-containing polymer resins are inexpensive and have excellent chemical, physical, and mechanical properties, so they are produced in large quantities and used for various purposes.
  • chlorine-containing polymers have the disadvantage of lacking heat resistance (low heat softening temperature), and for example, they have been measured by the 50 method (load 50N, heating rate 50°C/hour) based on JIS K7206:1999.
  • the Vicat softening temperature is around 82°C, and the softening temperature is further lowered by stabilizers and plasticizers that are usually added during molding.
  • Patent Documents 1 to 4 a method is known in which a resin that imparts heat resistance is mixed with polyvinyl chloride.
  • Patent 6475501 JP2006-265373 International publication WO2022/039098
  • a first aspect of the present invention is a modifier for chlorine-containing polymers that can improve the heat resistance and impact resistance of chlorine-containing polymers, a resin composition containing the modifier for chlorine-containing polymers, and a resin composition that can improve the heat resistance and impact resistance of chlorine-containing polymers.
  • the purpose of this paper is to provide a molded article using the following methods.
  • the second aspect of the present invention was made in view of the above circumstances, and even when an impact modifier and a heat resistance imparting agent are added, impact resistance and heat resistance, which are in a trade-off relationship, are good.
  • a resin composition containing a chlorine-containing polymer that is compatible with the following.
  • a modifier for chlorine-containing polymers A 10% by mass THF solution of the modifier for chlorine-containing polymers and 10% by mass of a chlorine-containing polymer having a K value of 66.7 ⁇ 1.0 and a degree of chlorination of 57.0 ⁇ 1.0%. % THF solution at a volume ratio of 1:1, and the lightness L * of the mixed solution is 40 or more.
  • % THF solution at a volume ratio of 1:1 the lightness L * of the mixed solution is 40 or more.
  • the modifier for chlorine-containing polymers according to [1-2] comprising: [1-4] A resin composition containing the chlorine-containing polymer modifier according to any one of [1-1] to [1-3] and a chlorine-containing polymer. [1-5] A molded article using the resin composition according to [1-4].
  • a resin composition comprising 100 parts by mass of a chlorine-containing polymer and 1 to 40 parts by mass of a maleimide copolymer, wherein the chlorine content of the chlorine-containing polymer is 60% to 70% by mass. %, and the maleimide copolymer has a vinyl cyanide monomer unit and a maleimide monomer unit.
  • the maleimide copolymer comprises an aromatic vinyl monomer unit, the vinyl cyanide monomer unit, and the A resin composition comprising a maleimide monomer unit.
  • a resin composition comprising: [2-5] The resin composition according to any one of [2-1] to [2-4], wherein the maleimide copolymer has a weight average molecular weight of 70,000 to 150,000.
  • a resin composition. [2-6] The resin composition according to any one of [2-1] to [2-5], which contains 4% by mass or more of the chlorine-containing polymer based on 100% by mass of the resin composition. , resin composition. [2-7] The resin composition according to any one of [2-1] to [2-6], further comprising an impact modifier. [2-8] A molded article using the resin composition according to any one of [2-1] to [2-7].
  • the modifier for chlorine-containing polymers according to an embodiment of the first aspect of the present invention is a 10% by mass THF solution of the modifier for chlorine-containing polymers. and a 10% by mass THF solution of a chlorine-containing polymer with a K value of 66.7 ⁇ 1.0 and a degree of chlorination of 57 ⁇ 1.0% in a 1:1 volume ratio.
  • the lightness L * of the mixed liquid is 40 or more, preferably 50 or more, and more preferably 60 or more.
  • the degree of chlorination refers to the content of chlorine (% by mass) in the chlorine-containing polymer.
  • the modifier for chlorine-containing polymers according to the present invention includes a 10% by mass THF solution of the modifier for chlorine-containing polymers and a chlorine content having a K value of 66.0 ⁇ 2.0.
  • the modifier for chlorine-containing polymers according to the present invention includes a 10% by mass THF solution of the modifier for chlorine-containing polymers, and a chlorine-containing modifier having a K value of 56.0 ⁇ 2.0.
  • the K value of the chlorine-containing polymer and the chlorine-containing polymer with a high chlorine content is a value obtained by measuring solution viscosity using a capillary viscometer in accordance with JISK 7367-2. It is an index showing the degree of polymerization and molecular weight of a chlorine-containing polymer with a high chlorine content.
  • the lightness L * in this embodiment is a mixture prepared by mixing a 10% by mass THF solution of a chlorine-containing polymer modifier and a 10% by mass THF solution of a chlorine-containing polymer at a volume ratio of 1:1.
  • the modifier for chlorine-containing polymers satisfactorily improves heat resistance and impact resistance when blended with chlorine-containing polymers to form a resin composition.
  • a method for adjusting the lightness L * in the mixed liquid for example, a specific method that satisfies the desired lightness L * by performing a precipitation operation and a filtration operation on a solution in which a crude product material containing a copolymer is dissolved by the method described below.
  • the modifier for chlorine-containing polymers according to the present embodiment may include a copolymer containing at least an aromatic vinyl monomer unit, a cyanide vinyl monomer unit, and a maleimide monomer unit.
  • the monomer units contained in the copolymer will be explained below.
  • aromatic vinyl monomer unit examples include styrene, o-methylstyrene, m-methylstyrene, p-methyl Examples include styrene, 2,4-dimethylstyrene, ethylstyrene, p-tert-butylstyrene, ⁇ -methylstyrene, ⁇ -methyl-p-methylstyrene, and the like. Among these, styrene is preferred from the viewpoint of heat resistance, affinity with chlorine-containing polymers, and fluidity balance.
  • the aromatic vinyl monomer may be used alone, or two or more types may be used in combination.
  • the copolymer according to this embodiment preferably contains 60 to 85% by mass of aromatic vinyl monomer units when the total amount of monomer units contained in the copolymer is 100% by mass,
  • the content is more preferably 65 to 85% by mass, and even more preferably 68 to 80% by mass. Specifically, for example, it is 60, 65, 68, 70, 72, 75, 80, or 85% by mass, and may be within a range between any two of the numerical values exemplified here.
  • the amount of aromatic vinyl monomer units By setting the amount of aromatic vinyl monomer units to 60% by mass or more, a balance between excellent fluidity and affinity with chlorine-containing polymers can be obtained, and by setting the amount to 85% by mass or less, sufficient heat resistance can be obtained. You can get sex.
  • the content of the aromatic vinyl monomer units means the total amount of the aromatic vinyl monomer units used together.
  • vinyl cyanide monomer unit examples include acrylonitrile, methacrylonitrile, ethacrylonitrile, fumaronitrile, and the like. . Among these, acrylonitrile is preferred from the viewpoint of hue and imparting heat resistance to the chlorine-containing polymer resin composition.
  • the vinyl cyanide monomer may be used alone, or two or more types may be used in combination.
  • the copolymer according to the present embodiment preferably contains vinyl cyanide monomer units in an amount of 0.5 to 20% by mass when the total amount of monomer units contained in the copolymer is 100% by mass.
  • the content is more preferably 3 to 20% by mass, and even more preferably 5 to 20% by mass. Specifically, for example, it is 0.5, 1, 5, 7, 10, 13, 15, or 20% by mass, and may be within a range between any two of the numerical values exemplified here.
  • the amount of vinyl cyanide monomer units By setting the amount of vinyl cyanide monomer units to 0.5% by mass, the heat resistance of the chlorine-containing polymer resin composition can be sufficiently improved, and by setting the amount to 20% by mass or less, the resin composition The balance between impact resistance and heat resistance of objects can be improved.
  • the content of vinyl cyanide monomer units means the total amount of vinyl cyanide monomer units used together.
  • maleimide monomer from which the maleimide monomer unit contained in the copolymer according to the present embodiment is derived examples include N-alkyl maleimide such as N-methylmaleimide, N-butylmaleimide, and N-cyclohexylmaleimide.
  • maleimide and N-arylmaleimides such as N-phenylmaleimide, N-chlorophenylmaleimide, N-methylphenylmaleimide, N-methoxyphenylmaleimide, and N-tribromophenylmaleimide.
  • N-arylmaleimide is preferred from the viewpoint of imparting heat resistance to the chlorine-containing polymer resin composition, and N-phenylmaleimide is more preferred.
  • the maleimide monomer may be used alone or in combination of two or more types.
  • a copolymer obtained by copolymerizing a raw material consisting of an unsaturated dicarboxylic acid monomer with other monomers is treated with ammonia or a primary amine. It can be imidized.
  • a raw material consisting of a maleimide monomer may be copolymerized with other monomers.
  • the copolymer according to the present embodiment preferably contains 10 to 30% by mass of maleimide monomer units, more preferably is contained in an amount of 12 to 25% by mass, more preferably 12 to 20% by mass. Specifically, for example, it is 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, or 30% by mass, and is within the range between any two of the numerical values exemplified here. Good too.
  • the amount of maleimide monomer units By setting the amount of maleimide monomer units to 10% by mass or more, the heat resistance of the chlorine-containing polymer resin composition can be sufficiently improved, and by setting the amount to 30% by mass or less, the copolymer contains chlorine. It can reduce the possibility that it will not melt with the polymer and cannot be kneaded.
  • the content of the maleimide monomer unit means the total amount of the maleimide monomer unit used in combination.
  • the copolymer according to this embodiment may further contain an unsaturated acid anhydride monomer unit.
  • unsaturated acid anhydride monomer from which the unsaturated acid anhydride monomer unit contained in the copolymer according to the present embodiment is derived include maleic anhydride, itaconic anhydride, and citraconic anhydride. and aconitic acid anhydride.
  • maleic anhydride is preferred from the viewpoint of imparting heat resistance to the chlorine-containing polymer resin composition.
  • the unsaturated acid anhydride monomer may be used alone, or two or more types may be used in combination.
  • the copolymer according to the present invention preferably contains 0 to 10% by mass of unsaturated acid anhydride monomer units when the total amount of monomer units contained in the copolymer is 100% by mass. , more preferably 0 to 5% by mass, still more preferably 0 to 3% by mass. Specifically, for example, it is 0, 1, 2, 3, 4, 5, 6, 8, or 10% by mass, and may be within a range between any two of the numerical values exemplified here.
  • the amount of the unsaturated acid anhydride monomer unit to 10% by mass or less, it is possible to reduce the decrease in fluidity and the decrease in kneadability with the chlorine-containing polymer.
  • the content of the unsaturated acid anhydride monomer unit means the total amount of the unsaturated acid anhydride monomer unit used together.
  • the copolymer according to this embodiment includes copolymerizable monomers other than aromatic vinyl monomers, vinyl cyanide monomers, maleimide monomers, and unsaturated acid anhydride monomers. may be copolymerized within a range that does not impede the effects of the present invention.
  • the monomers that can be copolymerized into the copolymer according to this embodiment include acrylic ester monomers such as methyl acrylate, ethyl acrylate, and butyl acrylate, methyl methacrylate, and ethyl methacrylate.
  • Examples include methacrylic acid ester monomers such as esters, vinyl carboxylic acid monomers such as acrylic acid and methacrylic acid, acrylamide and methacrylic acid amide.
  • the monomers that can be copolymerized into the copolymer may be used alone, or two or more types may be used in combination.
  • Such monomers can be copolymerized within a range that does not impede the effects of the present invention, but from the viewpoint of imparting heat resistance to the chlorine-containing polymer resin composition, the amount is preferably 20% by mass or less, and 10% by mass or less. % or less is more preferable.
  • the modifier for chlorine-containing polymers according to the present embodiment may contain additives as described below to the extent that the effects of the present invention are not impaired.
  • the polymerization solution may contain a hindered phenol compound, a lactone compound, a phosphorus compound, Additives such as heat stabilizers such as sulfur compounds, light stabilizers such as hindered amine compounds and benzotriazole compounds, lubricants, plasticizers, colorants, antistatic agents, and mineral oil may be added.
  • the amount added is preferably less than 0.2 parts by mass per 100 parts by mass of total monomer units.
  • the polymerization mode of the crude product raw material that is the raw material for the copolymer contained in the modifier for chlorine-containing polymers according to the present embodiment includes, for example, solution polymerization, bulk polymerization, and the like.
  • Solution polymerization is preferable from the viewpoint that a crude product raw material with a more uniform copolymerization composition can be obtained by polymerizing while carrying out fractional addition or the like.
  • the solvent for solution polymerization is non-polymerizable from the viewpoint that by-products are less likely to be produced and there are fewer adverse effects.
  • ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and acetophenone
  • ethers such as tetrahydrofuran and 1,4-dioxane
  • aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and chlorobenzene
  • N,N-dimethylformamide dimethyl sulfoxide, N-methyl-2-pyrrolidone, etc., and methyl ethyl ketone and methyl isobutyl ketone are preferred from the viewpoint of ease of solvent removal during devolatilization and recovery of crude product raw materials.
  • the polymerization process may be a continuous polymerization type, a batch type (batch type), or a semi-batch type.
  • the method for producing the crude product raw material is not particularly limited, but it can preferably be obtained by radical polymerization, and the polymerization temperature is preferably in the range of 80 to 150°C.
  • the polymerization initiator is not particularly limited, but includes known azo compounds such as azobisisobutyronitrile, azobiscyclohexanecarbonitrile, azobismethylpropionitrile, and azobismethylbutyronitrile, and benzoyl.
  • Peroxide t-butylperoxybenzoate, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethyl
  • organic peroxides such as hexanoate, di-t-butyl peroxide, dicumyl peroxide, and ethyl-3,3-di-(t-butylperoxy)butyrate can be used; You may use a species or a combination of two or more species.
  • the amount of the polymerization initiator used is not particularly limited, but it is preferably used in an amount of 0.1 to 1.5% by mass, more preferably 0.1 to 1.5% by mass based on 100% by mass of all monomer units. It is 1.0% by mass. It is preferable that the amount of the polymerization initiator used is 0.1% by mass or more because a sufficient polymerization rate can be obtained. When the amount of the polymerization initiator used is 1.5% by mass or less, the polymerization rate can be suppressed, so reaction control becomes easy and it becomes easy to obtain the target molecular weight.
  • Chain transfer agents can be used in the production of crude product raw materials.
  • the chain transfer agent used is not particularly limited, but includes, for example, n-octylmercaptan, n-dodecylmercaptan, t-dodecylmercaptan, ⁇ -methylstyrene dimer, ethyl thioglycolate, limonene, terpinolene, etc. be.
  • the amount of chain transfer used is not particularly limited as long as the target molecular weight can be obtained, but it should be 0.01 to 0.8% by mass based on 100% by mass of all monomer units. is preferable, and more preferably 0.1 to 0.5% by mass. If the amount of chain transfer agent used is 0.01% by mass to 0.8% by mass, the target molecular weight can be easily obtained.
  • Methods for introducing the maleimide monomer unit into the crude product raw material include a method of copolymerizing a maleimide monomer, an aromatic vinyl monomer, and a vinyl cyanide monomer (direct method); Alternatively, an unsaturated dicarboxylic anhydride, an aromatic vinyl monomer, and a vinyl cyanide monomer are copolymerized in advance, and the unsaturated dicarboxylic anhydride group is further reacted with ammonia or a primary amine. There is a method (post-imidization method) of converting an unsaturated dicarboxylic acid anhydride group into a maleimide monomer unit. The post-imidization method is preferable because it reduces the amount of maleimide monomer remaining in the copolymer.
  • the primary amines used in the post-imidization method include, for example, methylamine, ethylamine, n-propylamine, iso-propylamine, n-butylamine, n-pentylamine, n-hexylamine, n-octylamine, and cyclohexyl.
  • Examples include amines, alkylamines such as decylamine, chloro- or bromine-substituted alkylamines, aromatic amines such as aniline, toluidine, and naphthylamine, and among these, aniline and cyclohexylamine are preferred.
  • These primary amines may be used alone or in combination of two or more.
  • the amount of primary amine added is not particularly limited, but is preferably 0.7 to 1.1 molar equivalent, more preferably 0.85 to 1.05 mol, based on the unsaturated dicarboxylic anhydride group. It is equivalent. It is preferable that the amount is 0.7 molar equivalent or more based on the unsaturated dicarboxylic anhydride monomer unit in the crude product raw material because thermal stability will be good. Moreover, if it is 1.1 molar equivalent or less, it is preferable because the amount of primary amine remaining in the copolymer is reduced.
  • a catalyst may be used when introducing the maleimide monomer unit by the post-imidization method.
  • a catalyst can improve the dehydration ring closure reaction in the reaction between ammonia or a primary amine and an unsaturated dicarboxylic anhydride group, particularly in the reaction of converting an unsaturated dicarboxylic anhydride group into a maleimide group.
  • the type of catalyst is not particularly limited, for example, a tertiary amine can be used.
  • Tertiary amines are not particularly limited, but include, for example, trimethylamine, triethylamine, tripropylamine, tributylamine, N,N-dimethylaniline, N,N-diethylaniline, and the like.
  • the amount of the tertiary amine added is not particularly limited, it is preferably 0.01 molar equivalent or more based on the unsaturated dicarboxylic anhydride group.
  • the temperature of the imidization reaction in the present invention is preferably 100 to 250°C, more preferably 120 to 200°C. If the temperature of the imidization reaction is 100° C. or higher, the reaction rate is sufficiently high and it is preferable from the viewpoint of productivity. It is preferable that the temperature of the imidization reaction is 250° C. or lower because it is possible to suppress deterioration of physical properties due to thermal deterioration of the copolymer.
  • the method of removing volatile components such as the solvent used in solution polymerization and unreacted monomers from the solution after solution polymerization of the crude product raw material or the solution after post-imidization is known.
  • method can be adopted.
  • a vacuum devolatilization tank equipped with a heater or a devolatilization extruder equipped with a vent can be used.
  • the devolatilized crude product raw material in a molten state is transferred to the granulation process, extruded into strands from a multi-hole die, and can be processed into pellets using a cold cut method, an air hot cut method, or an underwater hot cut method. can.
  • the copolymer according to this embodiment can be produced, for example, from the crude product raw material obtained by the method described above. Specifically, for example, the following steps are performed.
  • a crude product raw material is dissolved in methyl ethyl ketone to obtain a methyl ethyl ketone solution of the crude product raw material.
  • Hexane is added dropwise to the methyl ethyl ketone solution to obtain a mixed solution in which a portion of the dissolved crude product raw material is precipitated.
  • Filter the mixed solution to separate the filtrate and the filtrate.
  • the filtrate is obtained through a drying step of air drying for 24 hours and then drying it in a vacuum dryer set at 70° C. for 4 hours.
  • the lightness L * of a mixed solution prepared by mixing the following at a volume ratio of 1:1 is measured.
  • the filter material is considered to be the copolymer according to the present embodiment.
  • hexane is added dropwise to the filtrate obtained in (3) to obtain a liquid mixture in which a portion of the crude product raw material is precipitated.
  • the lightness L * in this embodiment is a mixture prepared by mixing a 10% by mass THF solution of a chlorine-containing polymer modifier and a 10% by mass THF solution of a chlorine-containing polymer at a volume ratio of 1:1. This is a value measured under the conditions of measurement in the L * a * b * mode of a spectrophotometer V-670 manufactured by JASCO Corporation by placing a liquid in an optical cell with an optical path length of 10 mm and an optical path width of 10 mm.
  • the chlorine-containing polymer contained in the resin composition according to the present embodiment is obtained by polymerizing vinyl chloride monomer alone or a mixture of vinyl chloride monomer and one or more monomers copolymerizable with vinyl chloride monomer. and a chlorine-added polymer obtained by further adding chlorine to the polymer thus obtained.
  • the chlorine-containing polymer may also include a compound of the polymer thus obtained and a chlorine addition polymer.
  • Copolymerizable monomers include vinyl esters such as vinyl acetate and vinyl propionate, acrylic esters such as methyl acrylate and butyl acrylate, methacrylic esters such as methyl methacrylate and ethyl methacrylate, butyl maleate and diethyl ester.
  • fumaric acid esters such as esters, vinyl ethers such as vinyl methyl ether, vinyl butyl ether and vinyl octyl ether, vinyl cyanides such as acrylonitrile and methacrylonitrile, ⁇ -olefins such as ethylene and propylene, styrene, ⁇ -methyl Styrenes and their substituted products such as styrene, vinyltoluene, t-butylstyrene, and chlorostyrene, vinylidene halides other than vinyl chloride such as vinylidene chloride and vinyl bromide, vinyl halides, and phthalate esters such as diallylphthalate.
  • the chlorine-containing polymer is preferably polyvinyl chloride obtained by polymerizing vinyl chloride monomers.
  • the average degree of polymerization of the above chlorine-containing polymer is from 680 to 1,900, preferably from 700 to 1,700.
  • the modifier for chlorine-containing polymers can be uniformly dispersed, and by setting it to 1900 or less, the kneadability with the modifier for chlorine-containing polymers is excellent.
  • the chlorine content of the chlorine-containing polymer contained in the resin composition according to the present embodiment is preferably 50.0 to 70.0% by mass, more preferably 55.0 to 70.0% by mass. When the chlorine content of the chlorine-containing polymer is within this range, excellent processability and impact resistance can be obtained.
  • the chlorine-containing polymer contained in the resin composition according to this embodiment may be a chlorine-containing polymer with a high chlorine content.
  • a chlorine-containing polymer with a chlorine content of more than 60.0% by mass may be used, and by using a chlorine-containing polymer with a chlorine content of more than 60.0% by mass, excellent processability and impact resistance can be achieved. is obtained.
  • the method of polymerizing the chlorine-containing polymer is not particularly limited, and conventionally known bulk polymerization, solution polymerization, emulsion polymerization, etc. can be used.
  • Resin composition ⁇ Resin composition containing a chlorine-containing polymer modifier and a chlorine-containing polymer>
  • the blending ratio of the chlorine-containing polymer modifier and the chlorine-containing polymer in this embodiment is not particularly limited, but for example, 0.5 to 50 parts by mass of the chlorine-containing polymer modifier to 100 parts by mass of the chlorine-containing polymer.
  • the amount is preferably 2 to 25 parts by mass, and more preferably 2 to 25 parts by mass.
  • the resin composition according to this embodiment may further contain a filler, if necessary. By blending the filler, the effect of improving the flexural modulus of the molded article obtained from the resin composition can be expected.
  • fillers that can be used in this embodiment include silica, diatomaceous earth, alumina, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, ferrites, calcium hydroxide, water Magnesium oxide, aluminum hydroxide, basic magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dawnite, hydrotalcite, calcium sulfate, barium sulfate, gypsum fiber, calcium silicate, talc, clay, mica , montmorillonite, bentonite, activated clay, sepiolite, imogolite, sericite, glass fiber, glass beads, silica balloons, aluminum nitride, boron nitride, silicon nit
  • calcium carbonate, calcium silicate, calcium hydroxide, calcium oxide, magnesium carbonate, magnesium hydroxide, magnesium oxide, barium carbonate, aluminum hydroxide, and calcium oxide are highly effective in improving mechanical properties and Vicat softening temperature.
  • Basic inorganic fillers such as zinc, zinc hydroxide, iron oxide, and talc are preferred. These fillers may be used alone or in combination of two or more.
  • the blending amount of the filler according to this embodiment is 1 to 100 parts by mass, preferably 1 to 75 parts by mass, and more preferably 1 to 50 parts by mass, per 100 parts by mass of the chlorine-containing polymer. be.
  • the blending amount of the filler is 1, 3, 5, 10, 20, 40, 60, 80, or 100 parts by mass with respect to 100 parts by mass of the chlorine-containing polymer, and the numerical values exemplified here. It may be within the range between any two.
  • the amount of the filler used means the total amount of the filler used in combination.
  • the amount of the filler By setting the amount of the filler to be 1 part by mass or more to 100 parts by mass of the chlorine-containing polymer, the effect of improving the flexural modulus can be obtained, and by setting it to 50 parts by mass or less, a decrease in dispersibility can be suppressed.
  • the resin composition according to this embodiment may further contain an impact modifier, if necessary.
  • an impact modifier By blending an impact modifier, the effect of improving the impact resistance of molded products obtained from the resin composition can be expected.
  • impact modifiers that can be used in this embodiment include ABS (acrylonitrile-butadiene-styrene) resin, MBS (methyl methacrylate-butadiene-styrene) resin, acrylic rubber, chlorinated polyethylene, and NBR (acrylonitrile-butadiene rubber). ).
  • ABS acrylonitrile-butadiene-styrene
  • MBS methyl methacrylate-butadiene-styrene
  • acrylic rubber chlorinated polyethylene
  • NBR acrylonitrile-butadiene rubber
  • the amount of the impact modifier according to the present embodiment is 1 to 50 parts by weight, preferably 1 to 40 parts by weight, and more preferably 1 to 40 parts by weight, per 100 parts by weight of the chlorine-containing polymer. It is 30 parts by mass.
  • the amount of the impact modifier used means the total amount of the impact modifier used together.
  • the resin composition according to this embodiment may further contain a processing aid, if necessary.
  • a processing aid it can be expected that the effect of promoting gelation during processing and improving the moldability of molded articles obtained from the resin composition can be expected.
  • processing aids that can be used in this embodiment include acrylic copolymers. These processing aids may be used alone or in combination of two or more.
  • the amount of the processing aid according to this embodiment is 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, per 100 parts by mass of the chlorine-containing polymer.
  • the amount of processing aid added to 100 parts by mass of the chlorine-containing polymer is 0.01, 0.02, 0.05, 0.1, 0.2, 0.5, 1, 2, 5 or 10 parts by mass, and may be within a range between any two of the numerical values exemplified here.
  • the blending amount of the processing aid means the total amount of the processing aid used together.
  • the resin composition of the present invention may contain additives as described below within a range that does not impede the effects of the present invention, but may also consist of a chlorine-containing polymer modifier and a chlorine-containing polymer. If necessary, a reinforcing agent, a processability improver, a heat stabilizer, a lubricant, a plasticizer, etc. may be added to the resin composition of the present invention alone or in combination of two or more. As other additives, light stabilizers, ultraviolet absorbers, antioxidants, pigments, dyes, etc. can be optionally added.
  • melt-kneading devices include a single screw extruder, an intermeshing type co-rotating or intermeshing type counter-rotating twin screw extruder, a screw extruder such as a non-intermeshing type twin screw extruder, a Banbury mixer, There are co-kneaders, mixing rolls, etc. Moreover, a combination of two or more of these extruders can also be used.
  • a molded article can be obtained by molding the resin composition according to this embodiment by a known method.
  • the molding method include injection molding, sheet extrusion molding, vacuum molding, blow molding, foam molding, and profile extrusion molding.
  • the chlorine-containing polymer resin composition is usually heated to 170 to 200°C and then processed, preferably at 190 to 200°C.
  • a resin composition according to an embodiment of the second aspect of the present invention is a chlorine-containing polymer-based resin composition containing a chlorine-containing polymer and a maleimide-based copolymer.
  • the resin composition preferably includes a chlorine-containing polymer, a maleimide copolymer, and an impact modifier.
  • Chlorine-containing polymers include polymers obtained by polymerizing vinyl chloride monomer alone or a mixture of vinyl chloride monomer and one or more monomers copolymerizable therewith, and polymers obtained in this way. This is a chlorine-added polymer obtained by adding chlorine to the obtained polymer.
  • the chlorine-containing polymer may also include a mixture of the polymer thus obtained and a chlorine addition polymer.
  • Copolymerizable monomers include vinyl esters such as vinyl acetate and vinyl propionate, acrylic esters such as methyl acrylate and butyl acrylate, methacrylic esters such as methyl methacrylate and ethyl methacrylate, butyl maleate and diethyl ester.
  • fumaric acid esters such as esters, vinyl ethers such as vinyl methyl ether, vinyl butyl ether and vinyl octyl ether, vinyl cyanides such as acrylonitrile and methacrylonitrile, ⁇ -olefins such as ethylene and propylene, styrene, ⁇ -methyl Styrenes and their substituted products such as styrene, vinyltoluene, t-butylstyrene, and chlorostyrene, vinylidene halides other than vinyl chloride such as vinylidene chloride and vinyl bromide, vinyl halides, and phthalate esters such as diallylphthalate.
  • the chlorine-containing polymer is preferably chlorinated vinyl chloride obtained by further adding chlorine to polyvinyl chloride obtained by polymerizing vinyl chloride monomers.
  • the average degree of polymerization of the chlorine-containing polymer is 500 to 1,900, preferably 550 to 1,100.
  • the maleimide copolymer can be uniformly dispersed, and by setting the average degree to 1900 or less, the kneadability with the maleimide copolymer is excellent.
  • the chlorine content of the chlorine-containing polymer is 60 to 70% by mass based on 100% by mass of the chlorine-containing polymer, preferably more than 60% by mass and 70% by mass or less, and more preferably 63 to 68% by mass.
  • the chlorine content of the chlorine-containing polymer is, for example, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70 based on 100% by mass of the chlorine-containing polymer. It may be within the range between any two of the above values.
  • the chlorine content of the chlorine-containing polymer can be determined, for example, by neutralization titration using the oxygen flask combustion method (based on JIS K7229:1995).
  • the resin composition preferably contains 4% by mass or more of the chlorine-containing polymer based on 100% by mass of the resin composition.
  • the content of the chlorine-containing polymer in 100% by mass of the resin composition is preferably 4 to 95% by mass, more preferably 60 to 90% by mass, and even more preferably 71 to 90% by mass.
  • the content of the chlorine-containing polymer in 100% by mass of the resin composition is, for example, 4, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 90, 95, and between any two of the numerical values exemplified here. It may be within the range.
  • the resin composition contains 71 to 90% by weight of a chlorine-containing polymer having a chlorine content of more than 60% by weight and 70% by weight or less based on 100% by weight of the resin composition.
  • the method of polymerizing the chlorine-containing polymer is not particularly limited, and conventionally known bulk polymerization, solution polymerization, emulsion polymerization, etc. can be used.
  • the maleimide copolymer has a vinyl cyanide monomer unit and a maleimide monomer unit. Further, the maleimide copolymer may have a vinyl cyanide monomer unit, a maleimide monomer unit, and an aromatic vinyl monomer unit. Furthermore, the maleimide copolymer has a vinyl cyanide monomer unit, a maleimide monomer unit, an aromatic vinyl monomer unit, and an unsaturated acid anhydride monomer unit. You may do so.
  • vinyl cyanide monomer unit examples include acrylonitrile, methacrylonitrile, ethacrylonitrile, fumaronitrile, and the like. Among these, acrylonitrile is preferred from the viewpoint of hue and imparting heat resistance to the resin composition.
  • the vinyl cyanide monomer may be used alone, or two or more types may be used in combination.
  • the maleimide copolymer preferably contains vinyl cyanide monomer units in an amount of 0.5 to 20% by mass when the total amount of monomer units contained in the maleimide copolymer is 100% by mass.
  • the content is more preferably 0.5 to 15% by mass, and even more preferably 3 to 15% by mass.
  • the content of vinyl cyanide monomer units is, for example, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 , 15, 16, 17, 18, 19, 20% by mass, and may be within a range between any two of the numerical values exemplified here.
  • the heat resistance of the resin composition can be sufficiently improved, and by setting the amount to 20% by mass or less, the impact resistance of the resin composition can be improved.
  • the balance between heat resistance and heat resistance can be improved.
  • the content of vinyl cyanide monomer units means the total amount of vinyl cyanide monomer units used together.
  • maleimide monomer unit examples include N-alkylmaleimides such as N-methylmaleimide, N-butylmaleimide, and N-cyclohexylmaleimide; Examples include N-arylmaleimides such as N-phenylmaleimide, N-chlorophenylmaleimide, N-methylphenylmaleimide, N-methoxyphenylmaleimide, and N-tribromophenylmaleimide. Among these, N-arylmaleimide is preferred from the viewpoint of imparting heat resistance to the resin composition, and N-phenylmaleimide is more preferred.
  • the maleimide monomer may be used alone or in combination of two or more types.
  • a maleimide monomer unit in a maleimide copolymer for example, a copolymer obtained by copolymerizing a raw material consisting of an unsaturated dicarboxylic acid monomer with other monomers is mixed with ammonia or primary It can be imidized with an amine.
  • a raw material consisting of a maleimide monomer may be copolymerized with other monomers.
  • the maleimide copolymer preferably contains 10 to 30 mass% of maleimide monomer units, more preferably 10 to 30 mass% of the total monomer units contained in the maleimide copolymer. is contained in an amount of 10 to 25% by mass, more preferably 12 to 20% by mass.
  • the content of maleimide monomer units is, for example, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26 , 27, 28, 29, 30% by mass, and may be within the range between any two of the numerical values exemplified here.
  • the amount of the maleimide monomer unit By setting the amount of the maleimide monomer unit to 10% by mass or more, the heat resistance of the resin composition can be sufficiently improved, and by setting the amount to 30% by mass or less, the maleimide copolymer becomes chlorine-containing polymer. The possibility of not being able to melt and knead can be reduced.
  • the content of the maleimide monomer unit means the total amount of the maleimide monomer unit used in combination.
  • aromatic vinyl monomer unit examples include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2 , 4-dimethylstyrene, ethylstyrene, p-tert-butylstyrene, ⁇ -methylstyrene, ⁇ -methyl-p-methylstyrene, and the like.
  • styrene is preferred from the viewpoint of heat resistance, affinity with chlorine-containing polymers, and fluidity balance.
  • the aromatic vinyl monomer may be used alone, or two or more types may be used in combination.
  • the maleimide copolymer preferably contains 60 to 85% by mass of aromatic vinyl monomer units when the total monomer units contained in the maleimide copolymer is 100% by mass,
  • the content is more preferably 65 to 80% by mass, and even more preferably 68 to 80% by mass.
  • the content of aromatic vinyl monomer units is, for example, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75 , 76, 77, 78, 79, 80, 81, 82, 83, 84, 85% by mass, and may be within a range between any two of the numerical values exemplified here.
  • the amount of aromatic vinyl monomer units By setting the amount of aromatic vinyl monomer units to 60% by mass or more, a balance between excellent fluidity and affinity with chlorine-containing polymers can be obtained, and by setting the amount to 85% by mass or less, sufficient heat resistance can be obtained. You can get sex.
  • the content of the aromatic vinyl monomer units means the total amount of the aromatic vinyl monomer units used together.
  • Examples of the unsaturated acid anhydride monomer from which the unsaturated acid anhydride monomer unit contained in the maleimide copolymer is derived include maleic anhydride, itaconic anhydride, citraconic anhydride, and aconite. There are acid anhydrides, etc. Among these, maleic anhydride is preferred from the viewpoint of imparting heat resistance to the chlorine-containing polymer resin composition.
  • the unsaturated acid anhydride monomer may be used alone, or two or more types may be used in combination.
  • the maleimide copolymer may contain 0 to 10% by mass of unsaturated acid anhydride monomer units when the total amount of monomer units contained in the maleimide copolymer is 100% by mass.
  • the content is preferably 0 to 5% by mass, and even more preferably 0 to 3% by mass.
  • the content of the unsaturated acid anhydride monomer unit is, for example, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10% by mass, and the It may be within a range between any two values.
  • the amount of the unsaturated acid anhydride monomer unit means the total amount of the unsaturated acid anhydride monomer unit used together.
  • Maleimide copolymers contain monomer units other than vinyl cyanide monomer units, maleimide monomer units, aromatic vinyl monomer units, and unsaturated acid anhydride monomer units (other monomer units) may be copolymerized within a range that does not impede the effects of the present invention. Other monomer units may be used together with some or all of the vinyl cyanide monomer units, maleimide monomer units, aromatic vinyl monomer units, and unsaturated acid anhydride monomer units. It is derived from polymerizable monomers (other monomers).
  • Other monomers include acrylic ester monomers such as methyl acrylate, ethyl acrylate, and butyl acrylate, methacrylic ester monomers such as methyl methacrylate, and ethyl methacrylate, and acrylic ester monomers.
  • examples include acids, vinyl carboxylic acid monomers such as methacrylic acid, acrylamide, and methacrylic acid amide.
  • Other copolymerizable monomers may be used alone, or two or more types may be used in combination. Such monomers can be copolymerized within a range that does not impede the effects of the present invention, but from the viewpoint of imparting heat resistance to the resin composition, the amount is preferably 20% by mass or less, and 10% by mass or less. It is even more preferable.
  • the weight average molecular weight of the maleimide copolymer is preferably 70,000 to 150,000, more preferably 75,000 to 110,000. By setting the molecular weight to 70,000 or more, it is possible to suppress a decrease in the impact resistance of the resin composition, and by setting the molecular weight to 150,000 or less, it is possible to prevent a decrease in the kneading properties of the resin composition.
  • the maleimide copolymer has a K value of 66.7 ⁇ 1.0 and a chlorination degree of 57.0 ⁇ 1.0 when added to a 10% by mass THF solution of the maleimide copolymer.
  • the lightness L * of a mixed solution prepared by mixing a 0% chlorine-containing polymer with a 10% by mass THF solution at a volume ratio of 1:1 is 40 or more.
  • the degree of chlorination here refers to the content (% by mass) of chlorine in the chlorine-containing polymer.
  • the maleimide copolymer has a K value of 66.0 ⁇ 2.0 and a chlorination degree of 67.3 ⁇ when mixed with a 10% by mass THF solution of the maleimide copolymer.
  • the lightness L * of a mixed solution prepared by mixing a 1.0% chlorine-containing polymer with a 10% by mass THF solution at a volume ratio of 1:1 is 60 or more.
  • the maleimide copolymer has a K value of 56 ⁇ 2.0 and a chlorination degree of 63.5 ⁇ 1.
  • the lightness L * of a mixed solution prepared by mixing a 0% chlorine-containing polymer with a 10% by mass THF solution at a volume ratio of 1:1 is 60 or more.
  • the K value of the chlorine-containing polymer and the chlorine-containing polymer with a high chlorine content is a value obtained by measuring solution viscosity using a capillary viscometer in accordance with JISK 7367-2. It is an index showing the degree of polymerization and molecular weight of a chlorine-containing polymer with a high chlorine content.
  • the lightness L * in this embodiment is a mixture prepared by mixing a 10% by mass THF solution of a chlorine-containing polymer modifier and a 10% by mass THF solution of a chlorine-containing polymer at a volume ratio of 1:1. This is a value measured under the conditions of measurement in the L * a * b * mode of a spectrophotometer V-670 manufactured by JASCO Corporation by placing a liquid in an optical cell with an optical path length of 10 mm and an optical path width of 10 mm.
  • the modifier for chlorine-containing polymers satisfactorily improves heat resistance and impact resistance when blended with chlorine-containing polymers to form a resin composition.
  • a method for adjusting the lightness L * in the mixed liquid for example, a specific method that satisfies the desired lightness L * by performing a precipitation operation and a filtration operation on a solution in which a crude product material containing a copolymer is dissolved by the method described below.
  • the maleimide copolymer may contain additives such as those described below within a range that does not impede the effects of the present invention.
  • heat stabilizers such as hindered phenol compounds, lactone compounds, phosphorus compounds, and sulfur compounds, hindered amine compounds, and benzotriazole compounds may be added to the polymerization solution as necessary.
  • Additives such as light stabilizers, lubricants, plasticizers, colorants, antistatic agents, mineral oil, etc. may be added. The amount added is preferably less than 0.2 parts by mass per 100 parts by mass of total monomer units. These additives may be used alone or in combination of two or more.
  • the resin composition contains 1 to 40 parts by weight, preferably 5 to 32 parts by weight, and more preferably 15 to 30 parts by weight of the maleimide copolymer per 100 parts by weight of the chlorine-containing polymer.
  • the content of the maleimide copolymer is, for example, 1, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 35, 40 parts by mass, between any two of the numerical values exemplified here. It may be within the range. By setting it in such a range, both impact resistance and heat resistance are excellent even when an impact modifier is added.
  • chlorine-containing polymers contain chlorine
  • the higher the chlorine content the higher the heat resistance, but the higher the amount of toxic gas generated during heating, which can cause problems such as metal corrosion.
  • the addition of coalescent can reduce the amount of toxic gas generated during heating, and can also suppress metal corrosion.
  • Examples of the polymerization mode of the maleimide copolymer include solution polymerization and bulk polymerization.
  • Solution polymerization is preferable from the viewpoint that a copolymer having a more uniform copolymer composition can be obtained by polymerizing while performing partial addition or the like.
  • the solvent for solution polymerization is non-polymerizable from the viewpoint that by-products are less likely to be produced and there are fewer adverse effects.
  • ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and acetophenone
  • ethers such as tetrahydrofuran and 1,4-dioxane
  • aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and chlorobenzene
  • N,N-dimethylformamide dimethyl sulfoxide, N-methyl-2-pyrrolidone, etc., and methyl ethyl ketone and methyl isobutyl ketone are preferred from the viewpoint of ease of solvent removal during devolatilization and recovery of the maleimide copolymer.
  • the polymerization process may be a continuous polymerization type, a batch type (batch type), or a semi-batch type.
  • the method for producing the maleimide copolymer is not particularly limited, but it can preferably be obtained by radical polymerization, and the polymerization temperature is preferably in the range of 80 to 150°C.
  • the polymerization initiator is not particularly limited, but includes known azo compounds such as azobisisobutyronitrile, azobiscyclohexanecarbonitrile, azobismethylpropionitrile, and azobismethylbutyronitrile, and benzoyl.
  • Peroxide t-butylperoxybenzoate, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethyl
  • organic peroxides such as hexanoate, di-t-butyl peroxide, dicumyl peroxide, and ethyl-3,3-di-(t-butylperoxy)butyrate can be used; You may use a species or a combination of two or more species.
  • the amount of the polymerization initiator used is not particularly limited, but it is preferably used in an amount of 0.1 to 1.5% by mass, more preferably 0.1 to 1.5% by mass based on 100% by mass of all monomer units. It is 1.0% by mass. It is preferable that the amount of the polymerization initiator used is 0.1% by mass or more because a sufficient polymerization rate can be obtained. When the amount of the polymerization initiator used is 1.5% by mass or less, the polymerization rate can be suppressed, so reaction control becomes easy and it becomes easy to obtain the target molecular weight.
  • a chain transfer agent can be used in the production of maleimide copolymers.
  • the chain transfer agent used is not particularly limited, but includes, for example, n-octylmercaptan, n-dodecylmercaptan, t-dodecylmercaptan, ⁇ -methylstyrene dimer, ethyl thioglycolate, limonene, terpinolene, etc. be.
  • the amount of chain transfer used is not particularly limited as long as the target molecular weight can be obtained, but it should be 0.01 to 0.8% by mass based on 100% by mass of all monomer units. is preferable, and more preferably 0.1 to 0.5% by mass. If the amount of chain transfer agent used is 0.01% by mass to 0.8% by mass, the target molecular weight can be easily obtained.
  • the method for introducing maleimide monomer units into maleimide copolymers is to copolymerize maleimide monomers, aromatic vinyl monomers, and vinyl cyanide monomers (direct method). , or by copolymerizing an unsaturated dicarboxylic anhydride, an aromatic vinyl monomer, and a vinyl cyanide monomer in advance, and then reacting the unsaturated dicarboxylic anhydride group with ammonia or a primary amine.
  • the primary amines used in the post-imidization method include, for example, methylamine, ethylamine, n-propylamine, iso-propylamine, n-butylamine, n-pentylamine, n-hexylamine, n-octylamine, and cyclohexyl.
  • Examples include amines, alkylamines such as decylamine, chloro- or bromine-substituted alkylamines, aromatic amines such as aniline, toluidine, and naphthylamine, and among these, aniline and cyclohexylamine are preferred.
  • These primary amines may be used alone or in combination of two or more.
  • the amount of primary amine added is not particularly limited, but is preferably 0.7 to 1.1 molar equivalent, more preferably 0.85 to 1.05 mol, based on the unsaturated dicarboxylic anhydride group. It is equivalent. It is preferable that the amount is 0.7 molar equivalent or more based on the unsaturated dicarboxylic anhydride monomer unit in the maleimide copolymer because thermal stability will be good. Moreover, if it is 1.1 molar equivalent or less, it is preferable because the amount of primary amine remaining in the copolymer is reduced.
  • a catalyst may be used when introducing the maleimide monomer unit by the post-imidization method.
  • a catalyst can improve the dehydration ring closure reaction in the reaction between ammonia or a primary amine and an unsaturated dicarboxylic anhydride group, particularly in the reaction of converting an unsaturated dicarboxylic anhydride group into a maleimide group.
  • the type of catalyst is not particularly limited, for example, a tertiary amine can be used.
  • Tertiary amines are not particularly limited, but include, for example, trimethylamine, triethylamine, tripropylamine, tributylamine, N,N-dimethylaniline, N,N-diethylaniline, and the like.
  • the amount of the tertiary amine added is not particularly limited, it is preferably 0.01 molar equivalent or more based on the unsaturated dicarboxylic anhydride group.
  • the temperature of the imidization reaction in the present invention is preferably 100 to 250°C, more preferably 120 to 200°C. If the temperature of the imidization reaction is 100° C. or higher, the reaction rate is sufficiently high and it is preferable from the viewpoint of productivity. It is preferable that the temperature of the imidization reaction is 250° C. or lower because it is possible to suppress deterioration of physical properties due to thermal deterioration of the copolymer.
  • devolatilization method There is a known method for removing volatile components such as the solvent used in solution polymerization and unreacted monomers from a solution after solution polymerization of a maleimide copolymer or a solution after post-imidization (devolatilization method).
  • This method can be adopted.
  • a vacuum devolatilization tank equipped with a heater or a devolatilization extruder equipped with a vent can be used.
  • the devolatilized maleimide copolymer in a molten state is transferred to a granulation process, extruded into strands from a multi-hole die, and processed into pellets using a cold cut method, an air hot cut method, or an underwater hot cut method. I can do it.
  • the lightness L* of the maleimide copolymer may be adjusted, for example, by further refining the maleimide copolymer (crude product raw material) obtained by the above method. Specifically, for example, the following steps are performed.
  • a crude product raw material is dissolved in methyl ethyl ketone to obtain a solution of the crude product raw material in methyl ethyl ketone.
  • Hexane is added dropwise to the methyl ethyl ketone solution to obtain a mixed solution in which a portion of the dissolved crude product raw material is precipitated.
  • Hexane is added dropwise to the filtrate obtained in (3) to obtain a mixed solution in which a portion of the crude product raw material is precipitated.
  • (5) Repeat the operations (3) to (4) above to obtain a plurality of filtrates.
  • one having a desired lightness L * can be used as the purified maleimide copolymer.
  • the lightness L * in this embodiment refers to a liquid mixture prepared by mixing a 10% by mass THF solution of a maleimide copolymer and a 10% by mass THF solution of a chlorine-containing polymer at a volume ratio of 1:1. This is a value measured under the conditions of measurement in the L * a * b * mode of a spectrophotometer V-670 manufactured by JASCO Corporation, using an optical cell with an optical path length of 10 mm and an optical path width of 10 mm.
  • impact modifiers examples include ABS (acrylonitrile-butadiene-styrene) resin, MBS (methyl methacrylate-butadiene-styrene) resin, acrylic rubber, chlorinated polyethylene (chlorinated PE), and NBR (acrylonitrile butadiene rubber). Can be mentioned. Among these, MBS resin, acrylic rubber, and chlorinated polyethylene are preferable because they are highly effective in improving impact resistance. These impact modifiers may be used alone or in combination of two or more.
  • the resin composition preferably contains 1 to 50 parts by weight, more preferably 2 to 30 parts by weight, and even more preferably 5 to 15 parts by weight of an impact modifier per 100 parts by weight of the chlorine-containing polymer.
  • the content of the impact modifier is, for example, 1, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, The amount may be 20, 25, 30, 35, 40, 45, or 50 parts by mass, and may be within a range between any two of the numerical values exemplified here.
  • the content of the impact modifier means the total amount of the impact modifier used in combination.
  • the content of the impact modifier to 100 parts by mass of the chlorine-containing polymer to be 1 part by mass or more, the effect of improving impact resistance can be obtained, and by setting it to 50 parts by mass or less, the flexural modulus can be reduced. It can be suppressed.
  • the resin composition may further contain other additives as necessary.
  • additives include fillers, processing aids, reinforcing agents, processability improvers, heat stabilizers, lubricants, plasticizers, light stabilizers, ultraviolet absorbers, antioxidants, pigments, dyes, etc. Can be mentioned. These may be added alone or in combination of two or more.
  • filler By containing a filler, the resin composition can be expected to have the effect of improving the flexural modulus of a molded article obtained from the resin composition.
  • fillers include silica, diatomaceous earth, alumina, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, ferrites, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, and bases.
  • calcium carbonate, calcium silicate, calcium hydroxide, calcium oxide, magnesium carbonate, magnesium hydroxide, magnesium oxide, barium carbonate, aluminum hydroxide, and zinc oxide are highly effective in improving mechanical properties and Vicat softening temperature.
  • basic inorganic fillers such as zinc hydroxide, iron oxide, talc and the like are preferred. These fillers may be used alone or in combination of two or more.
  • the resin composition preferably contains 1 to 100 parts by weight, more preferably 1 to 75 parts by weight, and even more preferably 1 to 50 parts by weight of a filler per 100 parts by weight of the chlorine-containing polymer.
  • the content of the filler is, for example, 1, 3, 5, 10, 20, 40, 60, 80, 100 parts by mass with respect to 100 parts by mass of the chlorine-containing polymer, and the numerical values exemplified here. It may be within the range between any two.
  • the content of the filler means the total amount of the filler used together.
  • the filler content By setting the filler content to 1 part by mass or more with respect to 100 parts by mass of the chlorine-containing polymer, the effect of improving the flexural modulus can be obtained, and by setting it to 50 parts by mass or less, a decrease in dispersibility can be suppressed.
  • processing aids examples include acrylic copolymers. These processing aids may be used alone or in combination of two or more. By containing a processing aid, the resin composition can be expected to have the effect of promoting gelation during processing and improving the moldability of molded articles obtained from the resin composition.
  • the resin composition preferably contains 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight of a processing aid, per 100 parts by weight of the chlorine-containing polymer.
  • the content of the processing aid is, for example, 0.01, 0.02, 0.05, 0.1, 0.2, 0.5, 1, with respect to 100 parts by mass of the chlorine-containing polymer.
  • the amount may be 2, 5, or 10 parts by mass, and may be within a range between any two of the numerical values exemplified here.
  • the amount of the processing aid used means the total amount of the processing aid used together.
  • the content of the processing aid to 100 parts by mass of the chlorine-containing polymer to 0.01 parts by mass or more, the effect of improving processability can be obtained, and by setting it to 10 parts by mass or less, deterioration in mechanical properties can be suppressed. .
  • melt-kneading devices include a single screw extruder, an intermeshing type co-rotating or intermeshing type counter-rotating twin screw extruder, a screw extruder such as a non-intermeshing type twin screw extruder, a Banbury mixer, There are co-kneaders, mixing rolls, etc. Moreover, a plurality of these extruders can be used in combination.
  • a molded article can be obtained by molding the resin composition by a known method.
  • the molding method include injection molding, sheet extrusion molding, vacuum molding, blow molding, foam molding, and profile extrusion molding.
  • the resin composition is usually heated to 170 to 200°C and then processed, preferably at 190 to 200°C.
  • Sty represents styrene
  • AN represents acrylonitrile
  • NPMI N-phenylmaleimide
  • MAH represents maleic anhydride
  • MBS methyl methacrylate-butadiene-styrene resin
  • the filter material was obtained through a drying process of air drying for 24 hours and then drying in a vacuum dryer set at 70°C for 4 hours. (4) 0.5 liters of hexane was added dropwise to the filtrate obtained in (3) to obtain a mixed solution in which a portion of the crude product raw material was precipitated. (5) The above operations (3) and (4) were repeated to obtain five filtrates. Each filter material was obtained through a drying process of air drying for 24 hours and then drying in a vacuum dryer set at 70° C. for 4 hours. The weight of each filter material was 100 g, 140 g, 300 g, 260 g, and 200 g in the order obtained. (6) For each of the five filters, a 10% by mass THF solution of the filters was prepared.
  • composition of the copolymer (P-1) was confirmed using the C-13 NMR method described below, it was found to be 70% by mass of styrene, 8% by mass of acrylonitrile, 21% by mass of N-phenylmaleimide, and 1% by mass of maleic anhydride. .
  • the filter material was obtained through a drying process of air drying for 24 hours and then drying in a vacuum dryer set at 70°C for 4 hours. (4) 0.5 liters of hexane was added dropwise to the filtrate obtained in (3) to obtain a mixed solution in which a portion of the crude product raw material was precipitated. (5) The above operations (3) and (4) were repeated to obtain five filtrates. Each filter material was obtained through a drying process of air drying for 24 hours and then drying in a vacuum dryer set at 70° C. for 4 hours. The weight of each filter material was 130 g, 250 g, 280 g, 230 g, and 110 g in the order obtained. (6) For each of the five filters, a 10% by mass THF solution of the filters was prepared.
  • the filter material was obtained through a drying process of air drying for 24 hours and then drying in a vacuum dryer set at 70°C for 4 hours. (4) 0.5 liters of hexane was added dropwise to the filtrate obtained in (3) to obtain a mixed solution in which a portion of the crude product raw material was precipitated. (5) The above operations (3) and (4) were repeated to obtain five filtrates. Each filter material was obtained through a drying process of air drying for 24 hours and then drying in a vacuum dryer set at 70° C. for 4 hours. The weight of each filter material was 180 g, 200 g, 250 g, 200 g, and 170 g in the order obtained. (6) For each of the five filters, a 10% by mass THF solution of the filters was prepared.
  • the filter material was obtained through a drying process of air drying for 24 hours and then drying in a vacuum dryer set at 70°C for 4 hours. (4) 0.5 liters of hexane was added dropwise to the filtrate obtained in (3) to obtain a mixed solution in which a portion of the crude product raw material was precipitated. (5) The above operations (3) and (4) were repeated to obtain five filtrates. Each filter material was obtained through a drying process of air drying for 24 hours and then drying in a vacuum dryer set at 70° C. for 4 hours. The weight of each filter material was 180 g, 270 g, 320 g, 170 g, and 60 g in the order obtained. (6) For each of the five filters, a 10% by mass THF solution of the filters was prepared.
  • the filter material was obtained through a drying process of air drying for 24 hours and then drying in a vacuum dryer set at 70°C for 4 hours.
  • 4 liters of hexane was added dropwise to the filtrate obtained in (3) to obtain a mixed solution in which the dissolved crude product raw material was precipitated.
  • the mixed solution was filtered and separated into a filtrate and a filtrate.
  • Each filter material was obtained through a drying process of air drying for 24 hours and then drying in a vacuum dryer set at 70° C. for 4 hours.
  • the weight of each filter material was 130 g and 870 g in the order obtained.
  • Chlorine-containing polymer 1-2: HA-53K (product name), manufactured by Tokuyama Sekisui Kogyo Co., Ltd., K value 66.0 ⁇ 2.0, degree of chlorination 67.3 ⁇ 1.0% was used.
  • Chlorine-containing polymer 1-3 HA-15E (product name), manufactured by Tokuyama Sekisui Kogyo Co., Ltd., K value 56.0 ⁇ 2.0, degree of chlorination 63.5 ⁇ 1.0% was used.
  • (2) Modifier for chlorine-containing polymers Copolymers (P-1) to (P-5) obtained according to the above production examples were used as modifiers for chlorine-containing polymers according to the examples, and the crude Raw materials (R-1) to (R-5) were used as modifiers for chlorine-containing polymers according to comparative examples.
  • Impact modifier/MBS Metablen C-223A (product name), manufactured by Mitsubishi Chemical Corporation, was used.
  • Examples A1 to A7, B1 to B7, C1 to C7, Comparative Examples A1 to A8, B1 to B8, C1 to C8 (kneading and mixing of a chlorine-containing polymer modifier and a chlorine-containing polymer) After blending the modifier for chlorine-containing polymers and the chlorine-containing polymer, which was mixed in advance with a stabilizer and a lubricant using a Henschel mixer, in the proportions shown in Tables 1-1 to 1-3, a test roll ( ⁇ 6 ⁇ A roll sheet was created using an L15 test roll (manufactured by Kansai Roll Co., Ltd.), the roll sheets were stacked and press-formed, and a test piece was created by cutting or punching, and each physical property value was measured.
  • Examples A1 to A7 and Comparative Examples A1 to A8 is the value when each chlorine-containing polymer modifier and chlorine-containing polymer 1-1 are used, and Examples B1 to B7,
  • the lightness L * in Comparative Examples B1 to B8 is the value when using each chlorine-containing polymer modifier and chlorine-containing polymer 1-2, and the lightness L in Examples C1 to C7 and Comparative Examples C1 to C8 is * is the value when each chlorine-containing polymer modifier and chlorine-containing polymer 1-3 are used.
  • the results are shown in Tables 1-1 to 1-3.
  • Lightness L * is the optical path length of a mixed solution prepared by mixing a 10% by mass THF solution of a chlorine-containing polymer modifier and a 10% by mass THF solution of a chlorine-containing polymer at a volume ratio of 1:1. This value is measured under the conditions of measurement in the L * a * b * mode of a spectrophotometer V-670 manufactured by JASCO Corporation, in an optical cell with an optical path width of 10 mm. The lightness L * of each liquid mixture was measured under the measurement conditions described below.
  • composition analysis The compositional analysis of each chlorine-containing polymer modifier (copolymer and crude product raw material) was measured by C-13 NMR method under the measurement conditions described below.
  • the Vicat softening point of the resin composition was measured based on JIS K7206:1999 using the 50 method (load 50 N, temperature increase rate 50° C./hour) using a test piece measuring 20 mm ⁇ 20 mm and 4 mm thick.
  • the measuring device used was an HDT & VSPT testing device manufactured by Toyo Seiki Seisakusho.
  • the Charpy impact strength of the resin composition was measured in accordance with JIS K-7111 using a notched test piece and using an edgewise impact direction at a relative humidity of 50% and an ambient temperature of 23°C.
  • the measuring device used was a digital impact tester manufactured by Toyo Seiki Seisakusho.
  • the modifier (R-1) is the crude product raw material (R-1).
  • the modifier (P-1-1) was added to the first filtrate obtained by the first operation (3).
  • Modifiers (P-1-2) to (P-1-5) were obtained by repeating operations (3) to (4) after undergoing operations (1) to (7), respectively. In this case, these are the second to fifth filtrates obtained from the second to fifth operations (3).
  • the third filter material, the modifier (P-1-3), corresponds to the copolymer (P-1).
  • the modifier (R-5) is the crude product raw material (R-5).
  • the modifier (P-5-1) is the first filtrate obtained by the operation (3)
  • Modifier (P-5-2) is the second filtrate obtained by operation (5).
  • the first filter material, the modifier (P-5-1), corresponds to the copolymer (P-5).
  • a modifier for a chlorine-containing polymer that can improve the heat resistance and impact resistance of a chlorine-containing polymer, a resin composition containing a modifier for a chlorine-containing polymer and a chlorine-containing polymer, and a molded article thereof It is suitably used for molded products that require heat resistance and impact resistance.
  • Sty represents styrene
  • AN represents acrylonitrile
  • NPMI N-phenylmaleimide
  • MAH represents maleic anhydride
  • MBS represents methyl methacrylate-butadiene-styrene resin
  • PE represents polyethylene.
  • the imidization reaction solution was put into a vent type screw extruder, and volatile components were removed to obtain a crude biological raw material (R-2-1) for a maleimide copolymer in the form of pellets.
  • a crude biological raw material (R-2-1) for maleimide copolymer was analyzed using the C-13 NMR method described below, it was found to be 70% by mass of styrene, 8% by mass of acrylonitrile, and 21% by mass of N-phenylmaleimide. , 1% by mass of maleic anhydride.
  • the following operations (1) to (6) were performed to obtain a maleimide copolymer (P-2-1).
  • 1000 g of crude product raw material (R-2-1) was dissolved in 5 liters of methyl ethyl ketone to obtain a methyl ethyl ketone solution of the crude product raw material.
  • (2) 1.6 liters of hexane was added dropwise to the methyl ethyl ketone solution to obtain a mixed solution in which 10% by mass of the dissolved crude product raw material was precipitated.
  • the mixed solution was filtered and separated into a filtrate and a filtrate.
  • the filter material was obtained through a drying process of air drying for 24 hours and then drying in a vacuum dryer set at 70°C for 4 hours.
  • the composition of the maleimide copolymer (P-2-1) was confirmed using the C-13 NMR method described below, it was found to be 70% by mass of styrene, 8% by mass of acrylonitrile, 21% by mass of N-phenylmaleimide, and 1% by mass of maleic anhydride. %Met.
  • the analysis results of the obtained maleimide copolymer are shown in Table 2-1.
  • 10% by mass THF solutions of the maleimide copolymer (P-2-1) and chlorine-containing polymers 2-1, 2-2, and 2-3 were prepared, and the copolymer and chlorine-containing polymer were mixed.
  • the lightness L* of the mixed liquid prepared by mixing THF solutions at a volume ratio of 1:1 was measured, and the results were 98, 92, and 90, respectively.
  • the imidization reaction solution was put into a vent type screw extruder, and volatile components were removed to obtain a crude biological raw material (R-2-2) for a maleimide copolymer in the form of pellets.
  • a crude biological raw material (R-2-2) for maleimide copolymer was analyzed using the C-13 NMR method described below, it was found to be 65% by mass of styrene, 14% by mass of acrylonitrile, and 20% by mass of N-phenylmaleimide. , 1% by mass of maleic anhydride.
  • the following operations (1) to (6) were performed to obtain a maleimide copolymer (P-2-2).
  • 1000 g of crude product raw material (R-2-2) was dissolved in 5 liters of methyl ethyl ketone to obtain a methyl ethyl ketone solution of the crude product raw material.
  • (2) 1.6 liters of hexane was added dropwise to the methyl ethyl ketone solution to obtain a mixed solution in which 10% by mass of the dissolved crude product raw material was precipitated.
  • the mixed solution was filtered and separated into a filtrate and a filtrate.
  • the filter material was obtained through a drying process of air drying for 24 hours and then drying in a vacuum dryer set at 70°C for 4 hours.
  • the composition of the maleimide copolymer (P-2-2) was confirmed using the C-13 NMR method described below, it was found to be 65% by mass of styrene, 14% by mass of acrylonitrile, 20% by mass of N-phenylmaleimide, and 1% by mass of maleic anhydride. %Met.
  • the analysis results of the obtained maleimide copolymer are shown in Table 2-1.
  • 10% by mass THF solutions of the maleimide copolymer (P-2-2) and chlorine-containing polymers 2-1, 2-2, and 2-3 were prepared, and the copolymer and chlorine-containing polymer were mixed.
  • the lightness L* of the mixed liquid prepared by mixing THF solutions at a volume ratio of 1:1 was measured, and the results were 60, 50, and 43, respectively.
  • the imidization reaction solution was put into a vent type screw extruder, and volatile components were removed to obtain a crude biological raw material (R-2-3) for a maleimide copolymer in the form of pellets.
  • a compositional analysis of the crude biological raw material (R-2-3) for the maleimide copolymer using the C-13 NMR method described below revealed that it was 80% by mass of styrene, 4% by mass of acrylonitrile, and 15% by mass of N-phenylmaleimide. , 1% by mass of maleic anhydride.
  • the following operations (1) to (6) were performed to obtain a maleimide copolymer (P-2-3).
  • 1000 g of crude product raw material (R-2-3) was dissolved in 5 liters of methyl ethyl ketone to obtain a methyl ethyl ketone solution of the crude product raw material.
  • the mixed solution was filtered and separated into a filtrate and a filtrate.
  • the filter material was obtained through a drying process of air drying for 24 hours and then drying in a vacuum dryer set at 70°C for 4 hours.
  • the mixed solution was filtered and separated into a filtrate and a filtrate.
  • Each filter material was obtained through a drying process of air drying for 24 hours and then drying in a vacuum dryer set at 70° C. for 4 hours. The weight of each filter material was 130 g and 870 g in the order obtained.
  • the first filtrate obtained was obtained as a maleimide copolymer (P-2-3).
  • the composition of the maleimide copolymer (P-2-3) was confirmed using the C-13 NMR method described below, it was found to be 76% by mass of styrene, 8% by mass of acrylonitrile, 15% by mass of N-phenylmaleimide, and 1% by mass of maleic anhydride. %Met.
  • the analysis results of the obtained maleimide copolymer are shown in Table 2-1.
  • 10% by mass THF solutions of the maleimide copolymer (P-2-3) and chlorine-containing polymers 2-1, 2-2, and 2-3 were prepared, and the copolymer and chlorine-containing polymer were mixed.
  • the lightness L* of the mixed solution prepared by mixing THF solutions at a volume ratio of 1:1 was measured, and the results were 69, 67, and 42, respectively.
  • the imidization reaction solution was put into a vent type screw extruder, and the volatile components were removed to obtain a crude biological raw material (R-2-4) for a maleimide copolymer in the form of pellets.
  • R-2-4 crude biological raw material for maleimide copolymer
  • the composition of the crude biological raw material (R-2-4) for maleimide copolymer was analyzed using the C-13 NMR method described below, it was found to be 90% by mass of styrene, 0% by mass of acrylonitrile, and 10% by mass of N-phenylmaleimide. , maleic anhydride was 0% by mass.
  • the resulting maleimide copolymer was not purified, and the crude biological raw material (R-2-4) was used as a copolymer (P-2-4).
  • the analysis results of the obtained maleimide copolymer are shown in Table 2-1.
  • 10% by mass THF solutions of each of the maleimide copolymer (P-2-4) and chlorine-containing polymers 2-1, 2-2, and 2-3 were prepared, and the copolymer and chlorine-containing polymer were mixed.
  • the lightness L* of the mixed liquid prepared by mixing THF solutions at a volume ratio of 1:1 was measured, and the results were 18, 16, and 14, respectively.
  • the following operations (1) to (6) were performed to obtain a copolymer (P-2-5).
  • 1000 g of crude product raw material (R-2-5) was dissolved in 5 liters of methyl ethyl ketone to obtain a methyl ethyl ketone solution of the crude product raw material.
  • (2) 1.6 liters of hexane was added dropwise to the methyl ethyl ketone solution to obtain a mixed solution in which 10% by mass of the dissolved crude product raw material was precipitated.
  • the mixed solution was filtered and separated into a filtrate and a filtrate.
  • the filter material was obtained through a drying process of air drying for 24 hours and then drying in a vacuum dryer set at 70°C for 4 hours.
  • composition of the maleimide copolymer (P-2-5) was confirmed using the C-13 NMR method described below, it was found to be 77% by mass of styrene, 23% by mass of acrylonitrile, 0% by mass of N-phenylmaleimide, and 0% by mass of maleic anhydride. %Met.
  • the analysis results of the obtained copolymer are shown in Table 2-1.
  • a 10% by mass THF solution of each of the copolymer (P-2-5) and chlorine-containing polymers 2-1, 2-2, and 2-3 was prepared, and a THF solution of the copolymer and chlorine-containing polymer was prepared.
  • the lightness L* of the mixed liquid prepared by mixing the two in a volume ratio of 1:1 was 75, 70, and 44, respectively.
  • PVC Chlorine-containing polymer
  • R-4 Chlorine-containing polymer ⁇ Chlorine-containing polymer 2-1: HA-15E (product name), manufactured by Tokuyama Sekisui Kog
  • the test A roll sheet was created using a roll ( ⁇ 6 x L15 test roll, manufactured by Kansai Roll Co., Ltd.), the roll sheets were stacked and press molded, and a test piece was created by cutting or punching to determine each physical property of the resin composition. The value was measured.
  • composition analysis Compositional analysis of each copolymer was performed using the C-13 NMR method under the measurement conditions described below.
  • VST Vicat softening point
  • the Vicat softening point of the resin composition was determined based on JIS K7206:1999 using the 50 method (load 50N, elevation The temperature was measured at a temperature rate of 50° C./hour).
  • the measuring device used was an HDT & VSPT testing device manufactured by Toyo Seiki Seisakusho.
  • the Charpy impact strength of the resin composition was determined by punching out a rectangular test piece by press-molding stacked roll sheets.
  • a notched test piece was prepared by processing the rectangular test piece according to JIS K-7144:1999 using a notch processing machine (189-PNCA manufactured by Yasuda Seiki Seisakusho Co., Ltd.).
  • JIS K-7111:2012 using the notched test piece, the impact direction was edgewise, and the measurement was performed at a relative humidity of 50% and an ambient temperature of 23°C.
  • the measuring device used was a digital impact tester manufactured by Toyo Seiki Seisakusho.
  • a resin composition containing a chlorine-containing polymer that satisfies both impact resistance and heat resistance which are in a trade-off relationship, even when an impact modifier and a heat resistance imparting agent are added.
  • a product and a molded article thereof are provided, and are suitably used for molded products that require heat resistance and impact resistance.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Provided are a chlorine-containing polymer modifier that makes it possible to improve the heat resistance and impact resistance of a chlorine-containing polymer, a resin composition that includes the chlorine-containing polymer modifier, and a molded body of the resin composition.　The present invention provides a chlorine-containing polymer modifier. When a 10 mass% THF solution of the chlorine-containing polymer modifier and a 10 mass% THF solution of a chlorine-containing polymer that has a K value of 66.7±1.0 and a chlorination of 57±1.0% are mixed at a volume ratio of 1:1, the brightness L* of the resulting liquid mixture is at least 40.

Description

塩素含有ポリマー用改質剤、樹脂組成物、及び成形体Modifiers for chlorine-containing polymers, resin compositions, and molded bodies
　本発明は、塩素含有ポリマー用改質剤、塩素含有ポリマー用改質剤と塩素含有ポリマーを含む樹脂組成物、及び当該樹脂組成物を用いた成形体に関するものである。また、本発明は、樹脂組成物、成形体に関する。 The present invention relates to a modifier for chlorine-containing polymers, a resin composition containing the modifier for chlorine-containing polymers and a chlorine-containing polymer, and a molded article using the resin composition. The present invention also relates to a resin composition and a molded article.
　塩素含有ポリマー系樹脂は安価であり、優れた化学的、物理的、機械的性質を有しているため、大量に生産され、種々の用途に使用されている。
　しかしながら、塩素含有ポリマーは耐熱性に欠ける（熱軟化温度が低い）という欠点を有しており、例えばＪＩＳ　Ｋ７２０６：１９９９に基づき、５０法（荷重５０Ｎ、昇温速度５０℃／時間）により測定されるビカット軟化温度は８２℃前後であり、通常成形加工時に配合される安定剤、可塑剤により、更に軟化温度は低下する。
　ポリ塩化ビニルの耐熱性を向上する方法としては、耐熱性を付与する樹脂をポリ塩化ビニルと混合する方法（特許文献１～４）が知られている。 Chlorine-containing polymer resins are inexpensive and have excellent chemical, physical, and mechanical properties, so they are produced in large quantities and used for various purposes.
However, chlorine-containing polymers have the disadvantage of lacking heat resistance (low heat softening temperature), and for example, they have been measured by the 50 method (load 50N, heating rate 50°C/hour) based on JIS K7206:1999. The Vicat softening temperature is around 82°C, and the softening temperature is further lowered by stabilizers and plasticizers that are usually added during molding.
As a method for improving the heat resistance of polyvinyl chloride, a method is known in which a resin that imparts heat resistance is mixed with polyvinyl chloride (Patent Documents 1 to 4).
特許６４７５５０１Patent 6475501 特開２００６－２６５３７３JP2006-265373 国際公開ＷＯ２０２２／０３９０９８号International publication WO2022/039098 国際公開ＷＯ２０２２／０３９０９９号International publication WO2022/039099
（第１観点）
　本発明の第１観点は、塩素含有ポリマーの耐熱性及び耐衝撃性を向上することができる塩素含有ポリマー用改質剤、塩素含有ポリマー用改質剤を含む樹脂組成物及び当該樹脂組成物を用いた成形体を提供しようとするものである。 (First perspective)
A first aspect of the present invention is a modifier for chlorine-containing polymers that can improve the heat resistance and impact resistance of chlorine-containing polymers, a resin composition containing the modifier for chlorine-containing polymers, and a resin composition that can improve the heat resistance and impact resistance of chlorine-containing polymers. The purpose of this paper is to provide a molded article using the following methods.
（第２観点）
　塩素含有ポリマーに耐熱性付与材を添加した場合、耐衝撃性が低下してしまうため耐衝撃改質剤を添加して使用する場合があるが、それにより耐熱性が低下するため、耐熱性と耐衝撃性はトレードオフの関係にあり、耐熱性と耐衝撃性が両立した塩素含有ポリマー含有樹脂組成物を得ることは難しかった。 (Second perspective)
If a heat resistance imparting agent is added to a chlorine-containing polymer, the impact resistance will decrease, so an impact modifier may be added to the chlorine-containing polymer. Impact resistance is in a trade-off relationship, and it has been difficult to obtain a chlorine-containing polymer-containing resin composition that has both heat resistance and impact resistance.
　本発明の第２観点は、上記事情に鑑みてなされたものであり、耐衝撃改質剤及び耐熱性付与剤を添加した場合でも、トレードオフの関係にあった耐衝撃性と耐熱性が良好に両立される塩素含有ポリマーを含む樹脂組成物を提供する。 The second aspect of the present invention was made in view of the above circumstances, and even when an impact modifier and a heat resistance imparting agent are added, impact resistance and heat resistance, which are in a trade-off relationship, are good. Provided is a resin composition containing a chlorine-containing polymer that is compatible with the following.
（第１観点）　本発明者らの検討の結果、前記塩素含有ポリマー用改質剤の１０質量％のＴＨＦ溶液と、Ｋ値が６６．７±１．０であり、塩素化度が５７±１．０％である塩素含有ポリマーの１０質量％のＴＨＦ溶液とを１：１の容量比で混合して作製した混合液における明度Ｌ＊が４０以上である、塩素含有ポリマー用改質剤を採用すれば、塩素含有ポリマーの耐熱性及び耐衝撃性を向上させることができることを見出した。
　即ち、本発明の第１観点によれば、以下の発明が提供される。
［１－１］　塩素含有ポリマー用改質剤であり、
　前記塩素含有ポリマー用改質剤の１０質量％のＴＨＦ溶液と、Ｋ値が６６．７±１．０であり、塩素化度が５７．０±１．０％である塩素含有ポリマーの１０質量％のＴＨＦ溶液とを１：１の容量比で混合して作製した混合液における明度Ｌ＊が４０以上である、塩素含有ポリマー用改質剤。
［１－２］　少なくとも芳香族ビニル系単量体単位、シアン化ビニル系単量体単位、マレイミド系単量体単位を含む共重合体を含む、［１－１］に記載の塩素含有ポリマー用改質剤。
［１－３］　前記共重合体に含有される単量体単位の合計を１００質量％とした場合に、
　　前記芳香族ビニル系単量体単位６０～８５質量％、
　　前記シアン化ビニル系単量体単位０．５～２０質量％、
　　前記マレイミド系単量体単位１０～３０質量％
を含む、［１－２］に記載の塩素含有ポリマー用改質剤。
［１－４］　［１－１］～［１－３］のいずれか一つに記載の塩素含有ポリマー用改質剤と、塩素含有ポリマーを含有する樹脂組成物。
［１－５］　［１－４］に記載の樹脂組成物を用いた成形体。 (First viewpoint) As a result of the inventors' studies, it was found that a 10% by mass THF solution of the modifier for chlorine-containing polymer has a K value of 66.7±1.0 and a degree of chlorination of 57±1.0. A modifier for chlorine-containing polymers that has a lightness L * of 40 or more in a mixed solution prepared by mixing a 1.0% chlorine-containing polymer with a 10% by mass THF solution at a volume ratio of 1:1. It has been found that if employed, the heat resistance and impact resistance of chlorine-containing polymers can be improved.
That is, according to the first aspect of the present invention, the following invention is provided.
[1-1] A modifier for chlorine-containing polymers,
A 10% by mass THF solution of the modifier for chlorine-containing polymers and 10% by mass of a chlorine-containing polymer having a K value of 66.7 ± 1.0 and a degree of chlorination of 57.0 ± 1.0%. % THF solution at a volume ratio of 1:1, and the lightness L * of the mixed solution is 40 or more.
[1-2] For the chlorine-containing polymer according to [1-1], comprising a copolymer containing at least an aromatic vinyl monomer unit, a cyanide vinyl monomer unit, and a maleimide monomer unit. modifier.
[1-3] When the total of monomer units contained in the copolymer is 100% by mass,
60 to 85% by mass of the aromatic vinyl monomer unit,
0.5 to 20% by mass of the vinyl cyanide monomer unit,
10 to 30% by mass of the maleimide monomer unit
The modifier for chlorine-containing polymers according to [1-2], comprising:
[1-4] A resin composition containing the chlorine-containing polymer modifier according to any one of [1-1] to [1-3] and a chlorine-containing polymer.
[1-5] A molded article using the resin composition according to [1-4].
（第２観点）
　本発明者らは上記課題を解決するために鋭意検討した結果、特定の塩素含有量の塩素含有ポリマーを用い、特定のマレイミド系共重合体を特定の割合で配合することにより、上記課題を解決しうることを見出し、本発明を完成するに至った。 (Second perspective)
As a result of intensive studies to solve the above problems, the present inventors solved the above problems by using a chlorine-containing polymer with a specific chlorine content and blending a specific maleimide copolymer in a specific ratio. They have discovered that it is possible to do so, and have completed the present invention.
　すなわち、本発明の第２観点によれば、以下の発明が提供される。
［２－１］樹脂組成物であって、塩素含有ポリマー１００質量部と、マレイミド系共重合体１～４０質量部と、を含み、前記塩素含有ポリマーの塩素含有量が６０質量％～７０質量％であり、前記マレイミド系共重合体は、シアン化ビニル系単量体単位と、マレイミド系単量体単位と、を有する、樹脂組成物。
［２－２］［２－１］に記載の樹脂組成物であって、前記マレイミド系共重合体は、芳香族ビニル系単量体単位と、前記シアン化ビニル系単量体単位と、前記マレイミド系単量体単位と、を有する、樹脂組成物。
［２－３］［２－２］に記載の樹脂組成物であって、前記マレイミド系共重合体に含有される単量体単位の合計を１００質量％とした場合に、前記芳香族ビニル系単量体単位６０～８５質量％と、前記シアン化ビニル系単量体単位０．５～２０質量％と、前記マレイミド系単量体単位１０～３０質量％と、を有する、樹脂組成物。
［２－４］［２－２］又は［２－３］に記載の樹脂組成物であって、前記マレイミド系共重合体に含有される単量体単位の合計を１００質量％とした場合に、前記芳香族ビニル系単量体単位６５～８０質量％と、前記シアン化ビニル系単量体単位０．５～１５質量％と、前記マレイミド系単量体単位１０～２５質量％と、を有する、樹脂組成物。
［２－５］［２－１］～［２－４］の何れか１つに記載の樹脂組成物であって、前記マレイミド系共重合体の重量平均分子量が７０，０００～１５０，０００である、樹脂組成物。
［２－６］［２－１］～［２－５］の何れか１つに記載の樹脂組成物であって、前記樹脂組成物１００質量％中、前記塩素含有ポリマーを４質量％以上含む、樹脂組成物。
［２－７］［２－１］～［２－６］の何れか１つに記載の樹脂組成物であって、耐衝撃改質剤をさらに含む、樹脂組成物。
［２－８］［２－１］～［２－７］の何れか１つに記載の樹脂組成物を用いた成形体。 That is, according to the second aspect of the present invention, the following invention is provided.
[2-1] A resin composition comprising 100 parts by mass of a chlorine-containing polymer and 1 to 40 parts by mass of a maleimide copolymer, wherein the chlorine content of the chlorine-containing polymer is 60% to 70% by mass. %, and the maleimide copolymer has a vinyl cyanide monomer unit and a maleimide monomer unit.
[2-2] The resin composition according to [2-1], wherein the maleimide copolymer comprises an aromatic vinyl monomer unit, the vinyl cyanide monomer unit, and the A resin composition comprising a maleimide monomer unit.
[2-3] The resin composition according to [2-2], in which the aromatic vinyl-based A resin composition comprising 60 to 85% by mass of monomer units, 0.5 to 20% by mass of the vinyl cyanide monomer units, and 10 to 30% by mass of the maleimide monomer units.
[2-4] The resin composition according to [2-2] or [2-3], when the total of monomer units contained in the maleimide copolymer is 100% by mass. , 65 to 80% by mass of the aromatic vinyl monomer unit, 0.5 to 15% by mass of the vinyl cyanide monomer unit, and 10 to 25% by mass of the maleimide monomer unit. A resin composition comprising:
[2-5] The resin composition according to any one of [2-1] to [2-4], wherein the maleimide copolymer has a weight average molecular weight of 70,000 to 150,000. A resin composition.
[2-6] The resin composition according to any one of [2-1] to [2-5], which contains 4% by mass or more of the chlorine-containing polymer based on 100% by mass of the resin composition. , resin composition.
[2-7] The resin composition according to any one of [2-1] to [2-6], further comprising an impact modifier.
[2-8] A molded article using the resin composition according to any one of [2-1] to [2-7].
（第１観点）
　本発明の第１観点の塩素含有ポリマー用改質剤を採用すれば、塩素含有ポリマーの耐熱性及び耐衝撃性を向上させることができる。このため、耐熱性や耐衝撃性が要求される用途に好適に利用される。 (First perspective)
By employing the modifier for chlorine-containing polymers according to the first aspect of the present invention, the heat resistance and impact resistance of chlorine-containing polymers can be improved. Therefore, it is suitably used in applications requiring heat resistance and impact resistance.
（第２観点）
　本発明の第２観点によれば、塩素含有ポリマーを含む樹脂組成物において、耐衝撃改質剤及び耐熱性付与剤を添加した場合でも、トレードオフの関係にあった耐衝撃性と耐熱性が良好に両立される。このため、耐熱性や耐衝撃性が要求される用途に好適に利用される。 (Second perspective)
According to the second aspect of the present invention, even when an impact modifier and a heat resistance imparting agent are added to a resin composition containing a chlorine-containing polymer, impact resistance and heat resistance, which have a trade-off relationship, are maintained. Both are well compatible. Therefore, it is suitably used in applications requiring heat resistance and impact resistance.
＜用語の説明＞
　本願明細書において、「Ａ～Ｂ」なる記載は、Ａ以上でありＢ以下であることを意味する。 <Explanation of terms>
In the present specification, the description "A to B" means greater than or equal to A and less than or equal to B.
　以下、本発明の実施形態について、詳細に説明する。本発明はこれに限定されるものではなく、その要旨を逸脱しない範囲で様々な変形が可能である。以下に示す実施形態中で示した各種特徴事項は互いに組み合わせ可能である。また、各特徴事項について独立して発明が成立する。 Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited to this, and various modifications can be made without departing from the gist thereof. Various features shown in the embodiments described below can be combined with each other. Further, the invention is established independently for each characteristic matter.
（第１観点の実施形態）
１－１．塩素含有ポリマー用改質剤
　本発明の第１観点の一実施形態（以下、本実施形態）にかかる塩素含有ポリマー用改質剤は、当該塩素含有ポリマー用改質剤の１０質量％のＴＨＦ溶液と、Ｋ値が６６．７±１．０であり、塩素化度が５７±１．０％である塩素含有ポリマーの１０質量％のＴＨＦ溶液とを１：１の容量比で混合して作製した混合液における明度Ｌ＊が４０以上であり、好ましくは５０以上であり、さらに好ましくは６０以上である。具体的には、例えば、４０、４５、５０、５５、６０、６５、７０、７５、８０、８５、９０、又は９５であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。混合液における明度Ｌ＊を４０以上とすることで塩素含有ポリマーの耐熱性及び耐衝撃性を向上させることができる。
　なお、ここでいう塩素化度とは、塩素含有ポリマー中の塩素の含有量（質量％）である。 (Embodiment of the first viewpoint)
1-1. Modifier for chlorine-containing polymers The modifier for chlorine-containing polymers according to an embodiment of the first aspect of the present invention (hereinafter referred to as the present embodiment) is a 10% by mass THF solution of the modifier for chlorine-containing polymers. and a 10% by mass THF solution of a chlorine-containing polymer with a K value of 66.7 ± 1.0 and a degree of chlorination of 57 ± 1.0% in a 1:1 volume ratio. The lightness L * of the mixed liquid is 40 or more, preferably 50 or more, and more preferably 60 or more. Specifically, for example, it is 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95, and is within the range between any two of the numerical values exemplified here. You can. By setting the lightness L * of the mixed liquid to 40 or more, the heat resistance and impact resistance of the chlorine-containing polymer can be improved.
Note that the degree of chlorination here refers to the content of chlorine (% by mass) in the chlorine-containing polymer.
　本発明にかかる塩素含有ポリマー用改質剤は、一態様において、当該塩素含有ポリマー用改質剤の１０質量％のＴＨＦ溶液と、Ｋ値が６６．０±２．０である塩素含有率の高い塩素含有ポリマー（塩素化度＝６７．３±１．０％）の１０質量％のＴＨＦ溶液とを１：１の容量比で混合して作製した混合液における明度Ｌ＊が６０以上である。
　また、本発明にかかる塩素含有ポリマー用改質剤は、一態様において、当該塩素含有ポリマー用改質剤の１０質量％のＴＨＦ溶液と、Ｋ値が５６．０±２．０である塩素含有率の高い塩素含有ポリマー（塩素化度＝６３．５±１．０％）の１０質量％のＴＨＦ溶液とを１：１の容量比で混合して作製した混合液における明度Ｌ＊が６０以上である。 In one embodiment, the modifier for chlorine-containing polymers according to the present invention includes a 10% by mass THF solution of the modifier for chlorine-containing polymers and a chlorine content having a K value of 66.0±2.0. The lightness L * of the mixed liquid prepared by mixing a 10 mass% THF solution of a high chlorine-containing polymer (degree of chlorination = 67.3 ± 1.0%) at a volume ratio of 1:1 is 60 or more. .
In one aspect, the modifier for chlorine-containing polymers according to the present invention includes a 10% by mass THF solution of the modifier for chlorine-containing polymers, and a chlorine-containing modifier having a K value of 56.0±2.0. The lightness L * of a mixed solution prepared by mixing a 10% by mass THF solution of a highly chlorinated polymer (degree of chlorination = 63.5 ± 1.0%) at a volume ratio of 1:1 is 60 or more. It is.
　本実施形態にかかる塩素含有ポリマー及び塩素含有率の高い塩素含有ポリマーのＫ値とは、ＪＩＳＫ　７３６７－２に準拠し、毛細管粘度計を用いた溶液粘度測定により得られる値であり、塩素含有ポリマー及び塩素含有率の高い塩素含有ポリマーの重合度や分子量を示す指標である。
　本実施形態における明度Ｌ＊は、塩素含有ポリマー用改質剤の１０質量％のＴＨＦ溶液と、塩素含有ポリマーの１０質量％のＴＨＦ溶液とを１：１の容量比で混合して作製した混合液を光路長１０ｍｍであり光路幅１０ｍｍの光学セルにいれ、日本分光株式会社　分光光度計　Ｖ－６７０のＬ＊ａ＊ｂ＊モードで測定の条件において測定される値である。 The K value of the chlorine-containing polymer and the chlorine-containing polymer with a high chlorine content according to the present embodiment is a value obtained by measuring solution viscosity using a capillary viscometer in accordance with JISK 7367-2. It is an index showing the degree of polymerization and molecular weight of a chlorine-containing polymer with a high chlorine content.
The lightness L * in this embodiment is a mixture prepared by mixing a 10% by mass THF solution of a chlorine-containing polymer modifier and a 10% by mass THF solution of a chlorine-containing polymer at a volume ratio of 1:1. This is a value measured under the conditions of measurement in the L * a * b * mode of a spectrophotometer V-670 manufactured by JASCO Corporation by placing a liquid in an optical cell with an optical path length of 10 mm and an optical path width of 10 mm.
　混合液における明度Ｌ＊が所定の値以上である場合、塩素含有ポリマー用改質剤は、塩素含有ポリマーに配合して樹脂組成物とした場合に耐熱性及び耐衝撃性を良好に向上させることができる。
　混合液における明度Ｌ＊を調整する方法としては、例えば、後述する方法により共重合体を含む粗生成物原料を溶解させた溶液に対する沈殿操作及び濾過操作により所望の明度Ｌ＊を満たすような特定の共重合体を得る方法が挙げられる。 When the lightness L * of the mixed solution is equal to or higher than a predetermined value, the modifier for chlorine-containing polymers satisfactorily improves heat resistance and impact resistance when blended with chlorine-containing polymers to form a resin composition. Can be done.
As a method for adjusting the lightness L * in the mixed liquid, for example, a specific method that satisfies the desired lightness L * by performing a precipitation operation and a filtration operation on a solution in which a crude product material containing a copolymer is dissolved by the method described below. A method for obtaining a copolymer of
＜塩素含有ポリマー用改質剤に含有される共重合体＞
　本実施形態にかかる塩素含有ポリマー用改質剤は、少なくとも芳香族ビニル系単量体単位、シアン化ビニル系単量体単位、マレイミド系単量体単位を含む共重合体を含んでも良い。共重合体に含有される単量体単位について、以下説明する。 <Copolymer contained in modifier for chlorine-containing polymer>
The modifier for chlorine-containing polymers according to the present embodiment may include a copolymer containing at least an aromatic vinyl monomer unit, a cyanide vinyl monomer unit, and a maleimide monomer unit. The monomer units contained in the copolymer will be explained below.
＜芳香族ビニル系単量体単位＞
　本実施形態にかかる共重合体に含有される芳香族ビニル系単量体単位が由来する芳香族ビニル系単量体としては、例えば、スチレン、ｏ－メチルスチレン、ｍ－メチルスチレン、ｐ－メチルスチレン、２，４－ジメチルスチレン、エチルスチレン、ｐ－ｔｅｒｔ－ブチルスチレン、α－メチルスチレン、α－メチル－ｐ－メチルスチレン等が挙げられる。これらの中でも耐熱性、塩素含有ポリマーとの親和性、流動性のバランスの観点からスチレンが好ましい。芳香族ビニル系単量体は、単独でも良いが２種類以上を併用しても良い。 <Aromatic vinyl monomer unit>
Examples of the aromatic vinyl monomer from which the aromatic vinyl monomer unit contained in the copolymer according to the present embodiment is derived include styrene, o-methylstyrene, m-methylstyrene, p-methyl Examples include styrene, 2,4-dimethylstyrene, ethylstyrene, p-tert-butylstyrene, α-methylstyrene, α-methyl-p-methylstyrene, and the like. Among these, styrene is preferred from the viewpoint of heat resistance, affinity with chlorine-containing polymers, and fluidity balance. The aromatic vinyl monomer may be used alone, or two or more types may be used in combination.
　本実施形態にかかる共重合体は、共重合体に含有される単量体単位の合計を１００質量％とした場合に芳香族ビニル系単量体単位を好ましくは６０～８５質量％含有し、より好ましくは６５～８５質量％含有し、さらに好ましくは６８～８０質量％含有する。具体的には例えば、６０、６５、６８、７０、７２、７５、８０、又は８５質量％であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。芳香族ビニル系単量体単位の量を６０質量％以上とすることで優れた流動性と塩素含有ポリマーとの親和性のバランスで得られ、また、８５質量％以下とすることで十分な耐熱性が得られる。
　なお、芳香族ビニル系単量体単位を併用する場合には、芳香族ビニル系単量体単位の含有量は、併用する芳香族ビニル系単量体単位の合計量を意味する。 The copolymer according to this embodiment preferably contains 60 to 85% by mass of aromatic vinyl monomer units when the total amount of monomer units contained in the copolymer is 100% by mass, The content is more preferably 65 to 85% by mass, and even more preferably 68 to 80% by mass. Specifically, for example, it is 60, 65, 68, 70, 72, 75, 80, or 85% by mass, and may be within a range between any two of the numerical values exemplified here. By setting the amount of aromatic vinyl monomer units to 60% by mass or more, a balance between excellent fluidity and affinity with chlorine-containing polymers can be obtained, and by setting the amount to 85% by mass or less, sufficient heat resistance can be obtained. You can get sex.
In addition, when aromatic vinyl monomer units are used together, the content of the aromatic vinyl monomer units means the total amount of the aromatic vinyl monomer units used together.
＜シアン化ビニル系単量体単位＞
　本実施形態にかかる共重合体に含有されるシアン化ビニル系単量体単位が由来するシアン化ビニル系単量体としては、例えば、アクリロニトリル、メタクリロニトリル、エタクリロニトリル、フマロニトリル等が挙げられる。これらの中でも色相及び塩素含有ポリマー系樹脂組成物への耐熱性付与の観点からアクリロニトリルが好ましい。シアン化ビニル系単量体は単独でも良いが２種類以上を併用しても良い。 <Vinyl cyanide monomer unit>
Examples of the vinyl cyanide monomer from which the vinyl cyanide monomer unit contained in the copolymer according to the present embodiment is derived include acrylonitrile, methacrylonitrile, ethacrylonitrile, fumaronitrile, and the like. . Among these, acrylonitrile is preferred from the viewpoint of hue and imparting heat resistance to the chlorine-containing polymer resin composition. The vinyl cyanide monomer may be used alone, or two or more types may be used in combination.
　本実施形態にかかる共重合体は、共重合体に含有される単量体単位の合計を１００質量％とした場合にシアン化ビニル系単量体単位を好ましくは０．５～２０質量％含有し、より好ましくは３～２０質量％含有し、さらに好ましくは５～２０質量％含有する。具体的には例えば、０．５、１、５、７、１０、１３、１５、又は２０質量％であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。シアン化ビニル系単量体単位の量を０．５質量％とすることで、塩素含有ポリマー系樹脂組成物の耐熱性を十分に向上させることができ、２０質量％以下とすることで樹脂組成物の耐衝撃性と耐熱性のバランスを向上させることができる。
　なお、シアン化ビニル系単量体単位を併用する場合には、シアン化ビニル系単量体単位の含有量は、併用するシアン化ビニル系単量体単位の合計量を意味する。 The copolymer according to the present embodiment preferably contains vinyl cyanide monomer units in an amount of 0.5 to 20% by mass when the total amount of monomer units contained in the copolymer is 100% by mass. The content is more preferably 3 to 20% by mass, and even more preferably 5 to 20% by mass. Specifically, for example, it is 0.5, 1, 5, 7, 10, 13, 15, or 20% by mass, and may be within a range between any two of the numerical values exemplified here. By setting the amount of vinyl cyanide monomer units to 0.5% by mass, the heat resistance of the chlorine-containing polymer resin composition can be sufficiently improved, and by setting the amount to 20% by mass or less, the resin composition The balance between impact resistance and heat resistance of objects can be improved.
In addition, when vinyl cyanide monomer units are used together, the content of vinyl cyanide monomer units means the total amount of vinyl cyanide monomer units used together.
＜マレイミド系単量体単位＞
　本実施形態にかかる共重合体に含有されるマレイミド系単量体単位が由来するマレイミド系単量体としては、例えば、Ｎ－メチルマレイミド、Ｎ－ブチルマレイミド、Ｎ－シクロヘキシルマレイミド等のＮ－アルキルマレイミド、及びＮ－フェニルマレイミド、Ｎ－クロルフェニルマレイミド、Ｎ－メチルフェニルマレイミド、Ｎ－メトキシフェニルマレイミド、Ｎ－トリブロモフェニルマレイミド等のＮ－アリールマレイミド等がある。これらの中でも、塩素含有ポリマー系樹脂組成物への耐熱性付与の観点からＮ－アリールマレイミドが好ましく、Ｎ－フェニルマレイミドがさらに好ましい。マレイミド系単量体は、単独でも良いが２種類以上を併用しても良い。
　共重合体にマレイミド系単量体単位を含有させるには、例えば、不飽和ジカルボン酸単量体からなる原料を他の単量体と共重合させた共重合体をアンモニア又は第１級アミンでイミド化させればよい。あるいは、マレイミド系単量体からなる原料を他の単量体と共重合させてもよい。 <Maleimide monomer unit>
Examples of the maleimide monomer from which the maleimide monomer unit contained in the copolymer according to the present embodiment is derived include N-alkyl maleimide such as N-methylmaleimide, N-butylmaleimide, and N-cyclohexylmaleimide. Examples include maleimide and N-arylmaleimides such as N-phenylmaleimide, N-chlorophenylmaleimide, N-methylphenylmaleimide, N-methoxyphenylmaleimide, and N-tribromophenylmaleimide. Among these, N-arylmaleimide is preferred from the viewpoint of imparting heat resistance to the chlorine-containing polymer resin composition, and N-phenylmaleimide is more preferred. The maleimide monomer may be used alone or in combination of two or more types.
In order to make a copolymer contain a maleimide monomer unit, for example, a copolymer obtained by copolymerizing a raw material consisting of an unsaturated dicarboxylic acid monomer with other monomers is treated with ammonia or a primary amine. It can be imidized. Alternatively, a raw material consisting of a maleimide monomer may be copolymerized with other monomers.
　本実施形態にかかる共重合体は、共重合体に含有される単量体単位の合計を１００質量％とした場合にマレイミド系単量体単位を好ましくは１０～３０質量％含有し、より好ましくは１２～２５質量％含有し、さらに好ましくは１２～２０質量％含有する。具体的には例えば、１０、１２、１４、１６、１８、２０、２２、２４、２６、２８、又は３０質量％であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。マレイミド系単量体単位の量を１０質量％以上とすることで塩素含有ポリマー系樹脂組成物の耐熱性を十分に向上させることができ、３０質量％以下とすることで共重合体が塩素含有ポリマーと溶融せず混練できなくなる可能性を低減できる。
　なお、マレイミド系単量体単位を併用する場合には、マレイミド系単量体単位の含有量は、併用するマレイミド系単量体単位の合計量を意味する。 The copolymer according to the present embodiment preferably contains 10 to 30% by mass of maleimide monomer units, more preferably is contained in an amount of 12 to 25% by mass, more preferably 12 to 20% by mass. Specifically, for example, it is 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, or 30% by mass, and is within the range between any two of the numerical values exemplified here. Good too. By setting the amount of maleimide monomer units to 10% by mass or more, the heat resistance of the chlorine-containing polymer resin composition can be sufficiently improved, and by setting the amount to 30% by mass or less, the copolymer contains chlorine. It can reduce the possibility that it will not melt with the polymer and cannot be kneaded.
In addition, when a maleimide monomer unit is used in combination, the content of the maleimide monomer unit means the total amount of the maleimide monomer unit used in combination.
＜不飽和酸無水物単量体単位＞
　本実施形態にかかる共重合体は、さらに不飽和酸無水物単量体単位を含有してもよい。本実施形態にかかる共重合体に含有される不飽和酸無水物単量体単位が由来する不飽和酸無水物単量体としては、例えば、マレイン酸無水物、イタコン酸無水物、シトラコン酸無水物、アコニット酸無水物等がある。これらの中でも塩素含有ポリマー系樹脂組成物への耐熱性付与の観点からマレイン酸無水物が好ましい。不飽和酸無水物単量体は単独でも良いが２種類以上を併用しても良い。 <Unsaturated acid anhydride monomer unit>
The copolymer according to this embodiment may further contain an unsaturated acid anhydride monomer unit. Examples of the unsaturated acid anhydride monomer from which the unsaturated acid anhydride monomer unit contained in the copolymer according to the present embodiment is derived include maleic anhydride, itaconic anhydride, and citraconic anhydride. and aconitic acid anhydride. Among these, maleic anhydride is preferred from the viewpoint of imparting heat resistance to the chlorine-containing polymer resin composition. The unsaturated acid anhydride monomer may be used alone, or two or more types may be used in combination.
　本発明にかかる共重合体は、共重合体に含有される単量体単位の合計を１００質量％とした場合に不飽和酸無水物単量体単位を０～１０質量％含有することが好ましく、より好ましくは０～５質量％含有し、さらに好ましくは０～３質量％含有する。具体的には例えば、０、１、２、３、４、５、６、８、又は１０質量％であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。不飽和酸無水物単量体単位の量を１０質量％以下とすることで流動性の低下や、塩素含有ポリマーとの混練性の低下を低減することができる。
　なお、不飽和酸無水物単量体単位を併用する場合には、不飽和酸無水物単量体単位の含有量は、併用する不飽和酸無水物単量体単位の合計量を意味する。 The copolymer according to the present invention preferably contains 0 to 10% by mass of unsaturated acid anhydride monomer units when the total amount of monomer units contained in the copolymer is 100% by mass. , more preferably 0 to 5% by mass, still more preferably 0 to 3% by mass. Specifically, for example, it is 0, 1, 2, 3, 4, 5, 6, 8, or 10% by mass, and may be within a range between any two of the numerical values exemplified here. By controlling the amount of the unsaturated acid anhydride monomer unit to 10% by mass or less, it is possible to reduce the decrease in fluidity and the decrease in kneadability with the chlorine-containing polymer.
In addition, when an unsaturated acid anhydride monomer unit is used together, the content of the unsaturated acid anhydride monomer unit means the total amount of the unsaturated acid anhydride monomer unit used together.
＜共重合可能な単量体＞
　本実施形態にかかる共重合体は、芳香族ビニル系単量体、シアン化ビニル系単量体、マレイミド系単量体、及び不飽和酸無水物単量体以外の共重合可能な単量体を、本発明の効果を阻害しない範囲で共重合させても良い。本実施形態にかかる共重合体に共重合可能な単量体とは、メチルアクリル酸エステル、エチルアクリル酸エステル、ブチルアクリル酸エステル等のアクリル酸エステル単量体、メチルメタクリル酸エステル、エチルメタクリル酸エステル等のメタクリル酸エステル単量体、アクリル酸、メタクリル酸等のビニルカルボン酸単量体、アクリル酸アミド及びメタクリル酸アミド等があげられる。共重合体に共重合可能な単量体は、単独でも良いが２種類以上を併用しても良い。
　このような単量体は本発明の効果を阻害しない範囲で共重合可能であるが、塩素含有ポリマー系樹脂組成物への耐熱性付与の観点から２０質量％以下とすることが好ましく、１０質量％以下とすることがさらに好ましい。 <Copolymerizable monomer>
The copolymer according to this embodiment includes copolymerizable monomers other than aromatic vinyl monomers, vinyl cyanide monomers, maleimide monomers, and unsaturated acid anhydride monomers. may be copolymerized within a range that does not impede the effects of the present invention. The monomers that can be copolymerized into the copolymer according to this embodiment include acrylic ester monomers such as methyl acrylate, ethyl acrylate, and butyl acrylate, methyl methacrylate, and ethyl methacrylate. Examples include methacrylic acid ester monomers such as esters, vinyl carboxylic acid monomers such as acrylic acid and methacrylic acid, acrylamide and methacrylic acid amide. The monomers that can be copolymerized into the copolymer may be used alone, or two or more types may be used in combination.
Such monomers can be copolymerized within a range that does not impede the effects of the present invention, but from the viewpoint of imparting heat resistance to the chlorine-containing polymer resin composition, the amount is preferably 20% by mass or less, and 10% by mass or less. % or less is more preferable.
＜添加剤＞
　本実施形態にかかる塩素含有ポリマー用改質剤は、本発明の効果を阻害しない範囲において以下に説明されるような添加剤を含有し得る。
　塩素含有ポリマー用改質剤に含有される共重合体の原料となる粗生成物原料の重合終了後、重合液には必要に応じて、ヒンダードフェノール系化合物、ラクトン系化合物、リン系化合物、イオウ系化合物などの耐熱安定剤、ヒンダードアミン系化合物、ベンゾトリアゾール系化合物等の光安定剤、滑剤や可塑剤、着色剤、帯電防止剤、鉱油等の添加剤を加えても構わない。その添加量は全単量体単位１００質量部に対して０．２質量部未満であることが好ましい。これらの添加剤は単独で用いても、２種類以上を併用しても構わない。 <Additives>
The modifier for chlorine-containing polymers according to the present embodiment may contain additives as described below to the extent that the effects of the present invention are not impaired.
After completing the polymerization of the crude product raw material that is the raw material for the copolymer contained in the modifier for chlorine-containing polymers, the polymerization solution may contain a hindered phenol compound, a lactone compound, a phosphorus compound, Additives such as heat stabilizers such as sulfur compounds, light stabilizers such as hindered amine compounds and benzotriazole compounds, lubricants, plasticizers, colorants, antistatic agents, and mineral oil may be added. The amount added is preferably less than 0.2 parts by mass per 100 parts by mass of total monomer units. These additives may be used alone or in combination of two or more.
＜粗生成物原料の製造＞
　本実施形態にかかる塩素含有ポリマー用改質剤に含有される共重合体の原料となる粗生成物原料の重合様式は、例えば、溶液重合、塊状重合等がある。分添等を行いながら重合することで、共重合組成がより均一な粗生成物原料を得られるという観点から、溶液重合が好ましい。溶液重合の溶媒は、副生成物が出来難く、悪影響が少ないという観点から非重合性であることが好ましい。例えば、アセトン、メチルエチルケトン、メチルイソブチルケトン、アセトフェノン等のケトン類、テトラヒドロフラン、１，４－ジオキサン等のエーテル類、ベンゼン、トルエン、キシレン、エチルベンゼン、クロロベンゼン等の芳香族炭化水素、Ｎ，Ｎ－ジメチルホルムアミド、ジメチルスルホキシド、Ｎ－メチル－２－ピロリドン等であり、粗生成物原料の脱揮回収時における溶媒除去の容易性から、メチルエチルケトン、メチルイソブチルケトンが好ましい。重合プロセスは、連続重合式、バッチ式（回分式）、半回分式のいずれも適用できる。 <Manufacture of crude product raw materials>
The polymerization mode of the crude product raw material that is the raw material for the copolymer contained in the modifier for chlorine-containing polymers according to the present embodiment includes, for example, solution polymerization, bulk polymerization, and the like. Solution polymerization is preferable from the viewpoint that a crude product raw material with a more uniform copolymerization composition can be obtained by polymerizing while carrying out fractional addition or the like. It is preferable that the solvent for solution polymerization is non-polymerizable from the viewpoint that by-products are less likely to be produced and there are fewer adverse effects. For example, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and acetophenone, ethers such as tetrahydrofuran and 1,4-dioxane, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and chlorobenzene, and N,N-dimethylformamide. , dimethyl sulfoxide, N-methyl-2-pyrrolidone, etc., and methyl ethyl ketone and methyl isobutyl ketone are preferred from the viewpoint of ease of solvent removal during devolatilization and recovery of crude product raw materials. The polymerization process may be a continuous polymerization type, a batch type (batch type), or a semi-batch type.
　粗生成物原料の製造方法としては、特に限定されるものではないが、好ましくはラジカル重合により得ることができ、重合温度は８０～１５０℃の範囲であることが好ましい。重合開始剤としては特に限定されるものではないが、例えばアゾビスイソブチロニトリル、アゾビスシクロヘキサンカルボニトリル、アゾビスメチルプロピオニトリル、アゾビスメチルブチロニトリル等の公知のアゾ化合物や、ベンゾイルパーオキサイド、ｔ－ブチルパーオキシベンゾエート、１，１－ビス（ｔ－ブチルパーオキシ）－３，３，５－トリメチルシクロヘキサン、ｔ－ブチルパーオキシイソプロピルモノカーボネート、ｔ－ブチルパーオキシ－２－エチルヘキサノエート、ジ－ｔ－ブチルパーオキサイド、ジクミルパーオキサイド、エチル－３，３－ジ－（ｔ－ブチルパーオキシ）ブチレート等の公知の有機過酸化物を用いることができ、これらの１種あるいは２種類以上を組み合わせて使用しても良い。重合の反応速度や重合率制御の観点から、１０時間半減期が７０～１２０℃であるアゾ化合物や有機過酸化物を用いるのが好ましい。重合開始剤の使用量は、特に限定されるものではないが、全単量体単位１００質量％に対して０．１～１．５質量％使用することが好ましく、さらに好ましくは０．１～１．０質量％である。重合開始剤の使用量が０．１質量％以上であれば、十分な重合速度が得られるため好ましい。重合開始剤の使用量が１．５質量％以下であれば、重合速度が抑制できるため反応制御が容易になり、目標分子量を得ることが容易になる。 The method for producing the crude product raw material is not particularly limited, but it can preferably be obtained by radical polymerization, and the polymerization temperature is preferably in the range of 80 to 150°C. The polymerization initiator is not particularly limited, but includes known azo compounds such as azobisisobutyronitrile, azobiscyclohexanecarbonitrile, azobismethylpropionitrile, and azobismethylbutyronitrile, and benzoyl. Peroxide, t-butylperoxybenzoate, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethyl Known organic peroxides such as hexanoate, di-t-butyl peroxide, dicumyl peroxide, and ethyl-3,3-di-(t-butylperoxy)butyrate can be used; You may use a species or a combination of two or more species. From the viewpoint of polymerization reaction rate and polymerization rate control, it is preferable to use an azo compound or an organic peroxide having a 10-hour half-life of 70 to 120°C. The amount of the polymerization initiator used is not particularly limited, but it is preferably used in an amount of 0.1 to 1.5% by mass, more preferably 0.1 to 1.5% by mass based on 100% by mass of all monomer units. It is 1.0% by mass. It is preferable that the amount of the polymerization initiator used is 0.1% by mass or more because a sufficient polymerization rate can be obtained. When the amount of the polymerization initiator used is 1.5% by mass or less, the polymerization rate can be suppressed, so reaction control becomes easy and it becomes easy to obtain the target molecular weight.
　粗生成物原料の製造には、連鎖移動剤を使用することが出来る。使用される連鎖移動剤としては、特に限定されるものではないが、例えばｎ－オクチルメルカプタン、ｎ－ドデシルメルカプタン、ｔ－ドデシルメルカプタン、α－メチルスチレンダイマー、チオグリコール酸エチル、リモネン、ターピノーレン等がある。連鎖移動量の使用量は、目標分子量が得られる範囲であれば、特に限定されるものではないが、全単量体単位１００質量％に対して０．０１～０．８質量％であることが好ましく、さらに好ましくは０．１～０．５質量％である。連鎖移動剤の使用量が０．０１質量％～０．８質量％であれば、目標分子量を容易に得ることができる。 Chain transfer agents can be used in the production of crude product raw materials. The chain transfer agent used is not particularly limited, but includes, for example, n-octylmercaptan, n-dodecylmercaptan, t-dodecylmercaptan, α-methylstyrene dimer, ethyl thioglycolate, limonene, terpinolene, etc. be. The amount of chain transfer used is not particularly limited as long as the target molecular weight can be obtained, but it should be 0.01 to 0.8% by mass based on 100% by mass of all monomer units. is preferable, and more preferably 0.1 to 0.5% by mass. If the amount of chain transfer agent used is 0.01% by mass to 0.8% by mass, the target molecular weight can be easily obtained.
　粗生成物原料へのマレイミド系単量体単位の導入方法としては、マレイミド系単量体、芳香族ビニル系単量体、シアン化ビニル系単量体とを共重合する方法（直接法）、或いは不飽和ジカルボン酸無水物、芳香族ビニル系単量体、シアン化ビニル系単量体とを予め共重合しておき、更にアンモニア又は第１級アミンで不飽和ジカルボン酸無水物基を反応させる事により不飽和ジカルボン酸無水物基をマレイミド系単量体単位に変換する方法（後イミド化法）がある。後イミド化法の方が、共重合体中の残存マレイミド系単量体量が少なくなるので好ましい。 Methods for introducing the maleimide monomer unit into the crude product raw material include a method of copolymerizing a maleimide monomer, an aromatic vinyl monomer, and a vinyl cyanide monomer (direct method); Alternatively, an unsaturated dicarboxylic anhydride, an aromatic vinyl monomer, and a vinyl cyanide monomer are copolymerized in advance, and the unsaturated dicarboxylic anhydride group is further reacted with ammonia or a primary amine. There is a method (post-imidization method) of converting an unsaturated dicarboxylic acid anhydride group into a maleimide monomer unit. The post-imidization method is preferable because it reduces the amount of maleimide monomer remaining in the copolymer.
　後イミド化法で用いる第１級アミンとは、例えば、メチルアミン、エチルアミン、ｎ－プロピルアミン、ｉｓｏ－プロピルアミン、ｎ－ブチルアミン、ｎ－ペンチルアミン、ｎ－ヘキシルアミン、ｎ－オクチルアミン、シクロヘキシルアミン、デシルアミン等のアルキルアミン類及びクロル又はブロム置換アルキルアミン、アニリン、トルイジン、ナフチルアミン等の芳香族アミンがあり、この中でもアニリン、シクロヘキシルアミンが好ましい。これらの第１級アミンは、単独で使用しても２種類以上を組み合わせて使用しても良い。第１級アミンの添加量は特に限定されるものではないが、不飽和ジカルボン酸無水物基に対して好ましくは０．７～１．１モル当量、さらに好ましくは０．８５～１．０５モル当量である。粗生成物原料中の不飽和ジカルボン酸無水物単量体単位に対して０．７モル当量以上であれば、熱安定性が良好となるため好ましい。また、１．１モル当量以下であれば、共重合体中に残存する第１級アミン量が低減するため好ましい。 The primary amines used in the post-imidization method include, for example, methylamine, ethylamine, n-propylamine, iso-propylamine, n-butylamine, n-pentylamine, n-hexylamine, n-octylamine, and cyclohexyl. Examples include amines, alkylamines such as decylamine, chloro- or bromine-substituted alkylamines, aromatic amines such as aniline, toluidine, and naphthylamine, and among these, aniline and cyclohexylamine are preferred. These primary amines may be used alone or in combination of two or more. The amount of primary amine added is not particularly limited, but is preferably 0.7 to 1.1 molar equivalent, more preferably 0.85 to 1.05 mol, based on the unsaturated dicarboxylic anhydride group. It is equivalent. It is preferable that the amount is 0.7 molar equivalent or more based on the unsaturated dicarboxylic anhydride monomer unit in the crude product raw material because thermal stability will be good. Moreover, if it is 1.1 molar equivalent or less, it is preferable because the amount of primary amine remaining in the copolymer is reduced.
　マレイミド系単量体単位を後イミド化法で導入する際に触媒を用いてもよい。触媒は、アンモニア又は第１級アミンと不飽和ジカルボン酸無水物基との反応、特に不飽和ジカルボン酸無水物基からマレイミド基に変換する反応において、脱水閉環反応を向上させる事ができる。触媒の種類は特に限定されるものではないが、例えば第３級アミンを使用する事ができる。第３級アミンとしては特に限定されるものではないが、例えばトリメチルアミン、トリエチルアミン、トリプロピルアミン、トリブチルアミン、Ｎ、Ｎ－ジメチルアニリン、Ｎ、Ｎ－ジエチルアニリン等が挙げられる。第３級アミンの添加量は特に限定されるものではないが、不飽和ジカルボン酸無水物基に対し、０．０１モル当量以上が好ましい。本発明におけるイミド化反応の温度は好ましくは１００～２５０℃であり、さらに好ましくは１２０～２００℃である。イミド化反応の温度が１００℃以上であれば、反応速度が十分に早く生産性の面から好ましい。イミド化反応の温度が２５０℃以下であれば共重合体の熱劣化による物性低下を抑制できるため好ましい。 A catalyst may be used when introducing the maleimide monomer unit by the post-imidization method. A catalyst can improve the dehydration ring closure reaction in the reaction between ammonia or a primary amine and an unsaturated dicarboxylic anhydride group, particularly in the reaction of converting an unsaturated dicarboxylic anhydride group into a maleimide group. Although the type of catalyst is not particularly limited, for example, a tertiary amine can be used. Tertiary amines are not particularly limited, but include, for example, trimethylamine, triethylamine, tripropylamine, tributylamine, N,N-dimethylaniline, N,N-diethylaniline, and the like. Although the amount of the tertiary amine added is not particularly limited, it is preferably 0.01 molar equivalent or more based on the unsaturated dicarboxylic anhydride group. The temperature of the imidization reaction in the present invention is preferably 100 to 250°C, more preferably 120 to 200°C. If the temperature of the imidization reaction is 100° C. or higher, the reaction rate is sufficiently high and it is preferable from the viewpoint of productivity. It is preferable that the temperature of the imidization reaction is 250° C. or lower because it is possible to suppress deterioration of physical properties due to thermal deterioration of the copolymer.
　粗生成物原料の溶液重合終了後の溶液或いは後イミド化終了後の溶液から、溶液重合に用いた溶媒や未反応の単量体などの揮発分を取り除く方法（脱揮方法）は、公知の手法が採用できる。例えば、加熱器付きの真空脱揮槽やベント付き脱揮押出機を用いることができる。脱揮された溶融状態の粗生成物原料は、造粒工程に移送され、多孔ダイよりストランド状に押出し、コールドカット方式や空中ホットカット方式、水中ホットカット方式にてペレット状に加工することができる。 The method of removing volatile components such as the solvent used in solution polymerization and unreacted monomers from the solution after solution polymerization of the crude product raw material or the solution after post-imidization (devolatilization method) is known. method can be adopted. For example, a vacuum devolatilization tank equipped with a heater or a devolatilization extruder equipped with a vent can be used. The devolatilized crude product raw material in a molten state is transferred to the granulation process, extruded into strands from a multi-hole die, and can be processed into pellets using a cold cut method, an air hot cut method, or an underwater hot cut method. can.
＜共重合体の製造方法＞
　本実施形態にかかる共重合体は、例えば、上述の方法により得られる粗生成物原料から製造することができる。具体的には、例えば、以下の工程を実施する。 <Method for producing copolymer>
The copolymer according to this embodiment can be produced, for example, from the crude product raw material obtained by the method described above. Specifically, for example, the following steps are performed.
（１）粗生成物原料を、メチルエチルケトンに溶解させ、粗生成物原料のメチルエチルケトン溶液を得る。
（２）メチルエチルケトン溶液にヘキサンを滴下して、溶解させた粗生成物原料の一部を析出させた混合液を得る。
（３）混合液を濾過して、濾物と濾液に分離する。濾物は、２４時間風乾した後に、７０℃に設定した真空乾燥器で４時間乾燥させる乾燥工程を経て取得される。
（４）濾物を使用して、濾物の１０質量％のＴＨＦ溶液を調製する。
（５）濾物の１０質量％のＴＨＦ溶液と、Ｋ値が６６．７±１．０であり、塩素化度が５７±１．０％である塩素含有ポリマーの１０質量％のＴＨＦ溶液とを１：１の容量比で混合して作製した混合液における明度Ｌ＊を測定する。
（６）明度Ｌ＊が４０以上である場合、当該濾物を本実施形態にかかる共重合体とする。
（７）上記（６）において明度Ｌ＊が４０未満である場合、（３）で得た濾液にヘキサンを滴下して、粗生成物原料の一部を析出させた混合液を得る。
（８）上記（３）～（７）の操作を繰り返し、明度Ｌ＊が４０以上である濾物を本実施形態にかかる共重合体とする。
　なお、明度Ｌ＊が４０以上である濾物を得た後に、さらに上記（３）～（７）の操作を繰り返し、明度Ｌ＊が最も高い濾物を本実施形態にかかる共重合体としてもよく、明度Ｌ＊が４０以上となる全ての濾物を本実施形態にかかる共重合体としてもよい。 (1) A crude product raw material is dissolved in methyl ethyl ketone to obtain a methyl ethyl ketone solution of the crude product raw material.
(2) Hexane is added dropwise to the methyl ethyl ketone solution to obtain a mixed solution in which a portion of the dissolved crude product raw material is precipitated.
(3) Filter the mixed solution to separate the filtrate and the filtrate. The filtrate is obtained through a drying step of air drying for 24 hours and then drying it in a vacuum dryer set at 70° C. for 4 hours.
(4) Using the filtrate, prepare a 10% by mass THF solution of the filtrate.
(5) A 10% by mass THF solution of filter material and a 10% by mass THF solution of a chlorine-containing polymer having a K value of 66.7 ± 1.0 and a degree of chlorination of 57 ± 1.0%. The lightness L * of a mixed solution prepared by mixing the following at a volume ratio of 1:1 is measured.
(6) When the lightness L * is 40 or more, the filter material is considered to be the copolymer according to the present embodiment.
(7) When the lightness L * is less than 40 in the above (6), hexane is added dropwise to the filtrate obtained in (3) to obtain a liquid mixture in which a portion of the crude product raw material is precipitated.
(8) Repeat the operations (3) to (7) above, and use the filter cake having a lightness L * of 40 or more as the copolymer according to the present embodiment.
In addition, after obtaining the filtrate having a lightness L * of 40 or more, the above operations (3) to (7) are further repeated, and the filtrate having the highest lightness L * is also used as the copolymer according to the present embodiment. All filter material having a lightness L * of 40 or more may be used as the copolymer according to the present embodiment.
＜明度Ｌ＊の測定方法＞
　本実施形態における明度Ｌ＊は、塩素含有ポリマー用改質剤の１０質量％のＴＨＦ溶液と、塩素含有ポリマーの１０質量％のＴＨＦ溶液とを１：１の容量比で混合して作製した混合液を光路長１０ｍｍであり光路幅１０ｍｍの光学セルにいれ、日本分光株式会社　分光光度計　Ｖ－６７０のＬ＊ａ＊ｂ＊モードで測定の条件において測定される値である。 <Measurement method of lightness L * >
The lightness L * in this embodiment is a mixture prepared by mixing a 10% by mass THF solution of a chlorine-containing polymer modifier and a 10% by mass THF solution of a chlorine-containing polymer at a volume ratio of 1:1. This is a value measured under the conditions of measurement in the L * a * b * mode of a spectrophotometer V-670 manufactured by JASCO Corporation by placing a liquid in an optical cell with an optical path length of 10 mm and an optical path width of 10 mm.
＜塩素含有ポリマー＞
　本実施形態にかかる樹脂組成物に含まれる塩素含有ポリマーは、塩化ビニル単量体単独または塩化ビニル単量体とこれと共重合可能な１種類以上の単量体との混合物を重合して得られた重合体、及びこのようにして得られた重合体を更に塩素付加した塩素付加重合体である。また、塩素含有ポリマーには、このようにして得られた重合体と塩素付加重合体とのコンパウンドも含み得る。共重合可能な単量体としては、酢酸ビニルやプロピオン酸ビニル等のビニルエステル類、メチルアクリレートやブチルアクリレート等のアクリル酸エステル類、メチルメタクリレートやエチルメタクリレート等のメタクリル酸エステル類、ブチルマレートやジエチルマレート等のフマル酸エステル類、ビニルメチルエーテル、ビニルブチルエーテル及びビニルオクチルエーテル等のビニルエーテル類、アクリロニトリルやメタクリロニトリル等のシアン化ビニル類、エチレン、プロピレン等のα－オレフィン類、スチレン、α－メチルスチレン、ビニルトルエン、ｔ－ブチルスチレン、クロロスチレン等のスチレン類及びその置換体、塩化ビニリデンや臭化ビニル等の塩化ビニル以外のハロゲン化ビニリデンやハロゲン化ビニル類、ジアリルフタレート等のフタル酸エステル類が挙げられる。
　塩素含有ポリマーは、耐熱付与効果の観点から、塩化ビニル単量体を重合して得られるポリ塩化ビニルが好ましい。 <Chlorine-containing polymer>
The chlorine-containing polymer contained in the resin composition according to the present embodiment is obtained by polymerizing vinyl chloride monomer alone or a mixture of vinyl chloride monomer and one or more monomers copolymerizable with vinyl chloride monomer. and a chlorine-added polymer obtained by further adding chlorine to the polymer thus obtained. The chlorine-containing polymer may also include a compound of the polymer thus obtained and a chlorine addition polymer. Copolymerizable monomers include vinyl esters such as vinyl acetate and vinyl propionate, acrylic esters such as methyl acrylate and butyl acrylate, methacrylic esters such as methyl methacrylate and ethyl methacrylate, butyl maleate and diethyl ester. fumaric acid esters such as esters, vinyl ethers such as vinyl methyl ether, vinyl butyl ether and vinyl octyl ether, vinyl cyanides such as acrylonitrile and methacrylonitrile, α-olefins such as ethylene and propylene, styrene, α-methyl Styrenes and their substituted products such as styrene, vinyltoluene, t-butylstyrene, and chlorostyrene, vinylidene halides other than vinyl chloride such as vinylidene chloride and vinyl bromide, vinyl halides, and phthalate esters such as diallylphthalate. can be mentioned.
From the viewpoint of imparting heat resistance, the chlorine-containing polymer is preferably polyvinyl chloride obtained by polymerizing vinyl chloride monomers.
　上記塩素含有ポリマーの平均重合度は６８０～１９００であり、好ましくは７００～１７００である。平均重合度を６８０以上とすることで塩素含有ポリマー用改質剤を均一に分散させることでき、また、１９００以下とすることで塩素含有ポリマー用改質剤との混練性に優れる。 The average degree of polymerization of the above chlorine-containing polymer is from 680 to 1,900, preferably from 700 to 1,700. By setting the average degree of polymerization to 680 or more, the modifier for chlorine-containing polymers can be uniformly dispersed, and by setting it to 1900 or less, the kneadability with the modifier for chlorine-containing polymers is excellent.
＜塩素含有ポリマーの塩素含有率＞
　本実施形態にかかる樹脂組成物に含まれる塩素含有ポリマーの塩素含有率は、５０．０～７０．０質量％であることが好ましく、さらに好ましくは５５．０～７０．０質量％である。塩素含有ポリマーの塩素含有率がこの範囲内であると優れた加工性と耐衝撃性が得られる。 <Chlorine content of chlorine-containing polymer>
The chlorine content of the chlorine-containing polymer contained in the resin composition according to the present embodiment is preferably 50.0 to 70.0% by mass, more preferably 55.0 to 70.0% by mass. When the chlorine content of the chlorine-containing polymer is within this range, excellent processability and impact resistance can be obtained.
＜塩素含有率の高い塩素含有ポリマー＞
　本実施形態にかかる樹脂組成物に含まれる塩素含有ポリマーは、塩素含有率の高い塩素含有ポリマーであってもよい。例えば、塩素含有率が６０．０質量％を超える塩素含有ポリマーであってもよく、塩素含有率が６０．０質量％を超える塩素含有ポリマーを使用することにより、優れた加工性と耐衝撃性が得られる。 <Chlorine-containing polymer with high chlorine content>
The chlorine-containing polymer contained in the resin composition according to this embodiment may be a chlorine-containing polymer with a high chlorine content. For example, a chlorine-containing polymer with a chlorine content of more than 60.0% by mass may be used, and by using a chlorine-containing polymer with a chlorine content of more than 60.0% by mass, excellent processability and impact resistance can be achieved. is obtained.
＜塩素含有ポリマーの製造＞
　塩素含有ポリマーの重合方法は特に限定されず、従来公知の塊状重合、溶液重合、乳化重合等が用いられる。 <Production of chlorine-containing polymer>
The method of polymerizing the chlorine-containing polymer is not particularly limited, and conventionally known bulk polymerization, solution polymerization, emulsion polymerization, etc. can be used.
１－２．樹脂組成物
＜塩素含有ポリマー用改質剤と塩素含有ポリマーとを含有する樹脂組成物＞
　本実施形態における塩素含有ポリマー用改質剤と塩素含有ポリマーの配合割合は、特に限定されないが、例えば、塩素含有ポリマー１００質量部に対し、塩素含有ポリマー用改質剤０．５～５０質量部であることが好ましく、さらに好ましくは、２～２５質量部である。塩素含有ポリマー用改質剤の配合割合を０．５質量部以上とすることで十分な耐熱付与効果が得られ、また、５０質量部以下とすることで混練時の離型性悪化が抑えられる。 1-2. Resin composition <Resin composition containing a chlorine-containing polymer modifier and a chlorine-containing polymer>
The blending ratio of the chlorine-containing polymer modifier and the chlorine-containing polymer in this embodiment is not particularly limited, but for example, 0.5 to 50 parts by mass of the chlorine-containing polymer modifier to 100 parts by mass of the chlorine-containing polymer. The amount is preferably 2 to 25 parts by mass, and more preferably 2 to 25 parts by mass. By setting the blending ratio of the modifier for chlorine-containing polymer to 0.5 parts by mass or more, a sufficient heat resistance imparting effect can be obtained, and by setting it to 50 parts by mass or less, deterioration of mold release properties during kneading can be suppressed. .
＜樹脂組成物の充填剤＞
　本実施形態にかかる樹脂組成物は、必要に応じて充填剤をさらに配合してもよい。充填剤を配合することによって、樹脂組成物から得られる成形品の曲げ弾性率を向上させる効果が期待できる。本実施形態において用いることができる充填剤としては、例えば、シリカ、珪藻土、アルミナ、酸化亜鉛、酸化チタン、酸化カルシウム、酸化マグネシウム、酸化鉄、酸化錫、酸化アンチモン、フェライト類、水酸化カルシウム、水酸化マグネシウム、水酸化アルミニウム、塩基性炭 酸マグネシウム、炭酸カルシウム、炭酸マグネシウム、炭酸亜鉛、炭酸バリウム、ドーンナイト、ハイドロタルサイト、硫酸カルシウム、硫酸バリウム、石膏繊維、ケイ酸カルシウム、タルク、クレー、マイカ、モンモリロナイト、ベントナイト、活性白土、セピオライト、イモゴライト、セリサイト、ガラス繊維、ガラスビーズ、シリカ系バルン、窒化アルミニウム、窒化ホウ素、窒化ケイ素、カーボンブラック、グラファイト、炭素繊維、炭 素バルン、木炭粉末、各種金属粉、チタン酸カリウム、硫酸マグネシウム、チタン酸ジルコン酸鉛、アルミニウムボレート、硫化モリブデン、炭化ケイ素、ステンレス繊維、ホウ酸亜鉛、各種磁性粉、スラグ繊維、フライアッシュ、脱水汚泥等またこれらを表面処理したものが挙げられる。これらの中でも機械物性・ビカット軟化温度向上性を向上させる効果の高い炭酸カルシウム、ケイ酸カルシウム、水酸化カルシウム、酸化カルシウム、炭 酸マグネシウム、水酸化マグネシウム、酸化マグネシウム、炭酸バリウム、水酸化アルミニウム、酸化亜鉛、水酸化亜鉛、酸化鉄等の塩基性無機充填剤、タルクが好ましい。これらの充填剤は、１種を単独で用いてもよく、２種類以上を併用してもよい。 <Filler for resin composition>
The resin composition according to this embodiment may further contain a filler, if necessary. By blending the filler, the effect of improving the flexural modulus of the molded article obtained from the resin composition can be expected. Examples of fillers that can be used in this embodiment include silica, diatomaceous earth, alumina, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, ferrites, calcium hydroxide, water Magnesium oxide, aluminum hydroxide, basic magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dawnite, hydrotalcite, calcium sulfate, barium sulfate, gypsum fiber, calcium silicate, talc, clay, mica , montmorillonite, bentonite, activated clay, sepiolite, imogolite, sericite, glass fiber, glass beads, silica balloons, aluminum nitride, boron nitride, silicon nitride, carbon black, graphite, carbon fiber, carbon balloons, charcoal powder, various Metal powder, potassium titanate, magnesium sulfate, lead zirconate titanate, aluminum borate, molybdenum sulfide, silicon carbide, stainless fiber, zinc borate, various magnetic powders, slag fiber, fly ash, dehydrated sludge, etc. Also, surface treatment of these The following can be mentioned. Among these, calcium carbonate, calcium silicate, calcium hydroxide, calcium oxide, magnesium carbonate, magnesium hydroxide, magnesium oxide, barium carbonate, aluminum hydroxide, and calcium oxide are highly effective in improving mechanical properties and Vicat softening temperature. Basic inorganic fillers such as zinc, zinc hydroxide, iron oxide, and talc are preferred. These fillers may be used alone or in combination of two or more.
　本実施形態にかかる充填剤の配合量は、塩素含有ポリマー１００質量部に対して充填剤１～１００質量部であり、好ましくは１～７５質量部であり、さらに好ましくは１～５０質量部である。具体的には例えば、塩素含有ポリマー１００質量部に対して充填剤の配合量が１、３、５、１０、２０、４０、６０、８０、又は１００質量部であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。なお、充填剤を併用する場合には、充填剤の配合量は、併用する充填剤の合計量を意味する。塩素含有ポリマー１００質量部に対する充填剤の配合量を１質量部以上とすることで曲げ弾性率を向上させる効果が得られ、また、５０質量部以下とすることで分散性低下が抑えられる。 The blending amount of the filler according to this embodiment is 1 to 100 parts by mass, preferably 1 to 75 parts by mass, and more preferably 1 to 50 parts by mass, per 100 parts by mass of the chlorine-containing polymer. be. Specifically, for example, the blending amount of the filler is 1, 3, 5, 10, 20, 40, 60, 80, or 100 parts by mass with respect to 100 parts by mass of the chlorine-containing polymer, and the numerical values exemplified here. It may be within the range between any two. In addition, when a filler is used in combination, the amount of the filler used means the total amount of the filler used in combination. By setting the amount of the filler to be 1 part by mass or more to 100 parts by mass of the chlorine-containing polymer, the effect of improving the flexural modulus can be obtained, and by setting it to 50 parts by mass or less, a decrease in dispersibility can be suppressed.
＜樹脂組成物の衝撃改質剤＞
　本実施形態にかかる樹脂組成物は、必要に応じて衝撃改質剤をさらに配合してもよい。衝撃改質剤を配合することによって、樹脂組成物から得られる成形品の耐衝撃性を向上させる効果が期待できる。本実施形態において用いることができる衝撃改質剤としては、例えば、ＡＢＳ（アクリロニトリル－ブタジエン－スチレン）樹脂、ＭＢＳ（メチルメタクリレート－ブタジエン－スチレン）樹脂、アクリルゴム、塩素化ポリエチレン、ＮＢＲ（アクリロニトリルブタジエンゴム）が挙げられる。これらの中でも耐衝撃性を向上させる効果の高いＭＢＳ樹脂、アクリルゴム、塩素化ポリエチレンが好ましい。これらの衝撃改質剤は、１種を単独で用いてもよく、２種類以上を併用してもよい。
　本実施形態にかかる衝撃改質剤の配合量は、塩素含有ポリマー１００質量部に対して衝撃改質剤１～５０質量部であり、好ましくは１～４０質量部であり、さらに好ましくは１～３０質量部である。なお、衝撃改質剤を併用する場合には、衝撃改質剤の配合量は、併用する衝撃改質剤の合計量を意味する。塩素含有ポリマー１００質量部に対する衝撃改質剤の配合量を１質量部以上とすることで耐衝撃性を向上させる効果が得られ、また、５０質量部以下とすることで曲げ弾性率の低下が抑えられる。 <Impact modifier for resin composition>
The resin composition according to this embodiment may further contain an impact modifier, if necessary. By blending an impact modifier, the effect of improving the impact resistance of molded products obtained from the resin composition can be expected. Examples of impact modifiers that can be used in this embodiment include ABS (acrylonitrile-butadiene-styrene) resin, MBS (methyl methacrylate-butadiene-styrene) resin, acrylic rubber, chlorinated polyethylene, and NBR (acrylonitrile-butadiene rubber). ). Among these, MBS resin, acrylic rubber, and chlorinated polyethylene are preferable because they are highly effective in improving impact resistance. These impact modifiers may be used alone or in combination of two or more.
The amount of the impact modifier according to the present embodiment is 1 to 50 parts by weight, preferably 1 to 40 parts by weight, and more preferably 1 to 40 parts by weight, per 100 parts by weight of the chlorine-containing polymer. It is 30 parts by mass. In addition, when using an impact modifier together, the amount of the impact modifier used means the total amount of the impact modifier used together. By adding 1 part by mass or more of the impact modifier to 100 parts by mass of the chlorine-containing polymer, the effect of improving impact resistance can be obtained, and by setting it to 50 parts by mass or less, the flexural modulus can be reduced. It can be suppressed.
＜樹脂組成物の加工助剤＞
　本実施形態にかかる樹脂組成物は、必要に応じて加工助剤をさらに配合してもよい。加工助剤を配合することによって、加工時のゲル化の促進や樹脂組成物から得られる成形品の成形性を向上させる効果が期待できる。本実施形態において用いることができる加工助剤としては、例えば、アクリル系共重合体が挙げられる。これらの加工助剤は、１種を単独で用いてもよく、２種類以上を併用してもよい。
　本実施形態にかかる加工助剤の配合量は、塩素含有ポリマー１００質量部に対して加工助剤０．０１～１０質量部であり、好ましくは０．０５～５質量部である。具体的には例えば、塩素含有ポリマー１００質量部に対して加工助剤の配合量が０．０１、０．０２、０．０５、０．１、０．２、０．５、１、２、５又は１０質量部であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。なお、加工助剤を併用する場合には、加工助剤の配合量は、併用する加工助剤の合計量を意味する。塩素含有ポリマー１００質量部に対する加工助剤の配合量を０．０１質量部以上とすることで加工性を向上させる効果が得られ、また、１０質量部以下とすることで機械物性低下が抑えられる。 <Processing aid for resin composition>
The resin composition according to this embodiment may further contain a processing aid, if necessary. By incorporating a processing aid, it can be expected that the effect of promoting gelation during processing and improving the moldability of molded articles obtained from the resin composition can be expected. Examples of processing aids that can be used in this embodiment include acrylic copolymers. These processing aids may be used alone or in combination of two or more.
The amount of the processing aid according to this embodiment is 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, per 100 parts by mass of the chlorine-containing polymer. Specifically, for example, the amount of processing aid added to 100 parts by mass of the chlorine-containing polymer is 0.01, 0.02, 0.05, 0.1, 0.2, 0.5, 1, 2, 5 or 10 parts by mass, and may be within a range between any two of the numerical values exemplified here. In addition, when a processing aid is used together, the blending amount of the processing aid means the total amount of the processing aid used together. By setting the amount of the processing aid to 100 parts by mass of the chlorine-containing polymer to be 0.01 parts by mass or more, the effect of improving processability can be obtained, and by setting it to 10 parts by mass or less, deterioration of mechanical properties can be suppressed. .
＜樹脂組成物の添加剤＞
　本発明における樹脂組成物は、本発明の効果を阻害しない範囲において以下に説明されるような添加剤を含有し得るが、塩素含有ポリマー用改質剤と塩素含有ポリマーからなるものでも良い。
　本発明の樹脂組成物に、必要に応じ、更に強化剤、加工性改良剤、熱安定剤、滑剤、可塑剤等を単独または２種類以上組み合わせて添加することもできる。
　その他の添加剤としては、光安定剤、紫外線吸収剤、酸化防止剤、顔料、染料等を任意に添加することができる。 <Additives for resin composition>
The resin composition of the present invention may contain additives as described below within a range that does not impede the effects of the present invention, but may also consist of a chlorine-containing polymer modifier and a chlorine-containing polymer.
If necessary, a reinforcing agent, a processability improver, a heat stabilizer, a lubricant, a plasticizer, etc. may be added to the resin composition of the present invention alone or in combination of two or more.
As other additives, light stabilizers, ultraviolet absorbers, antioxidants, pigments, dyes, etc. can be optionally added.
＜樹脂組成物の製造＞
　塩素含有ポリマー用改質剤と塩素含有ポリマーとを混練混合して本発明にかかる樹脂組成物を得る方法については、特に限定はなく、公知の溶融混練技術を用いることが出来る。好適に使用できる溶融混練装置としては、単軸押出機、噛合形同方向回転または噛合形異方向回転二軸押出機、非または不完全噛合形二軸押出機等のスクリュー押出機、バンバリーミキサー、コニーダー及び混合ロール等がある。また、これらの押出機を複数組み合わせて使用することもできる。 <Manufacture of resin composition>
There is no particular limitation on the method of kneading and mixing the chlorine-containing polymer modifier and the chlorine-containing polymer to obtain the resin composition of the present invention, and any known melt-kneading technique can be used. Suitable melt-kneading devices include a single screw extruder, an intermeshing type co-rotating or intermeshing type counter-rotating twin screw extruder, a screw extruder such as a non-intermeshing type twin screw extruder, a Banbury mixer, There are co-kneaders, mixing rolls, etc. Moreover, a combination of two or more of these extruders can also be used.
　本実施形態にかかる樹脂組成物を、公知の方法により成形して成形体を得ることができる。成形方法としては、例えば、射出成形、シート押出成形、真空成形、ブロー成形、発泡成形、異型押出成形等が挙げられる。成形時には、通常、塩素含有ポリマー系樹脂組成物を１７０～２００℃に加熱した後、加工されるが、１９０～２００℃であることが好ましい。 A molded article can be obtained by molding the resin composition according to this embodiment by a known method. Examples of the molding method include injection molding, sheet extrusion molding, vacuum molding, blow molding, foam molding, and profile extrusion molding. During molding, the chlorine-containing polymer resin composition is usually heated to 170 to 200°C and then processed, preferably at 190 to 200°C.
（第２観点の実施形態）
２－１．樹脂組成物
　本発明の第２観点の一実施形態に係る樹脂組成物は、塩素含有ポリマーと、マレイミド系共重合体と、を含む塩素含有ポリマー系樹脂組成物である。樹脂組成物は、好ましくは、塩素含有ポリマーと、マレイミド系共重合体と、耐衝撃改質剤とを含む。 (Embodiment of second viewpoint)
2-1. Resin Composition A resin composition according to an embodiment of the second aspect of the present invention is a chlorine-containing polymer-based resin composition containing a chlorine-containing polymer and a maleimide-based copolymer. The resin composition preferably includes a chlorine-containing polymer, a maleimide copolymer, and an impact modifier.
＜塩素含有ポリマー＞
　塩素含有ポリマーは、塩化ビニル単量体単独または塩化ビニル単量体とこれと共重合可能な１種類以上の単量体との混合物を重合して得られた重合体、及びこのようにして得られた重合体を更に塩素付加した塩素付加重合体である。また、塩素含有ポリマーには、このようにして得られた重合体と塩素付加重合体との混合物も含み得る。共重合可能な単量体としては、酢酸ビニルやプロピオン酸ビニル等のビニルエステル類、メチルアクリレートやブチルアクリレート等のアクリル酸エステル類、メチルメタクリレートやエチルメタクリレート等のメタクリル酸エステル類、ブチルマレートやジエチルマレート等のフマル酸エステル類、ビニルメチルエーテル、ビニルブチルエーテル及びビニルオクチルエーテル等のビニルエーテル類、アクリロニトリルやメタクリロニトリル等のシアン化ビニル類、エチレン、プロピレン等のα－オレフィン類、スチレン、α－メチルスチレン、ビニルトルエン、ｔ－ブチルスチレン、クロロスチレン等のスチレン類及びその置換体、塩化ビニリデンや臭化ビニル等の塩化ビニル以外のハロゲン化ビニリデンやハロゲン化ビニル類、ジアリルフタレート等のフタル酸エステル類が挙げられる。
　塩素含有ポリマーは、耐熱付与効果の観点から、塩化ビニル単量体を重合して得られるポリ塩化ビニルをさらに塩素付加した塩素化塩化ビニルが好ましい。 <Chlorine-containing polymer>
Chlorine-containing polymers include polymers obtained by polymerizing vinyl chloride monomer alone or a mixture of vinyl chloride monomer and one or more monomers copolymerizable therewith, and polymers obtained in this way. This is a chlorine-added polymer obtained by adding chlorine to the obtained polymer. The chlorine-containing polymer may also include a mixture of the polymer thus obtained and a chlorine addition polymer. Copolymerizable monomers include vinyl esters such as vinyl acetate and vinyl propionate, acrylic esters such as methyl acrylate and butyl acrylate, methacrylic esters such as methyl methacrylate and ethyl methacrylate, butyl maleate and diethyl ester. fumaric acid esters such as esters, vinyl ethers such as vinyl methyl ether, vinyl butyl ether and vinyl octyl ether, vinyl cyanides such as acrylonitrile and methacrylonitrile, α-olefins such as ethylene and propylene, styrene, α-methyl Styrenes and their substituted products such as styrene, vinyltoluene, t-butylstyrene, and chlorostyrene, vinylidene halides other than vinyl chloride such as vinylidene chloride and vinyl bromide, vinyl halides, and phthalate esters such as diallylphthalate. can be mentioned.
From the viewpoint of the effect of imparting heat resistance, the chlorine-containing polymer is preferably chlorinated vinyl chloride obtained by further adding chlorine to polyvinyl chloride obtained by polymerizing vinyl chloride monomers.
　塩素含有ポリマーの平均重合度は５００～１９００であり、好ましくは５５０～１１００である。平均重合度を５００以上とすることでマレイミド系共重合体を均一に分散させることでき、また、１９００以下とすることでマレイミド系共重合体との混練性に優れる。 The average degree of polymerization of the chlorine-containing polymer is 500 to 1,900, preferably 550 to 1,100. By setting the average degree of polymerization to 500 or more, the maleimide copolymer can be uniformly dispersed, and by setting the average degree to 1900 or less, the kneadability with the maleimide copolymer is excellent.
　塩素含有ポリマーの塩素含有量は、塩素含有ポリマー１００質量％中、６０～７０質量％であり、好ましくは６０質量％超７０質量％以下であり、より好ましくは６３～６８質量％である。塩素含有ポリマーの塩素含有量は、塩素含有ポリマー１００質量％中、具体的には例えば、６０，６１，６２，６３，６４，６５，６６，６７，６８，６９，７０であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。塩素含有ポリマーの塩素含有量を６０質量％以上とすることで、優れた耐熱性及び耐衝撃性が得られる。塩素含有ポリマーの塩素含有量を７０質量％以下とすることで、有毒ガス発生ひいては金属腐食が抑えられる。なお、塩素含有ポリマーの塩素含有量は、例えば、酸素フラスコ燃焼法（ＪＩＳ　Ｋ７２２９：１９９５に準拠）による中和滴定により決定することができる。 The chlorine content of the chlorine-containing polymer is 60 to 70% by mass based on 100% by mass of the chlorine-containing polymer, preferably more than 60% by mass and 70% by mass or less, and more preferably 63 to 68% by mass. Specifically, the chlorine content of the chlorine-containing polymer is, for example, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70 based on 100% by mass of the chlorine-containing polymer. It may be within the range between any two of the above values. By setting the chlorine content of the chlorine-containing polymer to 60% by mass or more, excellent heat resistance and impact resistance can be obtained. By controlling the chlorine content of the chlorine-containing polymer to 70% by mass or less, toxic gas generation and metal corrosion can be suppressed. The chlorine content of the chlorine-containing polymer can be determined, for example, by neutralization titration using the oxygen flask combustion method (based on JIS K7229:1995).
　樹脂組成物は、樹脂組成物１００質量％中、好ましくは塩素含有ポリマーを４質量％以上含む。樹脂組成物１００質量％中の塩素含有ポリマーの含有量は、好ましくは４～９５質量％であり、より好ましくは６０～９０質量％であり、さらに好ましくは７１～９０質量％である。樹脂組成物１００質量％中の塩素含有ポリマーの含有量は、具体的には例えば、４，５，１０，１５，２０，２５，３０，３５，４０，４５，５０，５５，６０，６５，７０，７１，７２，７３，７４，７５，７６，７７，７８，７９，８０，８１，８２，８３，８４，８５，９０，９５であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。一例においては、樹脂組成物は、塩素含有量が６０質量％超７０質量％以下である塩素含有ポリマーを、樹脂組成物１００質量％中７１～９０質量％含む。 The resin composition preferably contains 4% by mass or more of the chlorine-containing polymer based on 100% by mass of the resin composition. The content of the chlorine-containing polymer in 100% by mass of the resin composition is preferably 4 to 95% by mass, more preferably 60 to 90% by mass, and even more preferably 71 to 90% by mass. Specifically, the content of the chlorine-containing polymer in 100% by mass of the resin composition is, for example, 4, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 90, 95, and between any two of the numerical values exemplified here. It may be within the range. In one example, the resin composition contains 71 to 90% by weight of a chlorine-containing polymer having a chlorine content of more than 60% by weight and 70% by weight or less based on 100% by weight of the resin composition.
（塩素含有ポリマーの製造）
　塩素含有ポリマーの重合方法は特に限定されず、従来公知の塊状重合、溶液重合、乳化重合等が用いられる。 (Production of chlorine-containing polymer)
The method of polymerizing the chlorine-containing polymer is not particularly limited, and conventionally known bulk polymerization, solution polymerization, emulsion polymerization, etc. can be used.
＜マレイミド系共重合体＞
　マレイミド系共重合体は、シアン化ビニル系単量体単位と、マレイミド系単量体単位と、を有する。また、マレイミド系共重合体は、シアン化ビニル系単量体単位と、マレイミド系単量体単位と、芳香族ビニル系単量体単位と、を有していてもよい。また、マレイミド系共重合体は、シアン化ビニル系単量体単位と、マレイミド系単量体単位と、芳香族ビニル系単量体単位と、不飽和酸無水物単量体単位と、を有していてもよい。 <Maleimide copolymer>
The maleimide copolymer has a vinyl cyanide monomer unit and a maleimide monomer unit. Further, the maleimide copolymer may have a vinyl cyanide monomer unit, a maleimide monomer unit, and an aromatic vinyl monomer unit. Furthermore, the maleimide copolymer has a vinyl cyanide monomer unit, a maleimide monomer unit, an aromatic vinyl monomer unit, and an unsaturated acid anhydride monomer unit. You may do so.
（シアン化ビニル系単量体単位）
　マレイミド系共重合体に含有されるシアン化ビニル系単量体単位が由来するシアン化ビニル系単量体としては、例えば、アクリロニトリル、メタクリロニトリル、エタクリロニトリル、フマロニトリル等が挙げられる。これらの中でも色相及び樹脂組成物への耐熱性付与の観点からアクリロニトリルが好ましい。シアン化ビニル系単量体は単独でも良いが２種類以上を併用してもよい。 (vinyl cyanide monomer unit)
Examples of the vinyl cyanide monomer from which the vinyl cyanide monomer unit contained in the maleimide copolymer is derived include acrylonitrile, methacrylonitrile, ethacrylonitrile, fumaronitrile, and the like. Among these, acrylonitrile is preferred from the viewpoint of hue and imparting heat resistance to the resin composition. The vinyl cyanide monomer may be used alone, or two or more types may be used in combination.
　マレイミド系共重合体は、当該マレイミド系共重合体に含有される単量体単位の合計を１００質量％とした場合にシアン化ビニル系単量体単位を好ましくは０．５～２０質量％含有し、より好ましくは０．５～１５質量％含有し、さらに好ましくは３～１５質量％含有する。シアン化ビニル系単量体単位の含有量は、具体的には例えば、０．５，１，２，３，４，５，６，７，８，９，１０，１１，１２，１３，１４，１５，１６，１７，１８，１９，２０質量％であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。シアン化ビニル系単量体単位の量を０．５質量％とすることで、樹脂組成物の耐熱性を十分に向上させることができ、２０質量％以下とすることで樹脂組成物の耐衝撃性と耐熱性のバランスを向上させることができる。
　なお、シアン化ビニル系単量体単位を併用する場合には、シアン化ビニル系単量体単位の含有量は、併用するシアン化ビニル系単量体単位の合計量を意味する。 The maleimide copolymer preferably contains vinyl cyanide monomer units in an amount of 0.5 to 20% by mass when the total amount of monomer units contained in the maleimide copolymer is 100% by mass. However, the content is more preferably 0.5 to 15% by mass, and even more preferably 3 to 15% by mass. Specifically, the content of vinyl cyanide monomer units is, for example, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 , 15, 16, 17, 18, 19, 20% by mass, and may be within a range between any two of the numerical values exemplified here. By setting the amount of vinyl cyanide monomer units to 0.5% by mass, the heat resistance of the resin composition can be sufficiently improved, and by setting the amount to 20% by mass or less, the impact resistance of the resin composition can be improved. The balance between heat resistance and heat resistance can be improved.
In addition, when vinyl cyanide monomer units are used together, the content of vinyl cyanide monomer units means the total amount of vinyl cyanide monomer units used together.
（マレイミド系単量体単位）
　マレイミド系共重合体に含有されるマレイミド系単量体単位が由来するマレイミド系単量体としては、例えば、Ｎ－メチルマレイミド、Ｎ－ブチルマレイミド、Ｎ－シクロヘキシルマレイミド等のＮ－アルキルマレイミド、及びＮ－フェニルマレイミド、Ｎ－クロルフェニルマレイミド、Ｎ－メチルフェニルマレイミド、Ｎ－メトキシフェニルマレイミド、Ｎ－トリブロモフェニルマレイミド等のＮ－アリールマレイミド等がある。これらの中でも、樹脂組成物への耐熱性付与の観点からＮ－アリールマレイミドが好ましく、Ｎ－フェニルマレイミドがさらに好ましい。マレイミド系単量体は、単独でも良いが２種類以上を併用してもよい。
　マレイミド系共重合体にマレイミド系単量体単位を含有させるには、例えば、不飽和ジカルボン酸単量体からなる原料を他の単量体と共重合させた共重合体をアンモニア又は第１級アミンでイミド化させればよい。あるいは、マレイミド系単量体からなる原料を他の単量体と共重合させてもよい。 (maleimide monomer unit)
Examples of maleimide monomers from which the maleimide monomer units contained in the maleimide copolymer are derived include N-alkylmaleimides such as N-methylmaleimide, N-butylmaleimide, and N-cyclohexylmaleimide; Examples include N-arylmaleimides such as N-phenylmaleimide, N-chlorophenylmaleimide, N-methylphenylmaleimide, N-methoxyphenylmaleimide, and N-tribromophenylmaleimide. Among these, N-arylmaleimide is preferred from the viewpoint of imparting heat resistance to the resin composition, and N-phenylmaleimide is more preferred. The maleimide monomer may be used alone or in combination of two or more types.
In order to contain a maleimide monomer unit in a maleimide copolymer, for example, a copolymer obtained by copolymerizing a raw material consisting of an unsaturated dicarboxylic acid monomer with other monomers is mixed with ammonia or primary It can be imidized with an amine. Alternatively, a raw material consisting of a maleimide monomer may be copolymerized with other monomers.
　マレイミド系共重合体は、当該マレイミド系共重合体に含有される単量体単位の合計を１００質量％とした場合にマレイミド系単量体単位を好ましくは１０～３０質量％含有し、より好ましくは１０～２５質量％含有し、さらに好ましくは１２～２０質量％含有する。マレイミド系単量体単位の含有量は、具体的には例えば、１０，１１，１２，１３，１４，１５，１６，１７，１８，１９，２０，２１，２２，２３，２４，２５，２６，２７，２８，２９，３０質量％であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。マレイミド系単量体単位の量を１０質量％以上とすることで樹脂組成物の耐熱性を十分に向上させることができ、３０質量％以下とすることでマレイミド系共重合体が塩素含有ポリマーと溶融せず混練できなくなる可能性を低減できる。
　なお、マレイミド系単量体単位を併用する場合には、マレイミド系単量体単位の含有量は、併用するマレイミド系単量体単位の合計量を意味する。 The maleimide copolymer preferably contains 10 to 30 mass% of maleimide monomer units, more preferably 10 to 30 mass% of the total monomer units contained in the maleimide copolymer. is contained in an amount of 10 to 25% by mass, more preferably 12 to 20% by mass. Specifically, the content of maleimide monomer units is, for example, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26 , 27, 28, 29, 30% by mass, and may be within the range between any two of the numerical values exemplified here. By setting the amount of the maleimide monomer unit to 10% by mass or more, the heat resistance of the resin composition can be sufficiently improved, and by setting the amount to 30% by mass or less, the maleimide copolymer becomes chlorine-containing polymer. The possibility of not being able to melt and knead can be reduced.
In addition, when a maleimide monomer unit is used in combination, the content of the maleimide monomer unit means the total amount of the maleimide monomer unit used in combination.
（芳香族ビニル系単量体単位）
　マレイミド系共重合体に含有される芳香族ビニル系単量体単位が由来する芳香族ビニル系単量体としては、例えば、スチレン、ｏ－メチルスチレン、ｍ－メチルスチレン、ｐ－メチルスチレン、２，４－ジメチルスチレン、エチルスチレン、ｐ－ｔｅｒｔ－ブチルスチレン、α－メチルスチレン、α－メチル－ｐ－メチルスチレン等が挙げられる。これらの中でも耐熱性、塩素含有ポリマーとの親和性、流動性のバランスの観点からスチレンが好ましい。芳香族ビニル系単量体は、単独でも良いが２種類以上を併用してもよい。 (Aromatic vinyl monomer unit)
Examples of the aromatic vinyl monomer from which the aromatic vinyl monomer unit contained in the maleimide copolymer is derived include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2 , 4-dimethylstyrene, ethylstyrene, p-tert-butylstyrene, α-methylstyrene, α-methyl-p-methylstyrene, and the like. Among these, styrene is preferred from the viewpoint of heat resistance, affinity with chlorine-containing polymers, and fluidity balance. The aromatic vinyl monomer may be used alone, or two or more types may be used in combination.
　マレイミド系共重合体は、当該マレイミド系共重合体に含有される単量体単位の合計を１００質量％とした場合に芳香族ビニル系単量体単位を好ましくは６０～８５質量％含有し、より好ましくは６５～８０質量％含有し、さらに好ましくは６８～８０質量％含有する。芳香族ビニル系単量体単位の含有量は、具体的には例えば、６０，６１，６２，６３，６４，６５，６６，６７，６８，６９，７０，７１，７２，７３，７４，７５，７６，７７，７８，７９，８０，８１，８２，８３，８４，８５質量％であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。芳香族ビニル系単量体単位の量を６０質量％以上とすることで優れた流動性と塩素含有ポリマーとの親和性のバランスで得られ、また、８５質量％以下とすることで十分な耐熱性が得られる。
　なお、芳香族ビニル系単量体単位を併用する場合には、芳香族ビニル系単量体単位の含有量は、併用する芳香族ビニル系単量体単位の合計量を意味する。 The maleimide copolymer preferably contains 60 to 85% by mass of aromatic vinyl monomer units when the total monomer units contained in the maleimide copolymer is 100% by mass, The content is more preferably 65 to 80% by mass, and even more preferably 68 to 80% by mass. Specifically, the content of aromatic vinyl monomer units is, for example, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75 , 76, 77, 78, 79, 80, 81, 82, 83, 84, 85% by mass, and may be within a range between any two of the numerical values exemplified here. By setting the amount of aromatic vinyl monomer units to 60% by mass or more, a balance between excellent fluidity and affinity with chlorine-containing polymers can be obtained, and by setting the amount to 85% by mass or less, sufficient heat resistance can be obtained. You can get sex.
In addition, when aromatic vinyl monomer units are used together, the content of the aromatic vinyl monomer units means the total amount of the aromatic vinyl monomer units used together.
（不飽和酸無水物単量体単位）
　マレイミド系共重合体に含有される不飽和酸無水物単量体単位が由来する不飽和酸無水物単量体としては、例えば、マレイン酸無水物、イタコン酸無水物、シトラコン酸無水物、アコニット酸無水物等がある。これらの中でも塩素含有ポリマー系樹脂組成物への耐熱性付与の観点からマレイン酸無水物が好ましい。不飽和酸無水物単量体は単独でも良いが２種類以上を併用してもよい。 (Unsaturated acid anhydride monomer unit)
Examples of the unsaturated acid anhydride monomer from which the unsaturated acid anhydride monomer unit contained in the maleimide copolymer is derived include maleic anhydride, itaconic anhydride, citraconic anhydride, and aconite. There are acid anhydrides, etc. Among these, maleic anhydride is preferred from the viewpoint of imparting heat resistance to the chlorine-containing polymer resin composition. The unsaturated acid anhydride monomer may be used alone, or two or more types may be used in combination.
　マレイミド系共重合体は、当該マレイミド系共重合体に含有される単量体単位の合計を１００質量％とした場合に不飽和酸無水物単量体単位を０～１０質量％含有することが好ましく、より好ましくは０～５質量％含有し、さらに好ましくは０～３質量％含有する。不飽和酸無水物単量体単位の含有量は、具体的には例えば、０，１，２，３，４，５，６，７，８，９，１０質量％であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。不飽和酸無水物単量体単位の量を１０質量％以下とすることで流動性の低下や、塩素含有ポリマーとの混練性の低下を低減することができる。
　なお、不飽和酸無水物単量体単位を併用する場合には、不飽和酸無水物単量体単位の含有量は、併用する不飽和酸無水物単量体単位の合計量を意味する。 The maleimide copolymer may contain 0 to 10% by mass of unsaturated acid anhydride monomer units when the total amount of monomer units contained in the maleimide copolymer is 100% by mass. The content is preferably 0 to 5% by mass, and even more preferably 0 to 3% by mass. Specifically, the content of the unsaturated acid anhydride monomer unit is, for example, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10% by mass, and the It may be within a range between any two values. By controlling the amount of the unsaturated acid anhydride monomer unit to 10% by mass or less, it is possible to reduce the decrease in fluidity and the decrease in kneadability with the chlorine-containing polymer.
In addition, when an unsaturated acid anhydride monomer unit is used together, the content of the unsaturated acid anhydride monomer unit means the total amount of the unsaturated acid anhydride monomer unit used together.
（共重合可能な他の単量体）
　マレイミド系共重合体は、シアン化ビニル系単量体単位、マレイミド系単量体単位、芳香族ビニル系単量体単位、及び不飽和酸無水物単量体単位以外の単量体単位（その他の単量体単位）を、本発明の効果を阻害しない範囲で共重合させてもよい。その他の単量体単位は、シアン化ビニル系単量体単位、マレイミド系単量体単位、芳香族ビニル系単量体単位、及び不飽和酸無水物単量体単位の一部又は全てと共重合可能な単量体（その他の単量体）に由来するである。その他の単量体とは、メチルアクリル酸エステル、エチルアクリル酸エステル、ブチルアクリル酸エステル等のアクリル酸エステル単量体、メチルメタクリル酸エステル、エチルメタクリル酸エステル等のメタクリル酸エステル単量体、アクリル酸、メタクリル酸等のビニルカルボン酸単量体、アクリル酸アミド及びメタクリル酸アミド等があげられる。共重合可能なその他の単量体は、単独でも良いが２種類以上を併用してもよい。
　このような単量体は本発明の効果を阻害しない範囲で共重合可能であるが、樹脂組成物への耐熱性付与の観点から２０質量％以下とすることが好ましく、１０質量％以下とすることがさらに好ましい。 (Other copolymerizable monomers)
Maleimide copolymers contain monomer units other than vinyl cyanide monomer units, maleimide monomer units, aromatic vinyl monomer units, and unsaturated acid anhydride monomer units (other monomer units) may be copolymerized within a range that does not impede the effects of the present invention. Other monomer units may be used together with some or all of the vinyl cyanide monomer units, maleimide monomer units, aromatic vinyl monomer units, and unsaturated acid anhydride monomer units. It is derived from polymerizable monomers (other monomers). Other monomers include acrylic ester monomers such as methyl acrylate, ethyl acrylate, and butyl acrylate, methacrylic ester monomers such as methyl methacrylate, and ethyl methacrylate, and acrylic ester monomers. Examples include acids, vinyl carboxylic acid monomers such as methacrylic acid, acrylamide, and methacrylic acid amide. Other copolymerizable monomers may be used alone, or two or more types may be used in combination.
Such monomers can be copolymerized within a range that does not impede the effects of the present invention, but from the viewpoint of imparting heat resistance to the resin composition, the amount is preferably 20% by mass or less, and 10% by mass or less. It is even more preferable.
（マレイミド系共重合体の重量平均分子量）
　マレイミド系共重合体の重量平均分子量は、好ましくは７０，０００～１５０，０００であり、より好ましくは７５，０００～１１０，０００である。分子量７０，０００以上とすることで、樹脂組成物の耐衝撃性の低下を抑えられ、１５０，０００以下とすることで樹脂組成物の混練性が低下するのを防ぐことができる。 (Weight average molecular weight of maleimide copolymer)
The weight average molecular weight of the maleimide copolymer is preferably 70,000 to 150,000, more preferably 75,000 to 110,000. By setting the molecular weight to 70,000 or more, it is possible to suppress a decrease in the impact resistance of the resin composition, and by setting the molecular weight to 150,000 or less, it is possible to prevent a decrease in the kneading properties of the resin composition.
　マレイミド系共重合体は、一態様においては、当該マレイミド系共重合体の１０質量％のＴＨＦ溶液と、Ｋ値が６６．７±１．０であり、塩素化度が５７．０±１．０％である塩素含有ポリマーの１０質量％のＴＨＦ溶液とを１：１の容量比で混合して作製した混合液における明度Ｌ＊が４０以上である。なお、ここでいう塩素化度とは、塩素含有ポリマー中の塩素の含有量（質量％）である。
　また、マレイミド系共重合体は、一態様においては、当該マレイミド系共重合体の１０質量％のＴＨＦ溶液と、Ｋ値が６６．０±２．０であり、塩素化度が６７．３±１．０％である塩素含有ポリマーの１０質量％のＴＨＦ溶液とを１：１の容量比で混合して作製した混合液における明度Ｌ＊が６０以上である。
　また、マレイミド系共重合体は、一態様においては、当該マレイミド系共重合体の１０質量％のＴＨＦ溶液と、Ｋ値が５６±２．０であり、塩素化度が６３．５±１．０％である塩素含有ポリマーの１０質量％のＴＨＦ溶液とを１：１の容量比で混合して作製した混合液における明度Ｌ＊が６０以上である。 In one embodiment, the maleimide copolymer has a K value of 66.7±1.0 and a chlorination degree of 57.0±1.0 when added to a 10% by mass THF solution of the maleimide copolymer. The lightness L * of a mixed solution prepared by mixing a 0% chlorine-containing polymer with a 10% by mass THF solution at a volume ratio of 1:1 is 40 or more. Note that the degree of chlorination here refers to the content (% by mass) of chlorine in the chlorine-containing polymer.
Further, in one embodiment, the maleimide copolymer has a K value of 66.0±2.0 and a chlorination degree of 67.3± when mixed with a 10% by mass THF solution of the maleimide copolymer. The lightness L * of a mixed solution prepared by mixing a 1.0% chlorine-containing polymer with a 10% by mass THF solution at a volume ratio of 1:1 is 60 or more.
In one embodiment, the maleimide copolymer has a K value of 56±2.0 and a chlorination degree of 63.5±1. The lightness L * of a mixed solution prepared by mixing a 0% chlorine-containing polymer with a 10% by mass THF solution at a volume ratio of 1:1 is 60 or more.
　本実施形態にかかる塩素含有ポリマー及び塩素含有率の高い塩素含有ポリマーのＫ値とは、ＪＩＳＫ　７３６７－２に準拠し、毛細管粘度計を用いた溶液粘度測定により得られる値であり、塩素含有ポリマー及び塩素含有率の高い塩素含有ポリマーの重合度や分子量を示す指標である。 The K value of the chlorine-containing polymer and the chlorine-containing polymer with a high chlorine content according to the present embodiment is a value obtained by measuring solution viscosity using a capillary viscometer in accordance with JISK 7367-2. It is an index showing the degree of polymerization and molecular weight of a chlorine-containing polymer with a high chlorine content.
　本実施形態における明度Ｌ＊は、塩素含有ポリマー用改質剤の１０質量％のＴＨＦ溶液と、塩素含有ポリマーの１０質量％のＴＨＦ溶液とを１：１の容量比で混合して作製した混合液を光路長１０ｍｍであり光路幅１０ｍｍの光学セルにいれ、日本分光株式会社　分光光度計　Ｖ－６７０のＬ＊ａ＊ｂ＊モードで測定の条件において測定される値である。 The lightness L * in this embodiment is a mixture prepared by mixing a 10% by mass THF solution of a chlorine-containing polymer modifier and a 10% by mass THF solution of a chlorine-containing polymer at a volume ratio of 1:1. This is a value measured under the conditions of measurement in the L * a * b * mode of a spectrophotometer V-670 manufactured by JASCO Corporation by placing a liquid in an optical cell with an optical path length of 10 mm and an optical path width of 10 mm.
　混合液における明度Ｌ＊が所定の値以上である場合、塩素含有ポリマー用改質剤は、塩素含有ポリマーに配合して樹脂組成物とした場合に耐熱性及び耐衝撃性を良好に向上させることができる。
　混合液における明度Ｌ＊を調整する方法としては、例えば、後述する方法により共重合体を含む粗生成物原料を溶解させた溶液に対する沈殿操作及び濾過操作により所望の明度Ｌ＊を満たすような特定の共重合体を得る方法が挙げられる。 When the lightness L * of the mixed solution is equal to or higher than a predetermined value, the modifier for chlorine-containing polymers satisfactorily improves heat resistance and impact resistance when blended with chlorine-containing polymers to form a resin composition. Can be done.
As a method for adjusting the lightness L * in the mixed liquid, for example, a specific method that satisfies the desired lightness L * by performing a precipitation operation and a filtration operation on a solution in which a crude product material containing a copolymer is dissolved by the method described below. A method for obtaining a copolymer of
（添加剤）
　マレイミド系共重合体は、本発明の効果を阻害しない範囲において以下に説明されるような添加剤を含有し得る。
　マレイミド系共重合体の重合終了後、重合液には必要に応じて、ヒンダードフェノール系化合物、ラクトン系化合物、リン系化合物、イオウ系化合物などの耐熱安定剤、ヒンダードアミン系化合物、ベンゾトリアゾール系化合物等の光安定剤、滑剤や可塑剤、着色剤、帯電防止剤、鉱油等の添加剤を加えても構わない。その添加量は全単量体単位１００質量部に対して０．２質量部未満であることが好ましい。これらの添加剤は単独で用いても、２種類以上を併用してもよい。 (Additive)
The maleimide copolymer may contain additives such as those described below within a range that does not impede the effects of the present invention.
After completing the polymerization of the maleimide copolymer, heat stabilizers such as hindered phenol compounds, lactone compounds, phosphorus compounds, and sulfur compounds, hindered amine compounds, and benzotriazole compounds may be added to the polymerization solution as necessary. Additives such as light stabilizers, lubricants, plasticizers, colorants, antistatic agents, mineral oil, etc. may be added. The amount added is preferably less than 0.2 parts by mass per 100 parts by mass of total monomer units. These additives may be used alone or in combination of two or more.
（マレイミド系共重合体の含有量）
　樹脂組成物は、塩素含有ポリマー１００質量部に対して、マレイミド系共重合体を１～４０質量部含み、好ましくは５～３２質量部含み、より好ましくは１５～３０質量部含む。マレイミド系共重合体の含有量は、塩素含有ポリマー１００質量部に対して、具体的には例えば、１，５，６，７，８，９，１０，１１，１２，１３，１４，１５，１６，１７，１８，１９，２０，２１，２２，２３，２４，２５，２６，２７，２８，２９，３０，３５，４０質量部であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。このような範囲とすることで、耐衝撃改質剤を添加した場合でも耐衝撃性と耐熱性がともに優れる。また、塩素含有ポリマーは塩素を有しているため、塩素含有量が多いほど耐熱性が挙がる一方で加熱時の有毒ガス発生量が多くなり金属腐食等の問題が生じうるが、マレイミド系共重合体の添加により加熱時の有毒ガス発生量を低減する、ひいては金属腐食を抑えることができる。 (Content of maleimide copolymer)
The resin composition contains 1 to 40 parts by weight, preferably 5 to 32 parts by weight, and more preferably 15 to 30 parts by weight of the maleimide copolymer per 100 parts by weight of the chlorine-containing polymer. Specifically, the content of the maleimide copolymer is, for example, 1, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 35, 40 parts by mass, between any two of the numerical values exemplified here. It may be within the range. By setting it in such a range, both impact resistance and heat resistance are excellent even when an impact modifier is added. In addition, since chlorine-containing polymers contain chlorine, the higher the chlorine content, the higher the heat resistance, but the higher the amount of toxic gas generated during heating, which can cause problems such as metal corrosion. The addition of coalescent can reduce the amount of toxic gas generated during heating, and can also suppress metal corrosion.
（マレイミド系共重合体の製造）
　マレイミド系共重合体の重合様式は、例えば、溶液重合、塊状重合等がある。分添等を行いながら重合することで、共重合組成がより均一な共重合体を得られるという観点から、溶液重合が好ましい。溶液重合の溶媒は、副生成物が出来難く、悪影響が少ないという観点から非重合性であることが好ましい。例えば、アセトン、メチルエチルケトン、メチルイソブチルケトン、アセトフェノン等のケトン類、テトラヒドロフラン、１，４－ジオキサン等のエーテル類、ベンゼン、トルエン、キシレン、エチルベンゼン、クロロベンゼン等の芳香族炭化水素、Ｎ，Ｎ－ジメチルホルムアミド、ジメチルスルホキシド、Ｎ－メチル－２－ピロリドン等であり、マレイミド系共重合体の脱揮回収時における溶媒除去の容易性から、メチルエチルケトン、メチルイソブチルケトンが好ましい。重合プロセスは、連続重合式、バッチ式（回分式）、半回分式のいずれも適用できる。 (Manufacture of maleimide copolymer)
Examples of the polymerization mode of the maleimide copolymer include solution polymerization and bulk polymerization. Solution polymerization is preferable from the viewpoint that a copolymer having a more uniform copolymer composition can be obtained by polymerizing while performing partial addition or the like. It is preferable that the solvent for solution polymerization is non-polymerizable from the viewpoint that by-products are less likely to be produced and there are fewer adverse effects. For example, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and acetophenone, ethers such as tetrahydrofuran and 1,4-dioxane, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and chlorobenzene, and N,N-dimethylformamide. , dimethyl sulfoxide, N-methyl-2-pyrrolidone, etc., and methyl ethyl ketone and methyl isobutyl ketone are preferred from the viewpoint of ease of solvent removal during devolatilization and recovery of the maleimide copolymer. The polymerization process may be a continuous polymerization type, a batch type (batch type), or a semi-batch type.
　マレイミド系共重合体の製造方法としては、特に限定されるものではないが、好ましくはラジカル重合により得ることができ、重合温度は８０～１５０℃の範囲であることが好ましい。重合開始剤としては特に限定されるものではないが、例えばアゾビスイソブチロニトリル、アゾビスシクロヘキサンカルボニトリル、アゾビスメチルプロピオニトリル、アゾビスメチルブチロニトリル等の公知のアゾ化合物や、ベンゾイルパーオキサイド、ｔ－ブチルパーオキシベンゾエート、１，１－ビス（ｔ－ブチルパーオキシ）－３，３，５－トリメチルシクロヘキサン、ｔ－ブチルパーオキシイソプロピルモノカーボネート、ｔ－ブチルパーオキシ－２－エチルヘキサノエート、ジ－ｔ－ブチルパーオキサイド、ジクミルパーオキサイド、エチル－３，３－ジ－（ｔ－ブチルパーオキシ）ブチレート等の公知の有機過酸化物を用いることができ、これらの１種あるいは２種類以上を組み合わせて使用しても良い。重合の反応速度や重合率制御の観点から、１０時間半減期が７０～１２０℃であるアゾ化合物や有機過酸化物を用いるのが好ましい。重合開始剤の使用量は、特に限定されるものではないが、全単量体単位１００質量％に対して０．１～１．５質量％使用することが好ましく、さらに好ましくは０．１～１．０質量％である。重合開始剤の使用量が０．１質量％以上であれば、十分な重合速度が得られるため好ましい。重合開始剤の使用量が１．５質量％以下であれば、重合速度が抑制できるため反応制御が容易になり、目標分子量を得ることが容易になる。 The method for producing the maleimide copolymer is not particularly limited, but it can preferably be obtained by radical polymerization, and the polymerization temperature is preferably in the range of 80 to 150°C. The polymerization initiator is not particularly limited, but includes known azo compounds such as azobisisobutyronitrile, azobiscyclohexanecarbonitrile, azobismethylpropionitrile, and azobismethylbutyronitrile, and benzoyl. Peroxide, t-butylperoxybenzoate, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethyl Known organic peroxides such as hexanoate, di-t-butyl peroxide, dicumyl peroxide, and ethyl-3,3-di-(t-butylperoxy)butyrate can be used; You may use a species or a combination of two or more species. From the viewpoint of polymerization reaction rate and polymerization rate control, it is preferable to use an azo compound or an organic peroxide having a 10-hour half-life of 70 to 120°C. The amount of the polymerization initiator used is not particularly limited, but it is preferably used in an amount of 0.1 to 1.5% by mass, more preferably 0.1 to 1.5% by mass based on 100% by mass of all monomer units. It is 1.0% by mass. It is preferable that the amount of the polymerization initiator used is 0.1% by mass or more because a sufficient polymerization rate can be obtained. When the amount of the polymerization initiator used is 1.5% by mass or less, the polymerization rate can be suppressed, so reaction control becomes easy and it becomes easy to obtain the target molecular weight.
　マレイミド系共重合体の製造には、連鎖移動剤を使用することが出来る。使用される連鎖移動剤としては、特に限定されるものではないが、例えばｎ－オクチルメルカプタン、ｎ－ドデシルメルカプタン、ｔ－ドデシルメルカプタン、α－メチルスチレンダイマー、チオグリコール酸エチル、リモネン、ターピノーレン等がある。連鎖移動量の使用量は、目標分子量が得られる範囲であれば、特に限定されるものではないが、全単量体単位１００質量％に対して０．０１～０．８質量％であることが好ましく、さらに好ましくは０．１～０．５質量％である。連鎖移動剤の使用量が０．０１質量％～０．８質量％であれば、目標分子量を容易に得ることができる。 A chain transfer agent can be used in the production of maleimide copolymers. The chain transfer agent used is not particularly limited, but includes, for example, n-octylmercaptan, n-dodecylmercaptan, t-dodecylmercaptan, α-methylstyrene dimer, ethyl thioglycolate, limonene, terpinolene, etc. be. The amount of chain transfer used is not particularly limited as long as the target molecular weight can be obtained, but it should be 0.01 to 0.8% by mass based on 100% by mass of all monomer units. is preferable, and more preferably 0.1 to 0.5% by mass. If the amount of chain transfer agent used is 0.01% by mass to 0.8% by mass, the target molecular weight can be easily obtained.
　マレイミド系共重合体へのマレイミド系単量体単位の導入方法としては、マレイミド系単量体、芳香族ビニル系単量体、シアン化ビニル系単量体とを共重合する方法（直接法）、或いは不飽和ジカルボン酸無水物、芳香族ビニル系単量体、シアン化ビニル系単量体とを予め共重合しておき、更にアンモニア又は第１級アミンで不飽和ジカルボン酸無水物基を反応させる事により不飽和ジカルボン酸無水物基をマレイミド系単量体単位に変換する方法（後イミド化法）がある。後イミド化法の方が、共重合体中の残存マレイミド系単量体量が少なくなるので好ましい。 The method for introducing maleimide monomer units into maleimide copolymers is to copolymerize maleimide monomers, aromatic vinyl monomers, and vinyl cyanide monomers (direct method). , or by copolymerizing an unsaturated dicarboxylic anhydride, an aromatic vinyl monomer, and a vinyl cyanide monomer in advance, and then reacting the unsaturated dicarboxylic anhydride group with ammonia or a primary amine. There is a method (post-imidization method) in which an unsaturated dicarboxylic acid anhydride group is converted into a maleimide monomer unit by The post-imidization method is preferable because it reduces the amount of maleimide monomer remaining in the copolymer.
　後イミド化法で用いる第１級アミンとは、例えば、メチルアミン、エチルアミン、ｎ－プロピルアミン、ｉｓｏ－プロピルアミン、ｎ－ブチルアミン、ｎ－ペンチルアミン、ｎ－ヘキシルアミン、ｎ－オクチルアミン、シクロヘキシルアミン、デシルアミン等のアルキルアミン類及びクロル又はブロム置換アルキルアミン、アニリン、トルイジン、ナフチルアミン等の芳香族アミンがあり、この中でもアニリン、シクロヘキシルアミンが好ましい。これらの第１級アミンは、単独で使用しても２種類以上を組み合わせて使用しても良い。第１級アミンの添加量は特に限定されるものではないが、不飽和ジカルボン酸無水物基に対して好ましくは０．７～１．１モル当量、さらに好ましくは０．８５～１．０５モル当量である。マレイミド系共重合体中の不飽和ジカルボン酸無水物単量体単位に対して０．７モル当量以上であれば、熱安定性が良好となるため好ましい。また、１．１モル当量以下であれば、共重合体中に残存する第１級アミン量が低減するため好ましい。 The primary amines used in the post-imidization method include, for example, methylamine, ethylamine, n-propylamine, iso-propylamine, n-butylamine, n-pentylamine, n-hexylamine, n-octylamine, and cyclohexyl. Examples include amines, alkylamines such as decylamine, chloro- or bromine-substituted alkylamines, aromatic amines such as aniline, toluidine, and naphthylamine, and among these, aniline and cyclohexylamine are preferred. These primary amines may be used alone or in combination of two or more. The amount of primary amine added is not particularly limited, but is preferably 0.7 to 1.1 molar equivalent, more preferably 0.85 to 1.05 mol, based on the unsaturated dicarboxylic anhydride group. It is equivalent. It is preferable that the amount is 0.7 molar equivalent or more based on the unsaturated dicarboxylic anhydride monomer unit in the maleimide copolymer because thermal stability will be good. Moreover, if it is 1.1 molar equivalent or less, it is preferable because the amount of primary amine remaining in the copolymer is reduced.
　マレイミド系単量体単位を後イミド化法で導入する際に触媒を用いてもよい。触媒は、アンモニア又は第１級アミンと不飽和ジカルボン酸無水物基との反応、特に不飽和ジカルボン酸無水物基からマレイミド基に変換する反応において、脱水閉環反応を向上させる事ができる。触媒の種類は特に限定されるものではないが、例えば第３級アミンを使用する事ができる。第３級アミンとしては特に限定されるものではないが、例えばトリメチルアミン、トリエチルアミン、トリプロピルアミン、トリブチルアミン、Ｎ、Ｎ－ジメチルアニリン、Ｎ、Ｎ－ジエチルアニリン等が挙げられる。第３級アミンの添加量は特に限定されるものではないが、不飽和ジカルボン酸無水物基に対し、０．０１モル当量以上が好ましい。本発明におけるイミド化反応の温度は好ましくは１００～２５０℃であり、さらに好ましくは１２０～２００℃である。イミド化反応の温度が１００℃以上であれば、反応速度が十分に早く生産性の面から好ましい。イミド化反応の温度が２５０℃以下であれば共重合体の熱劣化による物性低下を抑制できるため好ましい。 A catalyst may be used when introducing the maleimide monomer unit by the post-imidization method. A catalyst can improve the dehydration ring closure reaction in the reaction between ammonia or a primary amine and an unsaturated dicarboxylic anhydride group, particularly in the reaction of converting an unsaturated dicarboxylic anhydride group into a maleimide group. Although the type of catalyst is not particularly limited, for example, a tertiary amine can be used. Tertiary amines are not particularly limited, but include, for example, trimethylamine, triethylamine, tripropylamine, tributylamine, N,N-dimethylaniline, N,N-diethylaniline, and the like. Although the amount of the tertiary amine added is not particularly limited, it is preferably 0.01 molar equivalent or more based on the unsaturated dicarboxylic anhydride group. The temperature of the imidization reaction in the present invention is preferably 100 to 250°C, more preferably 120 to 200°C. If the temperature of the imidization reaction is 100° C. or higher, the reaction rate is sufficiently high and it is preferable from the viewpoint of productivity. It is preferable that the temperature of the imidization reaction is 250° C. or lower because it is possible to suppress deterioration of physical properties due to thermal deterioration of the copolymer.
　マレイミド系共重合体の溶液重合終了後の溶液或いは後イミド化終了後の溶液から、溶液重合に用いた溶媒や未反応の単量体などの揮発分を取り除く方法（脱揮方法）は、公知の手法が採用できる。例えば、加熱器付きの真空脱揮槽やベント付き脱揮押出機を用いることができる。脱揮された溶融状態のマレイミド系共重合体は、造粒工程に移送され、多孔ダイよりストランド状に押出し、コールドカット方式や空中ホットカット方式、水中ホットカット方式にてペレット状に加工することができる。 There is a known method for removing volatile components such as the solvent used in solution polymerization and unreacted monomers from a solution after solution polymerization of a maleimide copolymer or a solution after post-imidization (devolatilization method). This method can be adopted. For example, a vacuum devolatilization tank equipped with a heater or a devolatilization extruder equipped with a vent can be used. The devolatilized maleimide copolymer in a molten state is transferred to a granulation process, extruded into strands from a multi-hole die, and processed into pellets using a cold cut method, an air hot cut method, or an underwater hot cut method. I can do it.
　マレイミド系共重合体は、例えば、上述の方法により得られるマレイミド系共重合体（粗生成物原料）をさらに精製することにより明度Ｌ＊を調整してもよい。具体的には、例えば、以下の工程を実施する。 The lightness L* of the maleimide copolymer may be adjusted, for example, by further refining the maleimide copolymer (crude product raw material) obtained by the above method. Specifically, for example, the following steps are performed.
（１）粗生成物原料を、メチルエチルケトンに溶解させ、粗生成物原料のメチルエチルケトン溶液を得る。
（２）メチルエチルケトン溶液にヘキサンを滴下して、溶解させた粗生成物原料の一部を析出させた混合液を得る。
（３）混合液を濾過して、濾物と濾液に分離する。濾物は、２４時間風乾した後に、７０℃に設定した真空乾燥器で４時間乾燥させる乾燥工程を経て取得される。
（４）（３）で得た濾液にヘキサンを滴下して、粗生成物原料の一部を析出させた混合液を得る。
（５）上記（３）～（４）の操作を繰り返し、複数の濾物を得る。 (1) A crude product raw material is dissolved in methyl ethyl ketone to obtain a solution of the crude product raw material in methyl ethyl ketone.
(2) Hexane is added dropwise to the methyl ethyl ketone solution to obtain a mixed solution in which a portion of the dissolved crude product raw material is precipitated.
(3) Filter the mixture to separate the filtrate and the filtrate. The filtrate is obtained through a drying step of air drying for 24 hours and then drying it in a vacuum dryer set at 70° C. for 4 hours.
(4) Hexane is added dropwise to the filtrate obtained in (3) to obtain a mixed solution in which a portion of the crude product raw material is precipitated.
(5) Repeat the operations (3) to (4) above to obtain a plurality of filtrates.
　複数の濾物のうち所望の明度Ｌ＊を有するものを精製されたマレイミド系共重合体として用いることができる。 Among the plurality of filtrates, one having a desired lightness L * can be used as the purified maleimide copolymer.
＜明度Ｌ＊の測定方法＞
　本実施形態における明度Ｌ＊は、マレイミド系共重合体の１０質量％のＴＨＦ溶液と、塩素含有ポリマーの１０質量％のＴＨＦ溶液とを１：１の容量比で混合して作製した混合液を光路長１０ｍｍであり光路幅１０ｍｍの光学セルにいれ、日本分光株式会社　分光光度計　Ｖ－６７０のＬ＊ａ＊ｂ＊モードで測定の条件において測定される値である。　 <Measurement method of lightness L * >
The lightness L * in this embodiment refers to a liquid mixture prepared by mixing a 10% by mass THF solution of a maleimide copolymer and a 10% by mass THF solution of a chlorine-containing polymer at a volume ratio of 1:1. This is a value measured under the conditions of measurement in the L * a * b * mode of a spectrophotometer V-670 manufactured by JASCO Corporation, using an optical cell with an optical path length of 10 mm and an optical path width of 10 mm.
＜耐衝撃改質剤＞
　耐衝撃改質剤としては、例えば、ＡＢＳ（アクリロニトリル－ブタジエン－スチレン）樹脂、ＭＢＳ（メチルメタクリレート－ブタジエン－スチレン）樹脂、アクリルゴム、塩素化ポリエチレン（塩素化ＰＥ）、ＮＢＲ（アクリロニトリルブタジエンゴム）が挙げられる。これらの中でも耐衝撃性を向上させる効果の高いＭＢＳ樹脂、アクリルゴム、塩素化ポリエチレンが好ましい。これらの耐衝撃改質剤は、１種を単独で用いてもよく、２種類以上を併用してもよい。 <Impact modifier>
Examples of impact modifiers include ABS (acrylonitrile-butadiene-styrene) resin, MBS (methyl methacrylate-butadiene-styrene) resin, acrylic rubber, chlorinated polyethylene (chlorinated PE), and NBR (acrylonitrile butadiene rubber). Can be mentioned. Among these, MBS resin, acrylic rubber, and chlorinated polyethylene are preferable because they are highly effective in improving impact resistance. These impact modifiers may be used alone or in combination of two or more.
　樹脂組成物は、塩素含有ポリマー１００質量部に対して、耐衝撃改質剤を好ましくは１～５０質量部含み、より好ましくは２～３０質量部含み、さらに好ましくは５～１５質量部含む。耐衝撃改質剤の含有量は、塩素含有ポリマー１００質量部に対して、具体的には例えば、１，５，６，７，８，９，１０，１１，１２，１３，１４，１５，２０，２５，３０，３５，４０，４５，５０質量部であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。なお、耐衝撃改質剤を併用する場合には、耐衝撃改質剤の含有量は、併用する耐衝撃改質剤の合計量を意味する。塩素含有ポリマー１００質量部に対する衝撃改質剤の含有量を１質量部以上とすることで耐衝撃性を向上させる効果が得られ、また、５０質量部以下とすることで曲げ弾性率の低下が抑えられる。 The resin composition preferably contains 1 to 50 parts by weight, more preferably 2 to 30 parts by weight, and even more preferably 5 to 15 parts by weight of an impact modifier per 100 parts by weight of the chlorine-containing polymer. Specifically, the content of the impact modifier is, for example, 1, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, The amount may be 20, 25, 30, 35, 40, 45, or 50 parts by mass, and may be within a range between any two of the numerical values exemplified here. In addition, when an impact modifier is used in combination, the content of the impact modifier means the total amount of the impact modifier used in combination. By setting the content of the impact modifier to 100 parts by mass of the chlorine-containing polymer to be 1 part by mass or more, the effect of improving impact resistance can be obtained, and by setting it to 50 parts by mass or less, the flexural modulus can be reduced. It can be suppressed.
＜その他の添加剤＞
　樹脂組成物は、必要に応じてその他の添加剤をさらに含んでいてもよい。その他の添加剤としては、例えば、充填剤、加工助剤、強化剤、加工性改良剤、熱安定剤、滑剤、可塑剤、光安定剤、紫外線吸収剤、酸化防止剤、顔料、染料等が挙げられる。これらを単独または２種類以上組み合わせて添加することもできる。 <Other additives>
The resin composition may further contain other additives as necessary. Examples of other additives include fillers, processing aids, reinforcing agents, processability improvers, heat stabilizers, lubricants, plasticizers, light stabilizers, ultraviolet absorbers, antioxidants, pigments, dyes, etc. Can be mentioned. These may be added alone or in combination of two or more.
（充填剤）
　樹脂組成物は、充填剤を含有することによって、樹脂組成物から得られる成形品の曲げ弾性率を向上させる効果が期待できる。充填剤としては、例えば、シリカ、珪藻土、アルミナ、酸化亜鉛、酸化チタン、酸化カルシウム、酸化マグネシウム、酸化鉄、酸化錫、酸化アンチモン、フェライト類、水酸化カルシウム、水酸化マグネシウム、水酸化アルミニウム、塩基性炭酸マグネシウム、炭酸カルシウム、炭酸マグネシウム、炭酸亜鉛、炭酸バリウム、ドーンナイト、ハイドロタルサイト、硫酸カルシウム、硫酸バリウム、石膏繊維、ケイ酸カルシウム、タルク、クレー、マイカ、モンモリロナイト、ベントナイト、活性白土、セピオライト、イモゴライト、セリサイト、ガラス繊維、ガラスビーズ、シリカ系バルン、窒化アルミニウム、窒化ホウ素、窒化ケイ素、カーボンブラック、グラファイト、炭素繊維、炭素バルン、木炭粉末、各種金属粉、チタン酸カリウム、硫酸マグネシウム、チタン酸ジルコン酸鉛、アルミニウムボレート、硫化モリブデン、炭化ケイ素、ステンレス繊維、ホウ酸亜鉛、各種磁性粉、スラグ繊維、フライアッシュ、脱水汚泥等またこれらを表面処理したもの等が挙げられる。これらの中でも機械物性・ビカット軟化温度向上性を向上させる効果の高い炭酸カルシウム、ケイ酸カルシウム、水酸化カルシウム、酸化カルシウム、炭酸マグネシウム、水酸化マグネシウム、酸化マグネシウム、炭酸バリウム、水酸化アルミニウム、酸化亜鉛、水酸化亜鉛、酸化鉄等の塩基性無機充填剤、タルク等が好ましい。これらの充填剤は、１種を単独で用いてもよく、２種類以上を併用してもよい。 (filler)
By containing a filler, the resin composition can be expected to have the effect of improving the flexural modulus of a molded article obtained from the resin composition. Examples of fillers include silica, diatomaceous earth, alumina, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, ferrites, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, and bases. Magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dawnite, hydrotalcite, calcium sulfate, barium sulfate, gypsum fiber, calcium silicate, talc, clay, mica, montmorillonite, bentonite, activated clay, sepiolite , imogolite, sericite, glass fiber, glass beads, silica balloons, aluminum nitride, boron nitride, silicon nitride, carbon black, graphite, carbon fiber, carbon balloons, charcoal powder, various metal powders, potassium titanate, magnesium sulfate, Examples include lead zirconate titanate, aluminum borate, molybdenum sulfide, silicon carbide, stainless steel fibers, zinc borate, various magnetic powders, slag fibers, fly ash, dehydrated sludge, and surface-treated products of these. Among these, calcium carbonate, calcium silicate, calcium hydroxide, calcium oxide, magnesium carbonate, magnesium hydroxide, magnesium oxide, barium carbonate, aluminum hydroxide, and zinc oxide are highly effective in improving mechanical properties and Vicat softening temperature. , basic inorganic fillers such as zinc hydroxide, iron oxide, talc and the like are preferred. These fillers may be used alone or in combination of two or more.
　樹脂組成物は、塩素含有ポリマー１００質量部に対して、充填剤を好ましくは１～１００質量部含み、より好ましくは１～７５質量部含み、さらに好ましくは１～５０質量部含む。充填剤の含有量は、塩素含有ポリマー１００質量部に対して、具体的には例えば、１、３、５、１０、２０、４０、６０、８０、１００質量部であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。なお、充填剤を併用する場合には、充填剤の含有量は、併用する充填剤の合計量を意味する。塩素含有ポリマー１００質量部に対する充填剤の含有量を１質量部以上とすることで曲げ弾性率を向上させる効果が得られ、また、５０質量部以下とすることで分散性低下が抑えられる。 The resin composition preferably contains 1 to 100 parts by weight, more preferably 1 to 75 parts by weight, and even more preferably 1 to 50 parts by weight of a filler per 100 parts by weight of the chlorine-containing polymer. Specifically, the content of the filler is, for example, 1, 3, 5, 10, 20, 40, 60, 80, 100 parts by mass with respect to 100 parts by mass of the chlorine-containing polymer, and the numerical values exemplified here. It may be within the range between any two. In addition, when a filler is used together, the content of the filler means the total amount of the filler used together. By setting the filler content to 1 part by mass or more with respect to 100 parts by mass of the chlorine-containing polymer, the effect of improving the flexural modulus can be obtained, and by setting it to 50 parts by mass or less, a decrease in dispersibility can be suppressed.
（加工助剤）
　加工助剤としては、例えば、アクリル系共重合体が挙げられる。これらの加工助剤は、１種を単独で用いてもよく、２種類以上を併用してもよい。樹脂組成物は、加工助剤を含有することによって、加工時のゲル化の促進や樹脂組成物から得られる成形品の成形性を向上させる効果が期待できる。 (Processing aid)
Examples of processing aids include acrylic copolymers. These processing aids may be used alone or in combination of two or more. By containing a processing aid, the resin composition can be expected to have the effect of promoting gelation during processing and improving the moldability of molded articles obtained from the resin composition.
　樹脂組成物は、塩素含有ポリマー１００質量部に対して、加工助剤を好ましくは０．０１～１０質量部含み、より好ましくは０．０５～５質量部含む。加工助剤の含有量は、塩素含有ポリマー１００質量部に対して、具体的には例えば、０．０１、０．０２、０．０５、０．１、０．２、０．５、１、２、５、１０質量部であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。なお、加工助剤を併用する場合には、加工助剤の配合量は、併用する加工助剤の合計量を意味する。塩素含有ポリマー１００質量部に対する加工助剤の含有量を０．０１質量部以上とすることで加工性を向上させる効果が得られ、また、１０質量部以下とすることで機械物性低下が抑えられる。 The resin composition preferably contains 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight of a processing aid, per 100 parts by weight of the chlorine-containing polymer. Specifically, the content of the processing aid is, for example, 0.01, 0.02, 0.05, 0.1, 0.2, 0.5, 1, with respect to 100 parts by mass of the chlorine-containing polymer. The amount may be 2, 5, or 10 parts by mass, and may be within a range between any two of the numerical values exemplified here. In addition, when a processing aid is used together, the amount of the processing aid used means the total amount of the processing aid used together. By setting the content of the processing aid to 100 parts by mass of the chlorine-containing polymer to 0.01 parts by mass or more, the effect of improving processability can be obtained, and by setting it to 10 parts by mass or less, deterioration in mechanical properties can be suppressed. .
＜樹脂組成物の製造＞
　マレイミド系共重合体と塩素含有ポリマーとを混練混合して樹脂組成物を得る方法については、特に限定はなく、公知の溶融混練技術を用いることが出来る。好適に使用できる溶融混練装置としては、単軸押出機、噛合形同方向回転または噛合形異方向回転二軸押出機、非または不完全噛合形二軸押出機等のスクリュー押出機、バンバリーミキサー、コニーダー及び混合ロール等がある。また、これらの押出機を複数組み合わせて使用することもできる。 <Manufacture of resin composition>
There is no particular limitation on the method of kneading and mixing the maleimide copolymer and the chlorine-containing polymer to obtain the resin composition, and any known melt-kneading technique can be used. Suitable melt-kneading devices include a single screw extruder, an intermeshing type co-rotating or intermeshing type counter-rotating twin screw extruder, a screw extruder such as a non-intermeshing type twin screw extruder, a Banbury mixer, There are co-kneaders, mixing rolls, etc. Moreover, a plurality of these extruders can be used in combination.
　樹脂組成物を公知の方法により成形して成形体を得ることができる。成形方法としては、例えば、射出成形、シート押出成形、真空成形、ブロー成形、発泡成形、異型押出成形等が挙げられる。成形時には、通常、樹脂組成物を１７０～２００℃に加熱した後、加工されるが、１９０～２００℃であることが好ましい。 A molded article can be obtained by molding the resin composition by a known method. Examples of the molding method include injection molding, sheet extrusion molding, vacuum molding, blow molding, foam molding, and profile extrusion molding. During molding, the resin composition is usually heated to 170 to 200°C and then processed, preferably at 190 to 200°C.
　以下、詳細な内容について実施例を用いて説明するが、本発明は以下の実施例に限定されるものではない。 Hereinafter, detailed contents will be explained using examples, but the present invention is not limited to the following examples.
（第１観点）
表中、Ｓｔｙはスチレン、ＡＮはアクリロニトリル、ＮＰＭＩはＮ－フェニルマレイミド、ＭＡＨは無水マレイン酸、ＭＢＳはメチルメタクリレート－ブタジエン－スチレン樹脂を示す。 (First perspective)
In the table, Sty represents styrene, AN represents acrylonitrile, NPMI represents N-phenylmaleimide, MAH represents maleic anhydride, and MBS represents methyl methacrylate-butadiene-styrene resin.
　＜粗生成物原料（Ｒ－１）の製造例＞
　攪拌機を備えた容積約１２０リットルのオートクレーブ中にスチレン７７質量部、アクリロニトリル９質量部、マレイン酸無水物４質量部、α－メチルスチレンダイマーを０．４質量部、メチルエチルケトン３８質量部を仕込み、気相部を窒素ガスで置換した後、撹拌しながら４０分かけて９２℃まで昇温した。昇温後９２℃を保持しながら、マレイン酸無水物９質量部とｔ－ブチルパーオキシ－２－エチルヘキサノエート０．８質量部をメチルエチルケトン４７質量部に溶解した溶液を５時間かけて連続的に添加した。添加終了後、１２０℃に昇温し、１時間反応させて重合を終了させた。その後、重合液にアニリン１２質量部、トリエチルアミン０．２質量部を加え１４０℃で１０時間反応させた。反応終了後のイミド化反応液をベントタイプスクリュー式押出機に投入し、揮発分を除去してペレット状の粗生成物原料（Ｒ－１）を得た。後述のＣ－１３ＮＭＲ法にて粗生成物原料（Ｒ－１）の組成分析を行ったところ、スチレン７０質量％、アクリロニトリル８質量％、Ｎ－フェニルマレイミド２１質量％、無水マレイン酸１質量％であった。得られた粗生成物原料の分析結果を表１－１に示す。 <Production example of crude product raw material (R-1)>
In an autoclave with a capacity of approximately 120 liters equipped with a stirrer, 77 parts by mass of styrene, 9 parts by mass of acrylonitrile, 4 parts by mass of maleic anhydride, 0.4 parts by mass of α-methylstyrene dimer, and 38 parts by mass of methyl ethyl ketone were charged. After replacing the phase with nitrogen gas, the temperature was raised to 92° C. over 40 minutes while stirring. After raising the temperature, a solution of 9 parts by mass of maleic anhydride and 0.8 parts by mass of t-butylperoxy-2-ethylhexanoate dissolved in 47 parts by mass of methyl ethyl ketone was continuously heated for 5 hours while maintaining the temperature at 92°C. added. After the addition was completed, the temperature was raised to 120°C, and the reaction was carried out for 1 hour to complete the polymerization. Thereafter, 12 parts by mass of aniline and 0.2 parts by mass of triethylamine were added to the polymerization solution and reacted at 140° C. for 10 hours. After the completion of the reaction, the imidization reaction solution was put into a vent type screw extruder, and volatile components were removed to obtain a pellet-shaped crude product raw material (R-1). Composition analysis of the crude product raw material (R-1) using the C-13 NMR method described below revealed that it contained 70% by mass of styrene, 8% by mass of acrylonitrile, 21% by mass of N-phenylmaleimide, and 1% by mass of maleic anhydride. there were. The analysis results of the obtained crude product raw material are shown in Table 1-1.
　＜粗生成物原料（Ｒ－２）の製造例＞
　攪拌機を備えた容積約１２０リットルのオートクレーブ中にスチレン７８質量部、アクリロニトリル１３質量部、マレイン酸無水物２質量部、α－メチルスチレンダイマーを０．４質量部、メチルエチルケトン３０質量部を仕込み、気相部を窒素ガスで置換した後、撹拌しながら４０分かけて９２℃まで昇温した。昇温後９２℃を保持しながら、マレイン酸無水物６質量部とｔ－ブチルパーオキシ－２－エチルヘキサノエート０．７質量部をメチルエチルケトン３２質量部に溶解した溶液を４．５時間かけて連続的に添加した。添加終了後、１２０℃に昇温し、１．５時間反応させて重合を終了させた。その後、重合液にアニリン７質量部、トリエチルアミン０．１質量部を加え１４０℃で７時間反応させた。反応終了後のイミド化反応液をベントタイプスクリュー式押出機に投入し、揮発分を除去してペレット状の粗生成物原料（Ｒ－２）を得た。後述のＣ－１３ＮＭＲ法にて粗生成物原料（Ｒ－２）の組成分析を行ったところ、スチレン７２質量％、アクリロニトリル１２質量％、Ｎ－フェニルマレイミド１４質量％、無水マレイン酸２質量％であった。得られた粗生成物原料の分析結果を表１－１に示す。 <Production example of crude product raw material (R-2)>
In an autoclave with a capacity of approximately 120 liters equipped with a stirrer, 78 parts by mass of styrene, 13 parts by mass of acrylonitrile, 2 parts by mass of maleic anhydride, 0.4 parts by mass of α-methylstyrene dimer, and 30 parts by mass of methyl ethyl ketone were charged. After replacing the phase with nitrogen gas, the temperature was raised to 92° C. over 40 minutes while stirring. After raising the temperature, a solution of 6 parts by mass of maleic anhydride and 0.7 parts by mass of t-butylperoxy-2-ethylhexanoate dissolved in 32 parts by mass of methyl ethyl ketone was heated for 4.5 hours while maintaining the temperature at 92°C. was added continuously. After the addition was completed, the temperature was raised to 120° C., and the reaction was carried out for 1.5 hours to complete the polymerization. Thereafter, 7 parts by mass of aniline and 0.1 parts by mass of triethylamine were added to the polymerization solution, and the mixture was reacted at 140° C. for 7 hours. After the completion of the reaction, the imidization reaction solution was put into a vent type screw extruder, and volatile components were removed to obtain a pellet-shaped crude product raw material (R-2). Composition analysis of the crude product raw material (R-2) using the C-13 NMR method described below revealed that it contained 72% by mass of styrene, 12% by mass of acrylonitrile, 14% by mass of N-phenylmaleimide, and 2% by mass of maleic anhydride. there were. The analysis results of the obtained crude product raw material are shown in Table 1-1.
　＜粗生成物原料（Ｒ－３）の製造例＞
　攪拌機を備えた容積約１２０リットルのオートクレーブ中にスチレン７１質量部、アクリロニトリル１６質量部、マレイン酸無水物３質量部、α－メチルスチレンダイマーを０．４質量部、メチルエチルケトン３６質量部を仕込み、気相部を窒素ガスで置換した後、撹拌しながら４０分かけて９２℃まで昇温した。昇温後９２℃を保持しながら、マレイン酸無水物１０質量部とｔ－ブチルパーオキシ－２－エチルヘキサノエート０．８質量部をメチルエチルケトン５０質量部に溶解した溶液を５時間かけて連続的に添加した。添加終了後、１２０℃に昇温し、１時間反応させて重合を終了させた。その後、重合液にアニリン１１質量部、トリエチルアミン０．２質量部を加え１４０℃で１０時間反応させた。反応終了後のイミド化反応液をベントタイプスクリュー式押出機に投入し、揮発分を除去してペレット状の粗生成物原料（Ｒ－３）を得た。後述のＣ－１３ＮＭＲ法にて粗生成物原料（Ｒ－３）の組成分析を行ったところ、スチレン６５質量％、アクリロニトリル１４質量％、Ｎ－フェニルマレイミド２０質量％、無水マレイン酸１質量％であった。得られた粗生成物原料の分析結果を表１－１に示す。 <Production example of crude product raw material (R-3)>
In an autoclave with a capacity of approximately 120 liters equipped with a stirrer, 71 parts by mass of styrene, 16 parts by mass of acrylonitrile, 3 parts by mass of maleic anhydride, 0.4 parts by mass of α-methylstyrene dimer, and 36 parts by mass of methyl ethyl ketone were charged. After replacing the phase with nitrogen gas, the temperature was raised to 92° C. over 40 minutes while stirring. After raising the temperature, a solution of 10 parts by mass of maleic anhydride and 0.8 parts by mass of t-butylperoxy-2-ethylhexanoate dissolved in 50 parts by mass of methyl ethyl ketone was continuously heated for 5 hours while maintaining the temperature at 92°C. added. After the addition was completed, the temperature was raised to 120°C, and the reaction was carried out for 1 hour to complete the polymerization. Thereafter, 11 parts by mass of aniline and 0.2 parts by mass of triethylamine were added to the polymerization solution, and the mixture was reacted at 140° C. for 10 hours. After the completion of the reaction, the imidization reaction solution was charged into a vent type screw extruder, and volatile components were removed to obtain a pellet-shaped crude product raw material (R-3). Composition analysis of the crude product raw material (R-3) using the C-13 NMR method described below revealed that it contained 65% by mass of styrene, 14% by mass of acrylonitrile, 20% by mass of N-phenylmaleimide, and 1% by mass of maleic anhydride. there were. The analysis results of the obtained crude product raw material are shown in Table 1-1.
　＜粗生成物原料（Ｒ－４）の製造例＞
　攪拌機を備えた容積約１２０リットルのオートクレーブ中にスチレン８１質量部、アクリロニトリル１３質量部、マレイン酸無水物１質量部、α－メチルスチレンダイマーを０．４質量部、メチルエチルケトン２５質量部を仕込み、気相部を窒素ガスで置換した後、撹拌しながら４０分かけて９２℃まで昇温した。昇温後９２℃を保持しながら、マレイン酸無水物４質量部とｔ－ブチルパーオキシ－２－エチルヘキサノエート０．８質量部をメチルエチルケトン２２質量部に溶解した溶液を５時間かけて連続的に添加した。添加終了後、１２０℃に昇温し、１時間反応させて重合を終了させた。その後、重合液にアニリン５質量部、トリエチルアミン０．１質量部を加え１４０℃で１０時間反応させた。反応終了後のイミド化反応液をベントタイプスクリュー式押出機に投入し、揮発分を除去してペレット状の粗生成物原料Ｒ－４を得た。後述のＣ－１３ＮＭＲ法にて粗生成物原料（Ｒ－４）の組成分析を行ったところ、スチレン７５質量％、アクリロニトリル１４質量％、Ｎ－フェニルマレイミド１０質量％、無水マレイン酸１質量％であった。得られた粗生成物原料の分析結果を表１－１に示す。 <Production example of crude product raw material (R-4)>
In an autoclave with a capacity of approximately 120 liters equipped with a stirrer, 81 parts by mass of styrene, 13 parts by mass of acrylonitrile, 1 part by mass of maleic anhydride, 0.4 parts by mass of α-methylstyrene dimer, and 25 parts by mass of methyl ethyl ketone were charged. After replacing the phase with nitrogen gas, the temperature was raised to 92° C. over 40 minutes while stirring. After raising the temperature, a solution of 4 parts by mass of maleic anhydride and 0.8 parts by mass of t-butylperoxy-2-ethylhexanoate dissolved in 22 parts by mass of methyl ethyl ketone was continuously heated for 5 hours while maintaining the temperature at 92°C. added. After the addition was completed, the temperature was raised to 120°C, and the reaction was carried out for 1 hour to complete the polymerization. Thereafter, 5 parts by mass of aniline and 0.1 parts by mass of triethylamine were added to the polymerization solution, and the mixture was reacted at 140° C. for 10 hours. After the completion of the reaction, the imidization reaction solution was put into a vent type screw extruder, and volatile components were removed to obtain pellet-shaped crude product raw material R-4. Composition analysis of the crude product raw material (R-4) using the C-13 NMR method described below revealed that it contained 75% by mass of styrene, 14% by mass of acrylonitrile, 10% by mass of N-phenylmaleimide, and 1% by mass of maleic anhydride. there were. The analysis results of the obtained crude product raw material are shown in Table 1-1.
　＜粗生成物原料（Ｒ－５）の製造例＞
　攪拌機を備えた容積約１２０リットルのオートクレーブ中にスチレン８９質量部、アクリロニトリル３質量部、マレイン酸無水物２質量部、α－メチルスチレンダイマーを０．４質量部、メチルエチルケトン５質量部を仕込み、気相部を窒素ガスで置換した後、撹拌しながら４０分かけて９２℃まで昇温した。昇温後９２℃を保持しながら、マレイン酸無水物６質量部とｔ－ブチルパーオキシ－２－エチルヘキサノエート０．８質量部をメチルエチルケトン３１質量部に溶解した溶液を５時間かけて連続的に添加した。添加終了後、１２０℃に昇温し、１時間反応させて重合を終了させた。その後、重合液にアニリン７質量部、トリエチルアミン０．１質量部を加え１４０℃で１０時間反応させた。反応終了後のイミド化反応液をベントタイプスクリュー式押出機に投入し、揮発分を除去してペレット状の粗生成物原料（Ｒ－５）を得た。後述のＣ－１３ＮＭＲ法にて粗生成物原料（Ｒ－５）の組成分析を行ったところ、スチレン８０質量％、アクリロニトリル４質量％、Ｎ－フェニルマレイミド１５質量％、無水マレイン酸１質量％であった。得られた粗生成物原料の分析結果を表１－１に示す。 <Production example of crude product raw material (R-5)>
In an autoclave with a capacity of approximately 120 liters equipped with a stirrer, 89 parts by mass of styrene, 3 parts by mass of acrylonitrile, 2 parts by mass of maleic anhydride, 0.4 parts by mass of α-methylstyrene dimer, and 5 parts by mass of methyl ethyl ketone were charged. After replacing the phase with nitrogen gas, the temperature was raised to 92° C. over 40 minutes while stirring. After raising the temperature, a solution of 6 parts by mass of maleic anhydride and 0.8 parts by mass of t-butylperoxy-2-ethylhexanoate dissolved in 31 parts by mass of methyl ethyl ketone was continuously heated for 5 hours while maintaining the temperature at 92°C. added. After the addition was completed, the temperature was raised to 120°C, and the reaction was carried out for 1 hour to complete the polymerization. Thereafter, 7 parts by mass of aniline and 0.1 parts by mass of triethylamine were added to the polymerization solution, and the mixture was reacted at 140° C. for 10 hours. After the completion of the reaction, the imidization reaction solution was put into a vent type screw extruder, and volatile components were removed to obtain a pellet-shaped crude product raw material (R-5). Composition analysis of the crude product raw material (R-5) using the C-13 NMR method described below revealed that it contained 80% by mass of styrene, 4% by mass of acrylonitrile, 15% by mass of N-phenylmaleimide, and 1% by mass of maleic anhydride. there were. The analysis results of the obtained crude product raw material are shown in Table 1-1.
　＜共重合体（Ｐ－１）～（Ｐ－５）の製造例＞
　＜共重合体（Ｐ－１）の製造例＞
　以下の（１）～（８）の操作を実施し、共重合体（Ｐ－１）を得た。
　（１）粗生成物原料（Ｒ－１）１０００ｇを、５リットルのメチルエチルケトンに溶解させ、粗生成物原料のメチルエチルケトン溶液を得た。
（２）メチルエチルケトン溶液にヘキサン１．６リットルを滴下して、溶解させた粗生成物原料の１０質量％を析出させた混合液を得た。
（３）混合液を濾過して、濾物と濾液に分離した。濾物は、２４時間風乾した後に、７０℃に設定した真空乾燥器で４時間乾燥させる乾燥工程を経て得た。
（４）（３）で得た濾液にヘキサン０．５リットルを滴下して、粗生成物原料の一部を析出させた混合液を得た。
（５）上記（３）～（４）の操作を繰り返し、５つの濾物を得た。各濾物は、２４時間風乾した後に、７０℃に設定した真空乾燥器で４時間乾燥させる乾燥工程を経て得た。
各濾物の重量は、得られた順に、１００ｇ、１４０ｇ、３００ｇ、２６０ｇ、２００ｇであった。
（６）５つ濾物のそれぞれについて、濾物の１０質量％のＴＨＦ溶液を調製した。
（７）濾物の１０質量％のＴＨＦ溶液と、Ｋ値が６６．７±１．０であり、塩素化度が５７±１．０％である塩素含有ポリマーの１０質量％のＴＨＦ溶液とを１：１の容量比で混合して作製した混合液における明度Ｌ＊を測定した。
（８）５つの濾物について、明度Ｌ＊が最も高い３番目に得られた濾物を共重合体（Ｐ－１）として得た。後述のＣ－１３ＮＭＲ法にて共重合体（Ｐ－１）の組成を確認したところ、スチレン７０質量％、アクリロニトリル８質量％、Ｎ－フェニルマレイミド２１質量％、無水マレイン酸１質量％であった。 <Production examples of copolymers (P-1) to (P-5)>
<Production example of copolymer (P-1)>
The following operations (1) to (8) were performed to obtain a copolymer (P-1).
(1) 1000 g of crude product raw material (R-1) was dissolved in 5 liters of methyl ethyl ketone to obtain a methyl ethyl ketone solution of the crude product raw material.
(2) 1.6 liters of hexane was added dropwise to the methyl ethyl ketone solution to obtain a mixed solution in which 10% by mass of the dissolved crude product raw material was precipitated.
(3) The mixed solution was filtered and separated into a filtrate and a filtrate. The filter material was obtained through a drying process of air drying for 24 hours and then drying in a vacuum dryer set at 70°C for 4 hours.
(4) 0.5 liters of hexane was added dropwise to the filtrate obtained in (3) to obtain a mixed solution in which a portion of the crude product raw material was precipitated.
(5) The above operations (3) and (4) were repeated to obtain five filtrates. Each filter material was obtained through a drying process of air drying for 24 hours and then drying in a vacuum dryer set at 70° C. for 4 hours.
The weight of each filter material was 100 g, 140 g, 300 g, 260 g, and 200 g in the order obtained.
(6) For each of the five filters, a 10% by mass THF solution of the filters was prepared.
(7) A 10% by mass THF solution of filter material and a 10% by mass THF solution of a chlorine-containing polymer with a K value of 66.7 ± 1.0 and a degree of chlorination of 57 ± 1.0%. The lightness L * of a mixed solution prepared by mixing the following at a volume ratio of 1:1 was measured.
(8) Among the five filter cakes, the third filter cake with the highest lightness L * was obtained as a copolymer (P-1). When the composition of the copolymer (P-1) was confirmed using the C-13 NMR method described below, it was found to be 70% by mass of styrene, 8% by mass of acrylonitrile, 21% by mass of N-phenylmaleimide, and 1% by mass of maleic anhydride. .
　＜共重合体（Ｐ－２）の製造例＞
　以下の（１）～（８）の操作を実施し、共重合体（Ｐ－２）を得た。
　（１）粗生成物原料（Ｒ－２）１０００ｇを、５リットルのメチルエチルケトンに溶解させ、粗生成物原料のメチルエチルケトン溶液を得た。
（２）メチルエチルケトン溶液にヘキサン１．６リットルを滴下して、溶解させた粗生成物原料の１０質量％を析出させた混合液を得た。
（３）混合液を濾過して、濾物と濾液に分離した。濾物は、２４時間風乾した後に、７０℃に設定した真空乾燥器で４時間乾燥させる乾燥工程を経て得た。
（４）（３）で得た濾液にヘキサン０．５リットルを滴下して、粗生成物原料の一部を析出させた混合液を得た。
（５）上記（３）～（４）の操作を繰り返し、５つの濾物を得た。各濾物は、２４時間風乾した後に、７０℃に設定した真空乾燥器で４時間乾燥させる乾燥工程を経て得た。
各濾物の重量は、得られた順に、１３０ｇ、２５０ｇ、２８０ｇ、２３０ｇ、１１０ｇであった。
（６）５つ濾物のそれぞれについて、濾物の１０質量％のＴＨＦ溶液を調製した。
（７）濾物の１０質量％のＴＨＦ溶液と、Ｋ値が６６．７±１．０であり、塩素化度が５７±１．０％である塩素含有ポリマーの１０質量％のＴＨＦ溶液とを１：１の容量比で混合して作製した混合液における明度Ｌ＊を測定した。
（８）５つの濾物について、明度Ｌ＊が最も高い３番目に得られた濾物を共重合体（Ｐ－２）として得た。 <Production example of copolymer (P-2)>
The following operations (1) to (8) were performed to obtain a copolymer (P-2).
(1) 1000 g of crude product raw material (R-2) was dissolved in 5 liters of methyl ethyl ketone to obtain a methyl ethyl ketone solution of the crude product raw material.
(2) 1.6 liters of hexane was added dropwise to the methyl ethyl ketone solution to obtain a mixed solution in which 10% by mass of the dissolved crude product raw material was precipitated.
(3) The mixed solution was filtered and separated into a filtrate and a filtrate. The filter material was obtained through a drying process of air drying for 24 hours and then drying in a vacuum dryer set at 70°C for 4 hours.
(4) 0.5 liters of hexane was added dropwise to the filtrate obtained in (3) to obtain a mixed solution in which a portion of the crude product raw material was precipitated.
(5) The above operations (3) and (4) were repeated to obtain five filtrates. Each filter material was obtained through a drying process of air drying for 24 hours and then drying in a vacuum dryer set at 70° C. for 4 hours.
The weight of each filter material was 130 g, 250 g, 280 g, 230 g, and 110 g in the order obtained.
(6) For each of the five filters, a 10% by mass THF solution of the filters was prepared.
(7) A 10% by mass THF solution of filter material and a 10% by mass THF solution of a chlorine-containing polymer with a K value of 66.7 ± 1.0 and a degree of chlorination of 57 ± 1.0%. The lightness L * of a mixed solution prepared by mixing the following at a volume ratio of 1:1 was measured.
(8) Among the five filter cakes, the third filter cake with the highest lightness L * was obtained as a copolymer (P-2).
　＜共重合体（Ｐ－３）の製造例＞
　以下の（１）～（８）の操作を実施し、共重合体（Ｐ－３）を得た。
　（１）粗生成物原料（Ｒ－３）１０００ｇを、５リットルのメチルエチルケトンに溶解させ、粗生成物原料のメチルエチルケトン溶液を得た。
（２）メチルエチルケトン溶液にヘキサン１．６リットルを滴下して、溶解させた粗生成物原料の１０質量％を析出させた混合液を得た。
（３）混合液を濾過して、濾物と濾液に分離した。濾物は、２４時間風乾した後に、７０℃に設定した真空乾燥器で４時間乾燥させる乾燥工程を経て得た。
（４）（３）で得た濾液にヘキサン０．５リットルを滴下して、粗生成物原料の一部を析出させた混合液を得た。
（５）上記（３）～（４）の操作を繰り返し、５つの濾物を得た。各濾物は、２４時間風乾した後に、７０℃に設定した真空乾燥器で４時間乾燥させる乾燥工程を経て得た。
各濾物の重量は、得られた順に、１８０ｇ、２００ｇ、２５０ｇ、２００ｇ、１７０ｇであった。
（６）５つ濾物のそれぞれについて、濾物の１０質量％のＴＨＦ溶液を調製した。
（７）濾物の１０質量％のＴＨＦ溶液と、Ｋ値が６６．７±１．０であり、塩素化度が５７±１．０％である塩素含有ポリマーの１０質量％のＴＨＦ溶液とを１：１の容量比で混合して作製した混合液における明度Ｌ＊を測定した。
（８）５つの濾物について、明度Ｌ＊が最も高い３番目に得られた濾物を共重合体（Ｐ－３）として得た。 <Production example of copolymer (P-3)>
The following operations (1) to (8) were performed to obtain a copolymer (P-3).
(1) 1000 g of crude product raw material (R-3) was dissolved in 5 liters of methyl ethyl ketone to obtain a methyl ethyl ketone solution of the crude product raw material.
(2) 1.6 liters of hexane was added dropwise to the methyl ethyl ketone solution to obtain a mixed solution in which 10% by mass of the dissolved crude product raw material was precipitated.
(3) The mixed solution was filtered and separated into a filtrate and a filtrate. The filter material was obtained through a drying process of air drying for 24 hours and then drying in a vacuum dryer set at 70°C for 4 hours.
(4) 0.5 liters of hexane was added dropwise to the filtrate obtained in (3) to obtain a mixed solution in which a portion of the crude product raw material was precipitated.
(5) The above operations (3) and (4) were repeated to obtain five filtrates. Each filter material was obtained through a drying process of air drying for 24 hours and then drying in a vacuum dryer set at 70° C. for 4 hours.
The weight of each filter material was 180 g, 200 g, 250 g, 200 g, and 170 g in the order obtained.
(6) For each of the five filters, a 10% by mass THF solution of the filters was prepared.
(7) A 10% by mass THF solution of filter material and a 10% by mass THF solution of a chlorine-containing polymer with a K value of 66.7 ± 1.0 and a degree of chlorination of 57 ± 1.0%. The lightness L * of a mixed solution prepared by mixing the following at a volume ratio of 1:1 was measured.
(8) Among the five filter cakes, the third filter cake with the highest lightness L * was obtained as a copolymer (P-3).
　＜共重合体（Ｐ－４）の製造例＞
　以下の（１）～（８）の操作を実施し、共重合体（Ｐ－４）を得た。
　（１）粗生成物原料（Ｒ－４）１０００ｇを、５リットルのメチルエチルケトンに溶解させ、粗生成物原料のメチルエチルケトン溶液を得た。
（２）メチルエチルケトン溶液にヘキサン１．６リットルを滴下して、溶解させた粗生成物原料の１０質量％を析出させた混合液を得た。
（３）混合液を濾過して、濾物と濾液に分離した。濾物は、２４時間風乾した後に、７０℃に設定した真空乾燥器で４時間乾燥させる乾燥工程を経て得た。
（４）（３）で得た濾液にヘキサン０．５リットルを滴下して、粗生成物原料の一部を析出させた混合液を得た。
（５）上記（３）～（４）の操作を繰り返し、５つの濾物を得た。各濾物は、２４時間風乾した後に、７０℃に設定した真空乾燥器で４時間乾燥させる乾燥工程を経て得た。
各濾物の重量は、得られた順に、１８０ｇ、２７０ｇ、３２０ｇ、１７０ｇ、６０ｇであった。
（６）５つ濾物のそれぞれについて、濾物の１０質量％のＴＨＦ溶液を調製した。
（７）濾物の１０質量％のＴＨＦ溶液と、Ｋ値が６６．７±１．０であり、塩素化度が５７±１．０％である塩素含有ポリマーの１０質量％のＴＨＦ溶液とを１：１の容量比で混合して作製した混合液における明度Ｌ＊を測定した。
（８）５つの濾物について、明度Ｌ＊が最も高い３番目に得られた濾物を共重合体（Ｐ－４）として得た。 <Production example of copolymer (P-4)>
The following operations (1) to (8) were performed to obtain a copolymer (P-4).
(1) 1000 g of crude product raw material (R-4) was dissolved in 5 liters of methyl ethyl ketone to obtain a methyl ethyl ketone solution of the crude product raw material.
(2) 1.6 liters of hexane was added dropwise to the methyl ethyl ketone solution to obtain a mixed solution in which 10% by mass of the dissolved crude product raw material was precipitated.
(3) The mixed solution was filtered and separated into a filtrate and a filtrate. The filter material was obtained through a drying process of air drying for 24 hours and then drying in a vacuum dryer set at 70°C for 4 hours.
(4) 0.5 liters of hexane was added dropwise to the filtrate obtained in (3) to obtain a mixed solution in which a portion of the crude product raw material was precipitated.
(5) The above operations (3) and (4) were repeated to obtain five filtrates. Each filter material was obtained through a drying process of air drying for 24 hours and then drying in a vacuum dryer set at 70° C. for 4 hours.
The weight of each filter material was 180 g, 270 g, 320 g, 170 g, and 60 g in the order obtained.
(6) For each of the five filters, a 10% by mass THF solution of the filters was prepared.
(7) A 10% by mass THF solution of filter material and a 10% by mass THF solution of a chlorine-containing polymer with a K value of 66.7 ± 1.0 and a degree of chlorination of 57 ± 1.0%. The lightness L * of a mixed solution prepared by mixing the following at a volume ratio of 1:1 was measured.
(8) Among the five filter cakes, the third filter cake with the highest lightness L * was obtained as a copolymer (P-4).
　＜共重合体（Ｐ－５）の製造例＞
　以下の（１）～（８）の操作を実施し、共重合体（Ｐ－５）を得た。
　（１）粗生成物原料（Ｒ－５）１０００ｇを、５リットルのメチルエチルケトンに溶解させ、粗生成物原料のメチルエチルケトン溶液を得た。
（２）メチルエチルケトン溶液にヘキサン１．６リットルを滴下して、溶解させた粗生成物原料の１０質量％を析出させた混合液を得た。
（３）混合液を濾過して、濾物と濾液に分離した。濾物は、２４時間風乾した後に、７０℃に設定した真空乾燥器で４時間乾燥させる乾燥工程を経て得た。
（４）（３）で得た濾液にヘキサン４リットルを滴下して、溶解させた粗生成物原料を析出させた混合液を得た。
（５）混合液をろ過して、濾物と濾液に分離した。各濾物は、２４時間風乾した後に、７０℃に設定した真空乾燥器で４時間乾燥させる乾燥工程を経て得た。
各濾物の重量は、得られた順に、１３０ｇ、８７０gであった。
（６）２つ濾物のそれぞれについて、濾物の１０質量％のＴＨＦ溶液を調製した。
（７）濾物の１０質量％のＴＨＦ溶液と、Ｋ値が６６．７±１．０であり、塩素化度が５７±１．０％である塩素含有ポリマーの１０質量％のＴＨＦ溶液とを１：１の容量比で混合して作製した混合液における明度Ｌ＊を測定した。
（８）２つの濾物について、明度Ｌ＊が最も高い１番目に得られた濾物を共重合体（Ｐ－５）として得た。後述のＣ－１３ＮＭＲ法にて共重合体（Ｐ－５）の組成を確認したところ、スチレン７６質量％、アクリロニトリル８質量％、Ｎ－フェニルマレイミド１５質量％、無水マレイン酸１質量％であった。 <Production example of copolymer (P-5)>
The following operations (1) to (8) were performed to obtain a copolymer (P-5).
(1) 1000 g of crude product raw material (R-5) was dissolved in 5 liters of methyl ethyl ketone to obtain a methyl ethyl ketone solution of the crude product raw material.
(2) 1.6 liters of hexane was added dropwise to the methyl ethyl ketone solution to obtain a mixed solution in which 10% by mass of the dissolved crude product raw material was precipitated.
(3) The mixed solution was filtered and separated into a filtrate and a filtrate. The filter material was obtained through a drying process of air drying for 24 hours and then drying in a vacuum dryer set at 70°C for 4 hours.
(4) 4 liters of hexane was added dropwise to the filtrate obtained in (3) to obtain a mixed solution in which the dissolved crude product raw material was precipitated.
(5) The mixed solution was filtered and separated into a filtrate and a filtrate. Each filter material was obtained through a drying process of air drying for 24 hours and then drying in a vacuum dryer set at 70° C. for 4 hours.
The weight of each filter material was 130 g and 870 g in the order obtained.
(6) For each of the two filters, a 10% by mass THF solution of the filters was prepared.
(7) A 10% by mass THF solution of filter material and a 10% by mass THF solution of a chlorine-containing polymer with a K value of 66.7 ± 1.0 and a degree of chlorination of 57 ± 1.0%. The lightness L * of a mixed solution prepared by mixing the following at a volume ratio of 1:1 was measured.
(8) Of the two filtrates, the first filtrate with the highest lightness L * was obtained as a copolymer (P-5). When the composition of the copolymer (P-5) was confirmed using the C-13 NMR method described below, it was found to be 76% by mass of styrene, 8% by mass of acrylonitrile, 15% by mass of N-phenylmaleimide, and 1% by mass of maleic anhydride. .
＜樹脂組成物＞
（使用原材料）各実施例や各比較例に使用した原材料を以下に示す。
（１）塩素含有ポリマー（ＰＶＣ）
・塩素含有ポリマー１－１：ＴＨ－１０００（製品名）、大洋塩ビ社製、Ｋ値６６．７±１．０、塩素化度５７．０±１．０％を使用した。
・塩素含有ポリマー１－２：ＨＡ－５３Ｋ（製品名）、徳山積水工業社製、Ｋ値６６．０±２．０、塩素化度６７．３±１．０％を使用した。
・塩素含有ポリマー１－３：ＨＡ－１５Ｅ（製品名）、徳山積水工業社製、Ｋ値５６．０±２．０、塩素化度６３．５±１．０％を使用した。
（２）塩素含有ポリマー用改質剤
・上述の製造例に従い得た共重合体（Ｐ－１）～（Ｐ－５）を実施例にかかる塩素含有ポリマー用改質剤として使用し、粗生成物原料（Ｒ－１）～（Ｒ－５）を比較例にかかる塩素含有ポリマー用改質剤として使用した。
（３）衝撃改質剤
・ＭＢＳ：メタブレンＣ－２２３Ａ（製品名）、三菱ケミカル社製を使用した。 <Resin composition>
(Raw materials used) The raw materials used in each example and each comparative example are shown below.
(1) Chlorine-containing polymer (PVC)
- Chlorine-containing polymer 1-1: TH-1000 (product name), manufactured by Taiyo PVC Co., Ltd., K value 66.7 ± 1.0, degree of chlorination 57.0 ± 1.0% was used.
- Chlorine-containing polymer 1-2: HA-53K (product name), manufactured by Tokuyama Sekisui Kogyo Co., Ltd., K value 66.0±2.0, degree of chlorination 67.3±1.0% was used.
- Chlorine-containing polymer 1-3: HA-15E (product name), manufactured by Tokuyama Sekisui Kogyo Co., Ltd., K value 56.0±2.0, degree of chlorination 63.5±1.0% was used.
(2) Modifier for chlorine-containing polymers Copolymers (P-1) to (P-5) obtained according to the above production examples were used as modifiers for chlorine-containing polymers according to the examples, and the crude Raw materials (R-1) to (R-5) were used as modifiers for chlorine-containing polymers according to comparative examples.
(3) Impact modifier/MBS: Metablen C-223A (product name), manufactured by Mitsubishi Chemical Corporation, was used.
実施例Ａ１～Ａ７、Ｂ１～Ｂ７、Ｃ１～Ｃ７、比較例Ａ１～Ａ８、Ｂ１～Ｂ８、Ｃ１～Ｃ８（塩素含有ポリマー用改質剤と塩素含有ポリマーとの混練混合）
　塩素含有ポリマー用改質剤と、あらかじめ安定剤、滑剤を加えてヘンシェルミキサーで混合した塩素含有ポリマーとを表１－１～１－３に示した配合割合でブレンドした後、テストロール（φ６×Ｌ１５テストロール、関西ロール社製）を用いてロールシートを作成し、ロールシートを重ねてプレス成形し、切削加工または打ち抜き加工により試験片を作成して、各物性値の測定を行った。なお、実施例Ａ１～Ａ７、比較例Ａ１～Ａ８における明度Ｌ＊は、各塩素含有ポリマー用改質剤と塩素含有ポリマー１－１とを用いた場合の値であり、実施例Ｂ１～Ｂ７、比較例Ｂ１～Ｂ８における明度Ｌ＊は、各塩素含有ポリマー用改質剤と塩素含有ポリマー１－２とを用いた場合の値であり、実施例Ｃ１～Ｃ７、比較例Ｃ１～Ｃ８における明度Ｌ＊は、各塩素含有ポリマー用改質剤と塩素含有ポリマー１－３とを用いた場合の値である。結果を表１－１～１－３に示す。 Examples A1 to A7, B1 to B7, C1 to C7, Comparative Examples A1 to A8, B1 to B8, C1 to C8 (kneading and mixing of a chlorine-containing polymer modifier and a chlorine-containing polymer)
After blending the modifier for chlorine-containing polymers and the chlorine-containing polymer, which was mixed in advance with a stabilizer and a lubricant using a Henschel mixer, in the proportions shown in Tables 1-1 to 1-3, a test roll (φ6× A roll sheet was created using an L15 test roll (manufactured by Kansai Roll Co., Ltd.), the roll sheets were stacked and press-formed, and a test piece was created by cutting or punching, and each physical property value was measured. Note that the lightness L * in Examples A1 to A7 and Comparative Examples A1 to A8 is the value when each chlorine-containing polymer modifier and chlorine-containing polymer 1-1 are used, and Examples B1 to B7, The lightness L * in Comparative Examples B1 to B8 is the value when using each chlorine-containing polymer modifier and chlorine-containing polymer 1-2, and the lightness L in Examples C1 to C7 and Comparative Examples C1 to C8 is * is the value when each chlorine-containing polymer modifier and chlorine-containing polymer 1-3 are used. The results are shown in Tables 1-1 to 1-3.
（明度Ｌ＊）
　明度Ｌ＊は、塩素含有ポリマー用改質剤の１０質量％のＴＨＦ溶液と、塩素含有ポリマーの１０質量％のＴＨＦ溶液とを１：１の容量比で混合して作製した混合液を光路長１０ｍｍであり光路幅１０ｍｍの光学セルにいれ、日本分光株式会社　分光光度計　Ｖ－６７０のＬ＊ａ＊ｂ＊モードで測定の条件において測定される値である。
各混合液の明度Ｌ＊は、下記記載の測定条件で測定した。
     装置名：分光光度計　Ｖ－６７０　(日本分光株式会社)
溶媒：ＴＨＦ
濃度：１０質量％
温度：２３℃
測定モード：Ｌ＊ａ＊ｂ＊モード
光学セル：光路長１０ｍｍ、光路幅１０ｍｍ (Lightness L * )
Lightness L * is the optical path length of a mixed solution prepared by mixing a 10% by mass THF solution of a chlorine-containing polymer modifier and a 10% by mass THF solution of a chlorine-containing polymer at a volume ratio of 1:1. This value is measured under the conditions of measurement in the L * a * b * mode of a spectrophotometer V-670 manufactured by JASCO Corporation, in an optical cell with an optical path width of 10 mm.
The lightness L * of each liquid mixture was measured under the measurement conditions described below.
Equipment name: Spectrophotometer V-670 (JASCO Corporation)
Solvent: THF
Concentration: 10% by mass
Temperature: 23℃
Measurement mode: L * a * b * mode Optical cell: Optical path length 10mm, optical path width 10mm
（組成分析）
各塩素含有ポリマー用改質剤（共重合体及び粗生成物原料）の組成分析は、Ｃ－１３ＮＭＲ法にて下記記載の測定条件で測定した。
　　　装置名：ＦＴ－ＮＭＲ  ＡＶＡＮＣＥ３００（ＢＲＵＫＥＲ社製）
　　　溶媒：重水素化クロロホルム
　　　濃度：１４質量％
　　　温度：２７℃
　　　積算回数：８０００回 (composition analysis)
The compositional analysis of each chlorine-containing polymer modifier (copolymer and crude product raw material) was measured by C-13 NMR method under the measurement conditions described below.
Equipment name: FT-NMR AVANCE300 (manufactured by BRUKER)
Solvent: Deuterated chloroform Concentration: 14% by mass
Temperature: 27℃
Accumulated number of times: 8000 times
（ビカット軟化点）
　樹脂組成物のビカット軟化点は、ＪＩＳ　Ｋ７２０６：１９９９に基づき、５０法（荷重５０Ｎ、昇温速度５０℃／時間）で試験片は２０ｍｍ×２０ｍｍ、厚さ４ｍｍのものを用いて測定した。なお、測定機は東洋精機製作所社製ＨＤＴ＆ＶＳＰＴ試験装置を使用した。 (Vicat softening point)
The Vicat softening point of the resin composition was measured based on JIS K7206:1999 using the 50 method (load 50 N, temperature increase rate 50° C./hour) using a test piece measuring 20 mm×20 mm and 4 mm thick. The measuring device used was an HDT & VSPT testing device manufactured by Toyo Seiki Seisakusho.
（シャルピー衝撃強度）
　樹脂組成物のシャルピー衝撃強度は、ＪＩＳ　Ｋ－７１１１に準拠して、ノッチあり試験片を用い、打撃方向はエッジワイズを採用して相対湿度５０％、雰囲気温度２３℃の条件で測定した。なお、測定機は東洋精機製作所社製デジタル衝撃試験機を使用した。 (Charpy impact strength)
The Charpy impact strength of the resin composition was measured in accordance with JIS K-7111 using a notched test piece and using an edgewise impact direction at a relative humidity of 50% and an ambient temperature of 23°C. The measuring device used was a digital impact tester manufactured by Toyo Seiki Seisakusho.
　本発明にかかる塩素含有ポリマー用改質剤を採用した実施例Ａ１～Ａ５、Ｂ１～Ｂ５、Ｃ１～Ｃ５では、塩素含有ポリマーの耐熱性及び耐衝撃性が十分に向上された。
　これに対し、本発明の規定を満たさない塩素含有ポリマー用改質剤を採用した比較例Ａ１～Ａ５、Ｂ１～Ｂ５、Ｃ１～Ｃ５では、塩素含有ポリマーの耐熱性や耐衝撃性が十分に向上されないものがあった。 In Examples A1 to A5, B1 to B5, and C1 to C5 in which the modifier for chlorine-containing polymers according to the present invention was employed, the heat resistance and impact resistance of the chlorine-containing polymers were sufficiently improved.
On the other hand, in Comparative Examples A1 to A5, B1 to B5, and C1 to C5, which adopted modifiers for chlorine-containing polymers that do not meet the provisions of the present invention, the heat resistance and impact resistance of the chlorine-containing polymers were sufficiently improved. There was something that wasn't done.
　粗生成物原料（Ｒ－１）を用いた本発明にかかる塩素含有ポリマー用改質剤の製造方法の一実施態様を示す。表１－４中、改質剤（Ｒ－１）は、粗生成物原料（Ｒ－１）である。また、上述の共重合体（Ｐ－１）の製造例に関連して、改質剤（Ｐ－１－１）は、１回目の（３）の操作により得られた１つ目の濾物であり、改質剤（Ｐ－１－２）～（Ｐ－１－５）は、それぞれ、（１）～（７）の操作を経た後で（３）～（４）の操作を繰り返した際に、２～５回目の（３）の操作により得られた２つ目～５つ目の濾物である。３つ目の濾物である改質剤（Ｐ－１－３）が、共重合体（Ｐ－１）に該当する。 One embodiment of the method for producing a modifier for chlorine-containing polymers according to the present invention using the crude product raw material (R-1) is shown. In Table 1-4, the modifier (R-1) is the crude product raw material (R-1). In addition, in relation to the above-mentioned production example of copolymer (P-1), the modifier (P-1-1) was added to the first filtrate obtained by the first operation (3). Modifiers (P-1-2) to (P-1-5) were obtained by repeating operations (3) to (4) after undergoing operations (1) to (7), respectively. In this case, these are the second to fifth filtrates obtained from the second to fifth operations (3). The third filter material, the modifier (P-1-3), corresponds to the copolymer (P-1).
　粗生成物原料（Ｒ－５）を用いた本発明にかかる塩素含有ポリマー用改質剤の製造方法の一実施態様を示す。表１－５中、改質剤（Ｒ－５）は、粗生成物原料（Ｒ－５）である。また、上述の共重合体（Ｐ－５）の製造例に関連して、改質剤（Ｐ－５－１）は、（３）の操作により得られた１つ目の濾物であり、改質剤（Ｐ－５－２）は、（５）の操作により得られた２つ目の濾物である。１つ目の濾物である改質剤（Ｐ－５－１）が、共重合体（Ｐ－５）に該当する。 One embodiment of the method for producing a modifier for chlorine-containing polymers according to the present invention using a crude product raw material (R-5) is shown. In Table 1-5, the modifier (R-5) is the crude product raw material (R-5). Furthermore, in relation to the above-mentioned production example of the copolymer (P-5), the modifier (P-5-1) is the first filtrate obtained by the operation (3), Modifier (P-5-2) is the second filtrate obtained by operation (5). The first filter material, the modifier (P-5-1), corresponds to the copolymer (P-5).
［産業上の利用可能性］
　本発明の第１観点により、塩素含有ポリマーの耐熱性及び耐衝撃性を向上できる塩素含有ポリマー用改質剤、塩素含有ポリマー用改質剤と塩素含有ポリマーとを含む樹脂組成物及びその成形体が提供され、耐熱性及び耐衝撃性が要求される成形品に好適に利用される。 [Industrial applicability]
According to the first aspect of the present invention, a modifier for a chlorine-containing polymer that can improve the heat resistance and impact resistance of a chlorine-containing polymer, a resin composition containing a modifier for a chlorine-containing polymer and a chlorine-containing polymer, and a molded article thereof It is suitably used for molded products that require heat resistance and impact resistance.
（第２観点）
　表中、Ｓｔｙはスチレン、ＡＮはアクリロニトリル、ＮＰＭＩはＮ－フェニルマレイミド、ＭＡＨは無水マレイン酸、ＭＢＳはメチルメタクリレート－ブタジエン－スチレン樹脂、ＰＥはポリエチレンを示す。 (Second perspective)
In the table, Sty represents styrene, AN represents acrylonitrile, NPMI represents N-phenylmaleimide, MAH represents maleic anhydride, MBS represents methyl methacrylate-butadiene-styrene resin, and PE represents polyethylene.
　＜マレイミド系共重合体（Ｐ－２－１）の製造例＞
　攪拌機を備えた容積約１２０リットルのオートクレーブ中にスチレン７７質量部、アクリロニトリル９質量部、マレイン酸無水物４質量部、α－メチルスチレンダイマーを０．４質量部、メチルエチルケトン３８質量部を仕込み、気相部を窒素ガスで置換した後、撹拌しながら４０分かけて９２℃まで昇温した。昇温後９２℃を保持しながら、マレイン酸無水物９質量部とｔ－ブチルパーオキシ－２－エチルヘキサノエート０．８質量部をメチルエチルケトン４７質量部に溶解した溶液を５時間かけて連続的に添加した。添加終了後、１２０℃に昇温し、１時間反応させて重合を終了させた。その後、重合液にアニリン１２質量部、トリエチルアミン０．２質量部を加え１４０℃で１０時間反応させた。反応終了後のイミド化反応液をベントタイプスクリュー式押出機に投入し、揮発分を除去してペレット状のマレイミド系共重合体の粗成生物原料（Ｒ－２－１）を得た。後述のＣ－１３ＮＭＲ法にてマレイミド系共重合体の粗成生物原料（Ｒ－２－１）の組成分析を行ったところ、スチレン７０質量％、アクリロニトリル８質量％、Ｎ－フェニルマレイミド２１質量％、無水マレイン酸１質量％であった。 <Production example of maleimide copolymer (P-2-1)>
In an autoclave with a capacity of approximately 120 liters equipped with a stirrer, 77 parts by mass of styrene, 9 parts by mass of acrylonitrile, 4 parts by mass of maleic anhydride, 0.4 parts by mass of α-methylstyrene dimer, and 38 parts by mass of methyl ethyl ketone were charged. After replacing the phase with nitrogen gas, the temperature was raised to 92° C. over 40 minutes while stirring. After raising the temperature, a solution of 9 parts by mass of maleic anhydride and 0.8 parts by mass of t-butylperoxy-2-ethylhexanoate dissolved in 47 parts by mass of methyl ethyl ketone was continuously heated for 5 hours while maintaining the temperature at 92°C. added. After the addition was completed, the temperature was raised to 120°C, and the reaction was carried out for 1 hour to complete the polymerization. Thereafter, 12 parts by mass of aniline and 0.2 parts by mass of triethylamine were added to the polymerization solution and reacted at 140° C. for 10 hours. After the completion of the reaction, the imidization reaction solution was put into a vent type screw extruder, and volatile components were removed to obtain a crude biological raw material (R-2-1) for a maleimide copolymer in the form of pellets. When the composition of the crude biological raw material (R-2-1) for maleimide copolymer was analyzed using the C-13 NMR method described below, it was found to be 70% by mass of styrene, 8% by mass of acrylonitrile, and 21% by mass of N-phenylmaleimide. , 1% by mass of maleic anhydride.
　以下の（１）～（６）の操作を実施し、マレイミド系共重合体（Ｐ－２－１）を得た。
　（１）粗生成物原料（Ｒ－２－１）１０００ｇを、５リットルのメチルエチルケトンに溶解させ、粗生成物原料のメチルエチルケトン溶液を得た。
（２）メチルエチルケトン溶液にヘキサン１．６リットルを滴下して、溶解させた粗生成物原料の１０質量％を析出させた混合液を得た。
（３）混合液を濾過して、濾物と濾液に分離した。濾物は、２４時間風乾した後に、７０℃に設定した真空乾燥器で４時間乾燥させる乾燥工程を経て得た。
（４）（３）で得た濾液にヘキサン０．５リットルを滴下して、粗生成物原料の一部を析出させた混合液を得た。
（５）上記（３）～（４）の操作を繰り返し、５つの濾物を得た。各濾物は、２４時間風乾した後に、７０℃に設定した真空乾燥器で４時間乾燥させる乾燥工程を経て得た。
各濾物の重量は、得られた順に、１００ｇ、１４０ｇ、３００ｇ、２６０ｇ、２００ｇであった。
（６）５つの濾物について、３番目に得られた濾物をマレイミド系共重合体（Ｐ－２－１）として得た。後述のＣ－１３ＮＭＲ法にてマレイミド系共重合体（Ｐ－２－１）の組成を確認したところ、スチレン７０質量％、アクリロニトリル８質量％、Ｎ－フェニルマレイミド２１質量％、無水マレイン酸１質量％であった。得られたマレイミド系共重合体の分析結果を表２－１に示す。
　また、マレイミド系共重合体（Ｐ－２－１）、塩素含有ポリマー２－１、２－２、２－３のそれぞれの１０質量%のＴＨＦ溶液を調製し、共重合体と塩素含有ポリマーのＴＨＦ溶液を１：１の容量比で混合して作製した混合液における明度Ｌ＊を測定した結果、それぞれ、９８，９２，９０であった。 The following operations (1) to (6) were performed to obtain a maleimide copolymer (P-2-1).
(1) 1000 g of crude product raw material (R-2-1) was dissolved in 5 liters of methyl ethyl ketone to obtain a methyl ethyl ketone solution of the crude product raw material.
(2) 1.6 liters of hexane was added dropwise to the methyl ethyl ketone solution to obtain a mixed solution in which 10% by mass of the dissolved crude product raw material was precipitated.
(3) The mixed solution was filtered and separated into a filtrate and a filtrate. The filter material was obtained through a drying process of air drying for 24 hours and then drying in a vacuum dryer set at 70°C for 4 hours.
(4) 0.5 liters of hexane was added dropwise to the filtrate obtained in (3) to obtain a mixed solution in which a portion of the crude product raw material was precipitated.
(5) The above operations (3) and (4) were repeated to obtain five filtrates. Each filter material was obtained through a drying process of air drying for 24 hours and then drying in a vacuum dryer set at 70° C. for 4 hours.
The weight of each filter material was 100 g, 140 g, 300 g, 260 g, and 200 g in the order obtained.
(6) Among the five filtrates, the third one obtained was obtained as a maleimide copolymer (P-2-1). When the composition of the maleimide copolymer (P-2-1) was confirmed using the C-13 NMR method described below, it was found to be 70% by mass of styrene, 8% by mass of acrylonitrile, 21% by mass of N-phenylmaleimide, and 1% by mass of maleic anhydride. %Met. The analysis results of the obtained maleimide copolymer are shown in Table 2-1.
In addition, 10% by mass THF solutions of the maleimide copolymer (P-2-1) and chlorine-containing polymers 2-1, 2-2, and 2-3 were prepared, and the copolymer and chlorine-containing polymer were mixed. The lightness L* of the mixed liquid prepared by mixing THF solutions at a volume ratio of 1:1 was measured, and the results were 98, 92, and 90, respectively.
　＜マレイミド系共重合体（Ｐ－２－２）の製造例＞
　攪拌機を備えた容積約１２０リットルのオートクレーブ中にスチレン７１質量部、アクリロニトリル１６質量部、マレイン酸無水物３質量部、α－メチルスチレンダイマーを０．４質量部、メチルエチルケトン３６質量部を仕込み、気相部を窒素ガスで置換した後、撹拌しながら４０分かけて９２℃まで昇温した。昇温後９２℃を保持しながら、マレイン酸無水物１０質量部とｔ－ブチルパーオキシ－２－エチルヘキサノエート０．８質量部をメチルエチルケトン５０質量部に溶解した溶液を５時間かけて連続的に添加した。添加終了後、１２０℃に昇温し、１時間反応させて重合を終了させた。その後、重合液にアニリン１１質量部、トリエチルアミン０．２質量部を加え１４０℃で１０時間反応させた。反応終了後のイミド化反応液をベントタイプスクリュー式押出機に投入し、揮発分を除去してペレット状のマレイミド系共重合体の粗成生物原料（Ｒ－２－２）を得た。後述のＣ－１３ＮＭＲ法にてマレイミド系共重合体の粗成生物原料（Ｒ－２－２）の組成分析を行ったところ、スチレン６５質量％、アクリロニトリル１４質量％、Ｎ－フェニルマレイミド２０質量％、無水マレイン酸１質量％であった。 <Production example of maleimide copolymer (P-2-2)>
In an autoclave with a capacity of about 120 liters equipped with a stirrer, 71 parts by mass of styrene, 16 parts by mass of acrylonitrile, 3 parts by mass of maleic anhydride, 0.4 parts by mass of α-methylstyrene dimer, and 36 parts by mass of methyl ethyl ketone were charged. After replacing the phase with nitrogen gas, the temperature was raised to 92° C. over 40 minutes while stirring. After raising the temperature, a solution of 10 parts by mass of maleic anhydride and 0.8 parts by mass of t-butylperoxy-2-ethylhexanoate dissolved in 50 parts by mass of methyl ethyl ketone was continuously heated for 5 hours while maintaining the temperature at 92°C. added. After the addition was completed, the temperature was raised to 120°C, and the reaction was carried out for 1 hour to complete the polymerization. Thereafter, 11 parts by mass of aniline and 0.2 parts by mass of triethylamine were added to the polymerization solution, and the mixture was reacted at 140° C. for 10 hours. After the completion of the reaction, the imidization reaction solution was put into a vent type screw extruder, and volatile components were removed to obtain a crude biological raw material (R-2-2) for a maleimide copolymer in the form of pellets. When the composition of the crude biological raw material (R-2-2) for maleimide copolymer was analyzed using the C-13 NMR method described below, it was found to be 65% by mass of styrene, 14% by mass of acrylonitrile, and 20% by mass of N-phenylmaleimide. , 1% by mass of maleic anhydride.
　以下の（１）～（６）の操作を実施し、マレイミド系共重合体（Ｐ－２－２）を得た。
　（１）粗生成物原料（Ｒ－２－２）１０００ｇを、５リットルのメチルエチルケトンに溶解させ、粗生成物原料のメチルエチルケトン溶液を得た。
（２）メチルエチルケトン溶液にヘキサン１．６リットルを滴下して、溶解させた粗生成物原料の１０質量％を析出させた混合液を得た。
（３）混合液を濾過して、濾物と濾液に分離した。濾物は、２４時間風乾した後に、７０℃に設定した真空乾燥器で４時間乾燥させる乾燥工程を経て得た。
（４）（３）で得た濾液にヘキサン０．５リットルを滴下して、粗生成物原料の一部を析出させた混合液を得た。
（５）上記（３）～（４）の操作を繰り返し、５つの濾物を得た。各濾物は、２４時間風乾した後に、７０℃に設定した真空乾燥器で４時間乾燥させる乾燥工程を経て得た。
各濾物の重量は、得られた順に、１８０ｇ、２００ｇ、２５０ｇ、２００ｇ、１７０ｇであった。
（６）５つの濾物について、３番目に得られた濾物をマレイミド系共重合体（Ｐ－２－２）として得た。後述のＣ－１３ＮＭＲ法にてマレイミド系共重合体（Ｐ－２－２）の組成を確認したところ、スチレン６５質量％、アクリロニトリル１４質量％、Ｎ－フェニルマレイミド２０質量％、無水マレイン酸１質量％であった。得られたマレイミド系共重合体の分析結果を表２－１に示す。
また、マレイミド系共重合体（Ｐ－２－２）、塩素含有ポリマー２－１、２－２、２－３のそれぞれの１０質量%のＴＨＦ溶液を調製し、共重合体と塩素含有ポリマーのＴＨＦ溶液を１：１の容量比で混合して作製した混合液における明度Ｌ＊を測定した結果、それぞれ、６０，５０，４３であった。 The following operations (1) to (6) were performed to obtain a maleimide copolymer (P-2-2).
(1) 1000 g of crude product raw material (R-2-2) was dissolved in 5 liters of methyl ethyl ketone to obtain a methyl ethyl ketone solution of the crude product raw material.
(2) 1.6 liters of hexane was added dropwise to the methyl ethyl ketone solution to obtain a mixed solution in which 10% by mass of the dissolved crude product raw material was precipitated.
(3) The mixed solution was filtered and separated into a filtrate and a filtrate. The filter material was obtained through a drying process of air drying for 24 hours and then drying in a vacuum dryer set at 70°C for 4 hours.
(4) 0.5 liters of hexane was added dropwise to the filtrate obtained in (3) to obtain a mixed solution in which a portion of the crude product raw material was precipitated.
(5) The above operations (3) and (4) were repeated to obtain five filtrates. Each filter material was obtained through a drying process of air drying for 24 hours and then drying in a vacuum dryer set at 70° C. for 4 hours.
The weight of each filter material was 180 g, 200 g, 250 g, 200 g, and 170 g in the order obtained.
(6) Among the five filtrates, the third one obtained was obtained as a maleimide copolymer (P-2-2). When the composition of the maleimide copolymer (P-2-2) was confirmed using the C-13 NMR method described below, it was found to be 65% by mass of styrene, 14% by mass of acrylonitrile, 20% by mass of N-phenylmaleimide, and 1% by mass of maleic anhydride. %Met. The analysis results of the obtained maleimide copolymer are shown in Table 2-1.
In addition, 10% by mass THF solutions of the maleimide copolymer (P-2-2) and chlorine-containing polymers 2-1, 2-2, and 2-3 were prepared, and the copolymer and chlorine-containing polymer were mixed. The lightness L* of the mixed liquid prepared by mixing THF solutions at a volume ratio of 1:1 was measured, and the results were 60, 50, and 43, respectively.
　＜マレイミド系共重合体（Ｐ－２－３）の製造例＞
　攪拌機を備えた容積約１２０リットルのオートクレーブ中にスチレン８９質量部、アクリロニトリル３質量部、マレイン酸無水物２質量部、α－メチルスチレンダイマーを０．４質量部、メチルエチルケトン５質量部を仕込み、気相部を窒素ガスで置換した後、撹拌しながら４０分かけて９２℃まで昇温した。昇温後９２℃を保持しながら、マレイン酸無水物６質量部とｔ－ブチルパーオキシ－２－エチルヘキサノエート０．８質量部をメチルエチルケトン３１質量部に溶解した溶液を５時間かけて連続的に添加した。添加終了後、１２０℃に昇温し、１時間反応させて重合を終了させた。その後、重合液にアニリン７質量部、トリエチルアミン０．１質量部を加え１４０℃で１０時間反応させた。反応終了後のイミド化反応液をベントタイプスクリュー式押出機に投入し、揮発分を除去してペレット状のマレイミド系共重合体の粗成生物原料（Ｒ－２－３）を得た。後述のＣ－１３ＮＭＲ法にてマレイミド系共重合体の粗成生物原料（Ｒ－２－３）の組成分析を行ったところ、スチレン８０質量％、アクリロニトリル４質量％、Ｎ－フェニルマレイミド１５質量％、無水マレイン酸１質量％であった。 <Production example of maleimide copolymer (P-2-3)>
In an autoclave with a capacity of approximately 120 liters equipped with a stirrer, 89 parts by mass of styrene, 3 parts by mass of acrylonitrile, 2 parts by mass of maleic anhydride, 0.4 parts by mass of α-methylstyrene dimer, and 5 parts by mass of methyl ethyl ketone were charged. After replacing the phase with nitrogen gas, the temperature was raised to 92° C. over 40 minutes while stirring. After raising the temperature, a solution of 6 parts by mass of maleic anhydride and 0.8 parts by mass of t-butylperoxy-2-ethylhexanoate dissolved in 31 parts by mass of methyl ethyl ketone was continuously heated for 5 hours while maintaining the temperature at 92°C. added. After the addition was completed, the temperature was raised to 120°C, and the reaction was carried out for 1 hour to complete the polymerization. Thereafter, 7 parts by mass of aniline and 0.1 parts by mass of triethylamine were added to the polymerization solution, and the mixture was reacted at 140° C. for 10 hours. After the completion of the reaction, the imidization reaction solution was put into a vent type screw extruder, and volatile components were removed to obtain a crude biological raw material (R-2-3) for a maleimide copolymer in the form of pellets. A compositional analysis of the crude biological raw material (R-2-3) for the maleimide copolymer using the C-13 NMR method described below revealed that it was 80% by mass of styrene, 4% by mass of acrylonitrile, and 15% by mass of N-phenylmaleimide. , 1% by mass of maleic anhydride.
　以下の（１）～（６）の操作を実施し、マレイミド系共重合体（Ｐ－２－３）を得た。
　（１）粗生成物原料（Ｒ－２－３）１０００ｇを、５リットルのメチルエチルケトンに溶解させ、粗生成物原料のメチルエチルケトン溶液を得た。
（２）メチルエチルケトン溶液にヘキサン４リットルを滴下して、溶解させた粗生成物原料の１０質量％を析出させた混合液を得た。
（３）混合液を濾過して、濾物と濾液に分離した。濾物は、２４時間風乾した後に、７０℃に設定した真空乾燥器で４時間乾燥させる乾燥工程を経て得た。
（４）混合液をろ過して、濾物と濾液に分離した。各濾物は、２４時間風乾した後に、７０℃に設定した真空乾燥器で４時間乾燥させる乾燥工程を経て得た。
各濾物の重量は、得られた順に、１３０ｇ、８７０gであった。
（５）２つの濾物について、１番目に得られた濾物をマレイミド系共重合体（Ｐ－２－３）として得た。後述のＣ－１３ＮＭＲ法にてマレイミド系共重合体（Ｐ－２－３）の組成を確認したところ、スチレン７６質量％、アクリロニトリル８質量％、Ｎ－フェニルマレイミド１５質量％、無水マレイン酸１質量％であった。得られたマレイミド系共重合体の分析結果を表２－１に示す。
また、マレイミド系共重合体（Ｐ－２－３）、塩素含有ポリマー２－１、２－２、２－３のそれぞれの１０質量%のＴＨＦ溶液を調製し、共重合体と塩素含有ポリマーのＴＨＦ溶液を１：１の容量比で混合して作製した混合液における明度Ｌ＊を測定した結果、それぞれ、６９，６７，４２ であった。 The following operations (1) to (6) were performed to obtain a maleimide copolymer (P-2-3).
(1) 1000 g of crude product raw material (R-2-3) was dissolved in 5 liters of methyl ethyl ketone to obtain a methyl ethyl ketone solution of the crude product raw material.
(2) 4 liters of hexane was added dropwise to the methyl ethyl ketone solution to obtain a mixed solution in which 10% by mass of the dissolved crude product raw material was precipitated.
(3) The mixed solution was filtered and separated into a filtrate and a filtrate. The filter material was obtained through a drying process of air drying for 24 hours and then drying in a vacuum dryer set at 70°C for 4 hours.
(4) The mixed solution was filtered and separated into a filtrate and a filtrate. Each filter material was obtained through a drying process of air drying for 24 hours and then drying in a vacuum dryer set at 70° C. for 4 hours.
The weight of each filter material was 130 g and 870 g in the order obtained.
(5) Of the two filtrates, the first filtrate obtained was obtained as a maleimide copolymer (P-2-3). When the composition of the maleimide copolymer (P-2-3) was confirmed using the C-13 NMR method described below, it was found to be 76% by mass of styrene, 8% by mass of acrylonitrile, 15% by mass of N-phenylmaleimide, and 1% by mass of maleic anhydride. %Met. The analysis results of the obtained maleimide copolymer are shown in Table 2-1.
In addition, 10% by mass THF solutions of the maleimide copolymer (P-2-3) and chlorine-containing polymers 2-1, 2-2, and 2-3 were prepared, and the copolymer and chlorine-containing polymer were mixed. The lightness L* of the mixed solution prepared by mixing THF solutions at a volume ratio of 1:1 was measured, and the results were 69, 67, and 42, respectively.
　＜マレイミド系共重合体（Ｐ－２－４）の製造例＞
　攪拌機を備えた容積約１２０リットルのオートクレーブ中にスチレン９５質量部、マレイン酸無水物１質量部、α－メチルスチレンダイマーを０．４質量部、メチルエチルケトン４３質量部を仕込み、気相部を窒素ガスで置換した後、撹拌しながら４０分かけて９２℃まで昇温した。昇温後９２℃を保持しながら、マレイン酸無水物５質量部とｔ－ブチルパーオキシ－２－エチルヘキサノエート０．８質量部をメチルエチルケトン２３質量部に溶解した溶液を５時間かけて連続的に添加した。添加終了後、１２０℃に昇温し、１時間反応させて重合を終了させた。その後、重合液にアニリン５質量部、トリエチルアミン０．１質量部を加え１４０℃で１５時間反応させた。反応終了後のイミド化反応液をベントタイプスクリュー式押出機に投入し、揮発分を除去してペレット状のマレイミド系共重合体の粗成生物原料（Ｒ－２－４）を得た。後述のＣ－１３ＮＭＲ法にてマレイミド系共重合体の粗成生物原料（Ｒ－２－４）の組成分析を行ったところ、スチレン９０質量％、アクリロニトリル０質量％、Ｎ－フェニルマレイミド１０質量％、無水マレイン酸０質量％であった。 <Production example of maleimide copolymer (P-2-4)>
In an autoclave with a capacity of approximately 120 liters equipped with a stirrer, 95 parts by mass of styrene, 1 part by mass of maleic anhydride, 0.4 parts by mass of α-methylstyrene dimer, and 43 parts by mass of methyl ethyl ketone were charged, and the gas phase was filled with nitrogen gas. After replacing the mixture with , the temperature was raised to 92° C. over 40 minutes while stirring. After raising the temperature, a solution of 5 parts by mass of maleic anhydride and 0.8 parts by mass of t-butylperoxy-2-ethylhexanoate dissolved in 23 parts by mass of methyl ethyl ketone was continuously heated for 5 hours while maintaining the temperature at 92°C. added. After the addition was completed, the temperature was raised to 120°C, and the reaction was carried out for 1 hour to complete the polymerization. Thereafter, 5 parts by mass of aniline and 0.1 parts by mass of triethylamine were added to the polymerization solution, and the mixture was reacted at 140° C. for 15 hours. After the completion of the reaction, the imidization reaction solution was put into a vent type screw extruder, and the volatile components were removed to obtain a crude biological raw material (R-2-4) for a maleimide copolymer in the form of pellets. When the composition of the crude biological raw material (R-2-4) for maleimide copolymer was analyzed using the C-13 NMR method described below, it was found to be 90% by mass of styrene, 0% by mass of acrylonitrile, and 10% by mass of N-phenylmaleimide. , maleic anhydride was 0% by mass.
　得られたマレイミド系共重合体に精製操作は行わず、粗成生物原料(Ｒ－２－４)を共重合体(Ｐ－２－４)とした。得られたマレイミド系共重合体の分析結果を表２－１に示す。
また、マレイミド系共重合体（Ｐ－２－４）、塩素含有ポリマー２－１、２－２、２－３のそれぞれの１０質量%のＴＨＦ溶液を調製し、共重合体と塩素含有ポリマーのＴＨＦ溶液を１：１の容量比で混合して作製した混合液における明度Ｌ＊を測定した結果、それぞれ、１８，１６，１４ であった。 The resulting maleimide copolymer was not purified, and the crude biological raw material (R-2-4) was used as a copolymer (P-2-4). The analysis results of the obtained maleimide copolymer are shown in Table 2-1.
In addition, 10% by mass THF solutions of each of the maleimide copolymer (P-2-4) and chlorine-containing polymers 2-1, 2-2, and 2-3 were prepared, and the copolymer and chlorine-containing polymer were mixed. The lightness L* of the mixed liquid prepared by mixing THF solutions at a volume ratio of 1:1 was measured, and the results were 18, 16, and 14, respectively.
　＜共重合体（Ｐ－２－５）の製造例＞
　攪拌機を備えた容積約１２０リットルのオートクレーブ中にスチレン７７質量部、アクリロニトリル２３質量部、α－メチルスチレンダイマーを０．４質量部、メチルエチルケトン３８質量部を仕込み、気相部を窒素ガスで置換した後、撹拌しながら４０分かけて９２℃まで昇温した。昇温後９２℃を保持しながら、ｔ－ブチルパーオキシ－２－エチルヘキサノエート０．８質量部をメチルエチルケトン７質量部に溶解した溶液を５時間かけて連続的に添加した。添加終了後、１２０℃に昇温し、１時間反応させて重合を終了させた。反応終了後の反応液をベントタイプスクリュー式押出機に投入し、揮発分を除去してペレット状の共重合体の粗成生物原料（Ｒ－２－５）を得た。後述のＣ－１３ＮＭＲ法にて共重合体の粗成生物原料（Ｒ－２－５）の組成分析を行ったところ、スチレン７７質量％、アクリロニトリル２３質量％、Ｎ－フェニルマレイミド０質量％、無水マレイン酸０質量％であった。 <Production example of copolymer (P-2-5)>
In an autoclave with a volume of approximately 120 liters equipped with a stirrer, 77 parts by mass of styrene, 23 parts by mass of acrylonitrile, 0.4 parts by mass of α-methylstyrene dimer, and 38 parts by mass of methyl ethyl ketone were charged, and the gas phase was replaced with nitrogen gas. Thereafter, the temperature was raised to 92° C. over 40 minutes while stirring. After raising the temperature, a solution of 0.8 parts by mass of t-butylperoxy-2-ethylhexanoate dissolved in 7 parts by mass of methyl ethyl ketone was continuously added over 5 hours while maintaining the temperature at 92°C. After the addition was completed, the temperature was raised to 120°C, and the reaction was carried out for 1 hour to complete the polymerization. After the reaction was completed, the reaction solution was put into a vent type screw extruder to remove volatile components to obtain a crude biological raw material (R-2-5) of a copolymer in the form of pellets. When the composition of the crude biological raw material (R-2-5) of the copolymer was analyzed using the C-13 NMR method described below, it was found that 77% by mass of styrene, 23% by mass of acrylonitrile, 0% by mass of N-phenylmaleimide, and anhydrous. The maleic acid content was 0% by mass.
　以下の（１）～（６）の操作を実施し、共重合体（Ｐ－２－５）を得た。
　（１）粗生成物原料（Ｒ－２－５）１０００ｇを、５リットルのメチルエチルケトンに溶解させ、粗生成物原料のメチルエチルケトン溶液を得た。
（２）メチルエチルケトン溶液にヘキサン１．６リットルを滴下して、溶解させた粗生成物原料の１０質量％を析出させた混合液を得た。
（３）混合液を濾過して、濾物と濾液に分離した。濾物は、２４時間風乾した後に、７０℃に設定した真空乾燥器で４時間乾燥させる乾燥工程を経て得た。
（４）（３）で得た濾液にヘキサン０．５リットルを滴下して、粗生成物原料の一部を析出させた混合液を得た。
（５）上記（３）～（４）の操作を繰り返し、５つの濾物を得た。各濾物は、２４時間風乾した後に、７０℃に設定した真空乾燥器で４時間乾燥させる乾燥工程を経て得た。
各濾物の重量は、得られた順に、１５０ｇ、２３０ｇ、３７０ｇ、１７０ｇ、８０ｇであった。
（６）５つの濾物について、３番目に得られた濾物を共重合体（Ｐ－２－５）として得た。後述のＣ－１３ＮＭＲ法にてマレイミド系共重合体（Ｐ－２－５）の組成を確認したところ、スチレン７７質量％、アクリロニトリル２３質量％、Ｎ－フェニルマレイミド０質量％、無水マレイン酸０質量％であった。得られた共重合体の分析結果を表２－１に示す。
また、共重合体（Ｐ－２－５）、塩素含有ポリマー２－１、２－２、２－３のそれぞれの１０質量%のＴＨＦ溶液を調製し、共重合体と塩素含有ポリマーのＴＨＦ溶液を１：１の容量比で混合して作製した混合液における明度Ｌ＊を測定した結果、それぞれ、７５，７０，４４ であった。 The following operations (1) to (6) were performed to obtain a copolymer (P-2-5).
(1) 1000 g of crude product raw material (R-2-5) was dissolved in 5 liters of methyl ethyl ketone to obtain a methyl ethyl ketone solution of the crude product raw material.
(2) 1.6 liters of hexane was added dropwise to the methyl ethyl ketone solution to obtain a mixed solution in which 10% by mass of the dissolved crude product raw material was precipitated.
(3) The mixed solution was filtered and separated into a filtrate and a filtrate. The filter material was obtained through a drying process of air drying for 24 hours and then drying in a vacuum dryer set at 70°C for 4 hours.
(4) 0.5 liters of hexane was added dropwise to the filtrate obtained in (3) to obtain a mixed solution in which a portion of the crude product raw material was precipitated.
(5) The above operations (3) and (4) were repeated to obtain five filtrates. Each filter material was obtained through a drying process of air drying for 24 hours and then drying in a vacuum dryer set at 70° C. for 4 hours.
The weight of each filter material was 150 g, 230 g, 370 g, 170 g, and 80 g in the order obtained.
(6) Among the five filtrates, the third one obtained was obtained as a copolymer (P-2-5). When the composition of the maleimide copolymer (P-2-5) was confirmed using the C-13 NMR method described below, it was found to be 77% by mass of styrene, 23% by mass of acrylonitrile, 0% by mass of N-phenylmaleimide, and 0% by mass of maleic anhydride. %Met. The analysis results of the obtained copolymer are shown in Table 2-1.
In addition, a 10% by mass THF solution of each of the copolymer (P-2-5) and chlorine-containing polymers 2-1, 2-2, and 2-3 was prepared, and a THF solution of the copolymer and chlorine-containing polymer was prepared. The lightness L* of the mixed liquid prepared by mixing the two in a volume ratio of 1:1 was 75, 70, and 44, respectively.
＜樹脂組成物＞
（使用原材料）各実施例、比較例、参考例に使用した原材料を以下に示す。
（１）塩素含有ポリマー（ＰＶＣ）
・塩素含有ポリマー２－１：ＨＡ－１５Ｅ（製品名）、徳山積水工業社製、Ｋ値５６．０±２．０、塩素化度（塩素含有量）６３．５±１．０％
・塩素含有ポリマー２－２：ＨＡ－５３Ｋ（製品名）、徳山積水工業社製、Ｋ値６６．０±２．０、塩素化度（塩素含有量）６７．３±１．０％
・塩素含有ポリマー２－３：ＴＨ－１０００（製品名）、大洋塩ビ社製、Ｋ値６６．７±１．０、塩素化度（塩素含有量）５７．０±１．０％
（２）共重合体
・上述の製造例に従い得たマレイミド系共重合体（Ｒ－１）～（Ｒ－４）及び共重合体（Ｒ－５）を使用した。
（３）耐衝撃改質剤
・アクリルゴム：カネエースＦＭ－５０（製品名）、カネカ社製
・塩素化ポリエチレン（ＰＥ）：エラスレン３０１Ａ（製品名）、レゾナック社製
・ＭＢＳ：メタブレンＣ－２２３Ａ（製品名）、三菱ケミカル社製 <Resin composition>
(Raw materials used) The raw materials used in each example, comparative example, and reference example are shown below.
(1) Chlorine-containing polymer (PVC)
・Chlorine-containing polymer 2-1: HA-15E (product name), manufactured by Tokuyama Sekisui Kogyo Co., Ltd., K value 56.0 ± 2.0, degree of chlorination (chlorine content) 63.5 ± 1.0%
・Chlorine-containing polymer 2-2: HA-53K (product name), manufactured by Tokuyama Sekisui Kogyo Co., Ltd., K value 66.0 ± 2.0, degree of chlorination (chlorine content) 67.3 ± 1.0%
・Chlorine-containing polymer 2-3: TH-1000 (product name), manufactured by Taiyo PVC Co., Ltd., K value 66.7 ± 1.0, degree of chlorination (chlorine content) 57.0 ± 1.0%
(2) Copolymers Maleimide copolymers (R-1) to (R-4) and copolymer (R-5) obtained according to the above-mentioned production examples were used.
(3) Impact modifier/acrylic rubber: Kane Ace FM-50 (product name), manufactured by Kaneka; chlorinated polyethylene (PE): Elasthren 301A (product name); manufactured by Resonac; MBS: Metablane C-223A ( Product name), manufactured by Mitsubishi Chemical Corporation
［実施例（１－３～１－１２、２－３～２－８）、比較例（１－１３～１－１５、２－９～２－１１、３－３～３－１１）、参考例（１－１～１－２、２－１～２－２、３－１～３－２）］
　各共重合体（Ｐ－２－１～Ｐ－２－５）と、塩素含有ポリマーと、耐衝撃改質剤とを表２－２～２－４に示した配合割合でブレンドした後、テストロール（φ６×Ｌ１５テストロール、関西ロール社製）を用いてロールシートを作成し、ロールシートを重ねてプレス成形し、切削加工または打ち抜き加工により試験片を作成して、樹脂組成物の各物性値の測定を行った。なお、上記ブレンド前に、塩素含有ポリマーには安定剤（ＴＶＳ＃８８３２；日東化成社製）、滑剤（ロキシオールＶＰＮ９６３；エメリー・オレオケミカルズ・ジャパン株式会社製）を予め加えヘンシェルミキサーで混合して用いた。表中の塩素含有ポリマーの配合量は安定剤・滑剤の質量を含まない量である。結果を表２－２～２－４に示す。 [Examples (1-3 to 1-12, 2-3 to 2-8), Comparative Examples (1-13 to 1-15, 2-9 to 2-11, 3-3 to 3-11), Reference Examples (1-1 to 1-2, 2-1 to 2-2, 3-1 to 3-2)]
After blending each copolymer (P-2-1 to P-2-5), chlorine-containing polymer, and impact modifier in the proportions shown in Tables 2-2 to 2-4, the test A roll sheet was created using a roll (φ6 x L15 test roll, manufactured by Kansai Roll Co., Ltd.), the roll sheets were stacked and press molded, and a test piece was created by cutting or punching to determine each physical property of the resin composition. The value was measured. Before blending, a stabilizer (TVS #8832; manufactured by Nitto Kasei Co., Ltd.) and a lubricant (Roxiol VPN963; manufactured by Emery Oleochemicals Japan Co., Ltd.) were added to the chlorine-containing polymer in advance and mixed in a Henschel mixer. there was. The amount of chlorine-containing polymer in the table does not include the mass of stabilizers and lubricants. The results are shown in Tables 2-2 to 2-4.
（組成分析）
　各共重合体の組成分析は、Ｃ－１３ＮＭＲ法にて下記記載の測定条件で測定した。
　　　装置名：ＦＴ－ＮＭＲ  ＡＶＡＮＣＥ３００（ＢＲＵＫＥＲ社製）
　　　溶媒：重水素化クロロホルム
　　　濃度：１４質量％
　　　温度：２７℃
　　　積算回数：８０００回 (composition analysis)
Compositional analysis of each copolymer was performed using the C-13 NMR method under the measurement conditions described below.
Equipment name: FT-NMR AVANCE300 (manufactured by BRUKER)
Solvent: Deuterated chloroform Concentration: 14% by mass
Temperature: 27℃
Accumulated number of times: 8000 times
（ビカット軟化点：ＶＳＴ）
　樹脂組成物のビカット軟化点は、ロールシートを重ねてプレス成形したものを切削加工して２０ｍｍ×２０ｍｍ、厚さ４ｍｍとした試験片について、ＪＩＳ　Ｋ７２０６：１９９９に基づき、５０法（荷重５０Ｎ、昇温速度５０℃／時間）で測定した。なお、測定機は東洋精機製作所社製ＨＤＴ＆ＶＳＰＴ試験装置を使用した。 (Vicat softening point: VST)
The Vicat softening point of the resin composition was determined based on JIS K7206:1999 using the 50 method (load 50N, elevation The temperature was measured at a temperature rate of 50° C./hour). The measuring device used was an HDT & VSPT testing device manufactured by Toyo Seiki Seisakusho.
（シャルピー衝撃強度）
　樹脂組成物のシャルピー衝撃強度は、ロールシートを重ねてプレス成形したものを打ち抜き加工により角形の試験片を作製した。ノッチ加工機 (安田精機製作所社製　１８９－ＰＮＣＡ)により、ＪＩＳ　Ｋ－７１４４：１９９９に従って当該角形の試験片を加工しノッチあり試験片を用意した。ＪＩＳ　Ｋ－７１１１：２０１２に準拠して、当該ノッチあり試験片を用い、打撃方向はエッジワイズを採用して相対湿度５０％、雰囲気温度２３℃の条件で測定した。なお、測定機は東洋精機製作所社製デジタル衝撃試験機を使用した。 (Charpy impact strength)
The Charpy impact strength of the resin composition was determined by punching out a rectangular test piece by press-molding stacked roll sheets. A notched test piece was prepared by processing the rectangular test piece according to JIS K-7144:1999 using a notch processing machine (189-PNCA manufactured by Yasuda Seiki Seisakusho Co., Ltd.). In accordance with JIS K-7111:2012, using the notched test piece, the impact direction was edgewise, and the measurement was performed at a relative humidity of 50% and an ambient temperature of 23°C. The measuring device used was a digital impact tester manufactured by Toyo Seiki Seisakusho.
（金属腐食）
　各共重合体（Ｐ－２－１～Ｐ－２－５）と、塩素含有ポリマーと、耐衝撃改質剤とを表２－２～２－４に示した配合割合で混練し作成したロールシートを重ねてプレス成形した樹脂組成物の板状成形体を得た。
　脱脂処理（金型クリーナー[スミモールドクリーナー；住鉱潤滑剤株式会社製]で洗浄（２回）→ＭＥＫで洗浄（１回）→ＭｅＯＨで洗浄（１回）の処理）を行った鋼材（Ｓ５５Ｃ（ＪＩＳ　Ｇ　４０５１：機械構造用炭素鋼鋼材））表面上に当該表面を覆うように、塩素含有ポリマーの板状成形体又は樹脂組成物の板状成形体を配置した。続いて、オーブン（空気中）を用いて各板状成形体を配置した鋼材を１９０℃で４時間加熱し、その後室温に冷却した。冷却後、鋼材表面上の塩素含有ポリマー又は樹脂組成物を剥がし、鋼材表面の腐食具合を観察し、塩素含有ポリマーを単体で用いた場合と当該塩素含有ポリマーを含む樹脂組成物を用いた場合の違いについて、下記の基準で評価した。
◎：腐食がない
〇：塩素含有ポリマー単体より大幅に改善
△：塩素含有ポリマー単体より少し改善
×：塩素含有ポリマーと変わりない (metal corrosion)
A roll made by kneading each copolymer (P-2-1 to P-2-5), a chlorine-containing polymer, and an impact modifier at the blending ratios shown in Tables 2-2 to 2-4. A plate-shaped molded body of the resin composition was obtained by stacking the sheets and press-molding them.
Steel material (S55C) that has been degreased (cleaned with mold cleaner [Sumimold Cleaner; manufactured by Sumiko Lubricants Co., Ltd.] (twice) → cleaned with MEK (once) → cleaned with MeOH (once)) (JIS G 4051: Carbon Steel Materials for Machine Structures)) A plate-shaped molded body of a chlorine-containing polymer or a plate-shaped molded body of a resin composition was placed on the surface so as to cover the surface. Subsequently, the steel material on which each plate-shaped molded body was placed was heated at 190° C. for 4 hours using an oven (in air), and then cooled to room temperature. After cooling, the chlorine-containing polymer or resin composition on the surface of the steel material was peeled off, and the degree of corrosion on the surface of the steel material was observed. Differences were evaluated using the following criteria.
◎: No corrosion 〇: Significantly improved compared to chlorine-containing polymer alone △: Slightly improved than chlorine-containing polymer alone ×: Same as chlorine-containing polymer
　本発明の規定を満たす、特定の塩素含有量の塩素含有ポリマーを用い、特定のマレイミド系共重合体を特定の割合で配合した場合には、実施例（試験例：１－３～１－１１、２－３～２－８）では、樹脂組成物の耐熱性及び耐衝撃性が優れていた。また、金属腐食が抑えられていた。 When a chlorine-containing polymer with a specific chlorine content that satisfies the provisions of the present invention is used and a specific maleimide copolymer is blended in a specific ratio, Examples (Test Examples: 1-3 to 1-11) , 2-3 to 2-8), the resin compositions had excellent heat resistance and impact resistance. Furthermore, metal corrosion was suppressed.
　これに対し、本発明の規定を満たさない塩素含有ポリマー或いはマレイミド系共重合体の配合を採用した比較例（試験例：１－１２～１－１４、２－９～２－１１、３－３～３－１１）では、樹脂組成物の耐熱性や耐衝撃性が十分でないものがあった。 In contrast, comparative examples (test examples: 1-12 to 1-14, 2-9 to 2-11, 3-3 -3-11), some of the resin compositions did not have sufficient heat resistance or impact resistance.
［産業上の利用可能性］
　本発明の第２観点により、耐衝撃改質剤及び耐熱性付与剤を添加した場合でも、トレードオフの関係にあった耐衝撃性と耐熱性が良好に両立される塩素含有ポリマーを含む樹脂組成物及びその成形体が提供され、耐熱性及び耐衝撃性が要求される成形品に好適に利用される。 [Industrial applicability]
According to the second aspect of the present invention, a resin composition containing a chlorine-containing polymer that satisfies both impact resistance and heat resistance, which are in a trade-off relationship, even when an impact modifier and a heat resistance imparting agent are added. A product and a molded article thereof are provided, and are suitably used for molded products that require heat resistance and impact resistance.

Claims (13)

  1. 　塩素含有ポリマー用改質剤であり、
    　前記塩素含有ポリマー用改質剤の１０質量％のＴＨＦ溶液と、Ｋ値が６６．７±１．０であり、塩素化度が５７±１．０％である塩素含有ポリマーの１０質量％のＴＨＦ溶液とを１：１の容量比で混合して作製した混合液における明度Ｌ＊が４０以上である、塩素含有ポリマー用改質剤。     It is a modifier for chlorine-containing polymers,
    A 10% by mass THF solution of the modifier for chlorine-containing polymers and a 10% by mass solution of the chlorine-containing polymer having a K value of 66.7 ± 1.0 and a degree of chlorination of 57 ± 1.0%. A modifier for chlorine-containing polymers, which has a lightness L * of 40 or more in a mixed solution prepared by mixing with a THF solution at a volume ratio of 1:1.
  2. 　少なくとも芳香族ビニル系単量体単位、シアン化ビニル系単量体単位、マレイミド系単量体単位を含む共重合体を含む、請求項１に記載の塩素含有ポリマー用改質剤。 The modifier for chlorine-containing polymers according to claim 1, comprising a copolymer containing at least an aromatic vinyl monomer unit, a vinyl cyanide monomer unit, and a maleimide monomer unit.
  3. 　前記共重合体に含有される単量体単位の合計を１００質量％とした場合に、
    　　前記芳香族ビニル系単量体単位６０～８５質量％、
    　　前記シアン化ビニル系単量体単位０．５～２０質量％、
    　　前記マレイミド系単量体単位１０～３０質量％
    を含む、請求項２に記載の塩素含有ポリマー用改質剤。     When the total of monomer units contained in the copolymer is 100% by mass,
    60 to 85% by mass of the aromatic vinyl monomer unit,
    0.5 to 20% by mass of the vinyl cyanide monomer unit,
    10 to 30% by mass of the maleimide monomer unit
    The modifier for chlorine-containing polymers according to claim 2, comprising:
  4. 　請求項１～請求項３のいずれか一項に記載の塩素含有ポリマー用改質剤と、塩素含有ポリマーを含有する樹脂組成物。 A resin composition containing the chlorine-containing polymer modifier according to any one of claims 1 to 3 and a chlorine-containing polymer.
  5. 　請求項４に記載の樹脂組成物を用いた成形体。 A molded article using the resin composition according to claim 4.
  6. 樹脂組成物であって、
    　塩素含有ポリマー１００質量部と、マレイミド系共重合体１～４０質量部と、を含み、
    　前記塩素含有ポリマーの塩素含有量が６０質量％～７０質量％であり、
    　前記マレイミド系共重合体は、シアン化ビニル系単量体単位と、マレイミド系単量体単位と、を有する、
    樹脂組成物。     A resin composition,
    100 parts by mass of a chlorine-containing polymer and 1 to 40 parts by mass of a maleimide copolymer,
    The chlorine content of the chlorine-containing polymer is 60% by mass to 70% by mass,
    The maleimide copolymer has a vinyl cyanide monomer unit and a maleimide monomer unit,
    Resin composition.
  7. 請求項６に記載の樹脂組成物であって、
    　前記マレイミド系共重合体は、芳香族ビニル系単量体単位と、前記シアン化ビニル系単量体単位と、前記マレイミド系単量体単位と、を有する、
    樹脂組成物。     The resin composition according to claim 6,
    The maleimide copolymer has an aromatic vinyl monomer unit, the vinyl cyanide monomer unit, and the maleimide monomer unit,
    Resin composition.
  8. 請求項７に記載の樹脂組成物であって、
    　前記マレイミド系共重合体に含有される単量体単位の合計を１００質量％とした場合に、
    　　前記芳香族ビニル系単量体単位６０～８５質量％と、
    　　前記シアン化ビニル系単量体単位０．５～２０質量％と、
    　　前記マレイミド系単量体単位１０～３０質量％と、
    を有する、樹脂組成物。     The resin composition according to claim 7,
    When the total amount of monomer units contained in the maleimide copolymer is 100% by mass,
    60 to 85% by mass of the aromatic vinyl monomer unit,
    0.5 to 20% by mass of the vinyl cyanide monomer unit,
    10 to 30% by mass of the maleimide monomer unit,
    A resin composition comprising:
  9. 請求項８に記載の樹脂組成物であって、
    　前記マレイミド系共重合体に含有される単量体単位の合計を１００質量％とした場合に、
    　　前記芳香族ビニル系単量体単位６５～８０質量％と、
    　　前記シアン化ビニル系単量体単位０．５～１５質量％と、
    　　前記マレイミド系単量体単位１０～２５質量％と、
    を有する、樹脂組成物。     The resin composition according to claim 8,
    When the total amount of monomer units contained in the maleimide copolymer is 100% by mass,
    65 to 80% by mass of the aromatic vinyl monomer unit,
    0.5 to 15% by mass of the vinyl cyanide monomer unit,
    10 to 25% by mass of the maleimide monomer unit,
    A resin composition comprising:
  10. 請求項６に記載の樹脂組成物であって、
    　前記マレイミド系共重合体の重量平均分子量が７０，０００～１５０，０００である、樹脂組成物。     The resin composition according to claim 6,
    A resin composition, wherein the maleimide copolymer has a weight average molecular weight of 70,000 to 150,000.
  11. 請求項６に記載の樹脂組成物であって、
    　前記樹脂組成物１００質量％中、前記塩素含有ポリマーを４質量％以上含む、樹脂組成物。     The resin composition according to claim 6,
    A resin composition containing 4% by mass or more of the chlorine-containing polymer based on 100% by mass of the resin composition.
  12. 請求項６に記載の樹脂組成物であって、耐衝撃改質剤をさらに含む、樹脂組成物。 The resin composition according to claim 6, further comprising an impact modifier.
  13. 請求項６～請求項１２の何れか１つに記載の樹脂組成物を用いた成形体。 A molded article using the resin composition according to any one of claims 6 to 12.
PCT/JP2023/013573 2022-03-31 2023-03-31 Chlorine-containing polymer modifier, resin composition, and molded body WO2023191062A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2022-059144 2022-03-31
JP2022059144 2022-03-31

Publications (1)

Publication Number Publication Date
WO2023191062A1 true WO2023191062A1 (en) 2023-10-05

Family

ID=88202344

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2023/013573 WO2023191062A1 (en) 2022-03-31 2023-03-31 Chlorine-containing polymer modifier, resin composition, and molded body

Country Status (2)

Country Link
TW (1) TW202402838A (en)
WO (1) WO2023191062A1 (en)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0229404A (en) * 1988-07-20 1990-01-31 San Aroo Kagaku Kk Production of aromatic vinyl copolymer
JPH02265944A (en) * 1989-04-05 1990-10-30 Nippon Oil & Fats Co Ltd Vinyl chloride resin composition
JPH04122759A (en) * 1990-09-14 1992-04-23 Sekisui Chem Co Ltd Vinyl chloride resin composition
JPH04353508A (en) * 1991-05-31 1992-12-08 Sumitomo Dow Ltd Production of thermoplastic resin
JPH11302482A (en) * 1998-04-22 1999-11-02 Mitsui Chem Inc Vinyl chloride resin composition and molded product using the same
WO2022039098A1 (en) * 2020-08-19 2022-02-24 デンカ株式会社 Maleimide copolymer, and chlorine-containing polymer resin composition including maleimide copolymer and chlorine-containing polymer
WO2022039099A1 (en) * 2020-08-19 2022-02-24 デンカ株式会社 Maleimide copolymer, and chlorine-containing polymer resin composition including maleimide copolymer and chlorine-containing polymer

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0229404A (en) * 1988-07-20 1990-01-31 San Aroo Kagaku Kk Production of aromatic vinyl copolymer
JPH02265944A (en) * 1989-04-05 1990-10-30 Nippon Oil & Fats Co Ltd Vinyl chloride resin composition
JPH04122759A (en) * 1990-09-14 1992-04-23 Sekisui Chem Co Ltd Vinyl chloride resin composition
JPH04353508A (en) * 1991-05-31 1992-12-08 Sumitomo Dow Ltd Production of thermoplastic resin
JPH11302482A (en) * 1998-04-22 1999-11-02 Mitsui Chem Inc Vinyl chloride resin composition and molded product using the same
WO2022039098A1 (en) * 2020-08-19 2022-02-24 デンカ株式会社 Maleimide copolymer, and chlorine-containing polymer resin composition including maleimide copolymer and chlorine-containing polymer
WO2022039099A1 (en) * 2020-08-19 2022-02-24 デンカ株式会社 Maleimide copolymer, and chlorine-containing polymer resin composition including maleimide copolymer and chlorine-containing polymer

Also Published As

Publication number Publication date
TW202402838A (en) 2024-01-16

Similar Documents

Publication Publication Date Title
JP2020204037A (en) Thermoplastic resin composition
CN115443294A (en) Maleimide copolymer, and chlorine-containing polymer resin composition containing maleimide copolymer and chlorine-containing polymer
CN115427468A (en) Maleimide copolymer, and chlorine-containing polymer resin composition containing maleimide copolymer and chlorine-containing polymer
JPWO2019138996A1 (en) Maleimide-based copolymer, method for producing the same, and resin composition using the same
WO2016186142A1 (en) Copolymer for use as polymer blend compatibilizer, and resin composition
JP7245334B2 (en) Maleimide-based copolymer, method for producing the same, and resin composition using the same
JP2006265373A (en) Vinyl chloride resin composition comprising maleimide copolymer and vinyl chloride polymer
JPS5943494B2 (en) thermoplastic resin composition
WO2023191062A1 (en) Chlorine-containing polymer modifier, resin composition, and molded body
JP7492952B2 (en) Thermoplastic resin composition and molded article thereof
JP2023150180A (en) Production method of modifier for chlorine-containing polymer, modifier for chlorine-containing polymer, resin composition, and molding
KR20230062847A (en) Heat resistant resin composition and injection molded product thereof
CN116133821A (en) Maleimide copolymer, maleimide copolymer composition, resin composition, and injection molded article
JP3141707B2 (en) High nitrile-containing vinyl copolymer and method for producing the same
WO2023191064A1 (en) Heat-resistance imparter for chlorinated polymers, resin composition, and molded object formed from said resin composition
WO2022234816A1 (en) Resin composition including maleimide copolymer and chlorine-containing polymer, and gutters, gutter parts, joinery profiles, pipes, and joints molded from said resin composition
JP2996115B2 (en) Thermoplastic resin composition
CN117460788A (en) Resin composition containing maleimide copolymer and chlorine-containing polymer, gutter and gutter member molded from the resin composition, door/window profile, and pipe and joint
JPH1160640A (en) Maleimide-based copolymer and thermoplastic resin composition
JP2009298965A (en) Resin composition or molding thereof
JPH06293815A (en) New maleimide copolymer and its production
JPH0262585B2 (en)
JPS62179553A (en) Thermoplastic resin composition
JPH06200104A (en) Vinyl chloride-based resin composition
JPS632282B2 (en)

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23781070

Country of ref document: EP

Kind code of ref document: A1