WO2022039099A1 - Maleimide copolymer, and chlorine-containing polymer resin composition including maleimide copolymer and chlorine-containing polymer - Google Patents

Maleimide copolymer, and chlorine-containing polymer resin composition including maleimide copolymer and chlorine-containing polymer Download PDF

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WO2022039099A1
WO2022039099A1 PCT/JP2021/029721 JP2021029721W WO2022039099A1 WO 2022039099 A1 WO2022039099 A1 WO 2022039099A1 JP 2021029721 W JP2021029721 W JP 2021029721W WO 2022039099 A1 WO2022039099 A1 WO 2022039099A1
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mass
maleimide
chlorine
containing polymer
parts
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PCT/JP2021/029721
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French (fr)
Japanese (ja)
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達宏 松原
広平 西野
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デンカ株式会社
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Priority to KR1020237009304A priority Critical patent/KR20230052943A/en
Priority to JP2022543918A priority patent/JPWO2022039099A1/ja
Priority to CN202180029357.0A priority patent/CN115427468A/en
Publication of WO2022039099A1 publication Critical patent/WO2022039099A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/42—Nitriles
    • C08F220/44—Acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/04—Anhydrides, e.g. cyclic anhydrides
    • C08F222/06—Maleic anhydride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/36—Amides or imides
    • C08F222/40—Imides, e.g. cyclic imides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/12—Copolymers of styrene with unsaturated nitriles
    • 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 maleimide-based copolymer and a chlorine-containing polymer-based resin composition containing a maleimide-based copolymer and a chlorine-containing polymer.
  • Chlorine-containing polymer resins are inexpensive and have excellent chemical, physical, and mechanical properties, so they are mass-produced and used in a variety of applications.
  • the chlorine-containing polymer has a drawback of lacking heat resistance (heat softening temperature), and is measured by the 50 method (load 50 N, heating rate 50 ° C./hour) based on, for example, JIS K7206: 1999.
  • the softening temperature is around 82 ° C., and the softening temperature is further lowered by the stabilizer and the plasticizer usually blended during the molding process.
  • a method for improving the heat resistance of the chlorine-containing polymer resin a method of mixing the resin imparting heat resistance with the chlorine-containing polymer (Patent Documents 1 and 2) is known.
  • the present invention is a maleimide-based copolymer capable of obtaining a chlorine-containing polymer-based resin composition in which coloring is suppressed while improving the heat resistance of the chlorine-containing polymer, and chlorine containing a maleimide-based copolymer and a chlorine-containing polymer.
  • An object of the present invention is to provide a polymer-based resin composition containing a compound and a molded product thereof. Further, it is an object of the present invention to provide a chlorine-containing polymer-based resin composition having excellent extrusion moldability.
  • a maleimide-based copolymer having a specific monomer unit composition, a specific range of melt viscosities, and a specific range of weight average molecular weight and having a low yellowness is adopted.
  • heat resistance can be imparted to the chlorine-containing polymer and coloring in the resin composition and its molded product can be suppressed.
  • the resin composition has good extrusion moldability. That is, the present invention (1) The fragrance when the total of the aromatic vinyl-based monomer unit, the cyanide vinyl-based monomer unit, the unsaturated acid anhydride monomer unit, and the maleimide-based monomer unit is 100% by mass.
  • the group vinyl-based monomer unit 50 to 90% by mass, the cyanide vinyl-based monomer unit 0.5 to 25% by mass, the unsaturated acid anhydride monomer unit 0 to 10% by mass, and the above. It has a maleimide-based monomer unit of 5 to 25% by mass, has a melt viscosity of 200 to 100,000 Pa ⁇ sec measured under the conditions of 190 ° C. and a shear rate of 100 / sec, and has a weight average molecular weight of 250,000 to 120,000.
  • Maleimide-based copolymer for chlorine-containing polymers (2) A chlorine-containing polymer-based resin composition containing 5 to 50% by mass of the maleimide-based copolymer and 50 to 95% by mass of the chlorine-containing polymer according to (1).
  • Composition (8) The chlorine-containing polymer-based resin composition according to any one of (2) to (7), wherein the maleimide-based copolymer has 5 to 24% by mass of a maleimide-based monomer unit.
  • the maleimide-based copolymer of the present invention is adopted, heat resistance can be imparted to the chlorine-containing polymer, and coloring in the resin composition and its molded body can be suppressed. Therefore, it is suitably used for applications that require heat resistance and applications that require good appearance. Further, since it is excellent in kneading property, it is suitably used for extrusion molding.
  • the maleimide-based copolymer in the present invention contains an aromatic vinyl-based monomer unit, a cyanide vinyl-based monomer unit, an unsaturated acid anhydride monomer unit, and a maleimide-based monomer unit.
  • the monomer unit contained in the maleimide-based copolymer will be described below.
  • Aromatic vinyl-based monomer unit examples of the aromatic vinyl monomer that can be used in the maleimide-based copolymer according to the present invention include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, and ethyl. Examples thereof include styrene, p-tert-butyl styrene, ⁇ -methyl styrene, ⁇ -methyl-p-methyl styrene and the like. Among these, styrene, which has a high effect of improving hue, is preferable.
  • the styrene-based monomer may be used alone or in combination of two or more.
  • the maleimide-based copolymer according to the present invention has a total of 100 mass by mass of an aromatic vinyl-based monomer unit, a cyanide vinyl-based monomer unit, an unsaturated acid anhydride monomer unit, and a maleimide-based monomer unit. %,
  • the aromatic vinyl-based monomer unit is contained in an amount of 50 to 90% by mass, preferably 50 to 80% by mass, and more preferably 60 to 70% by mass. Specifically, for example, it is 50, 45, 50, 55, 60, 65, 70, 75, 80, 85, or 90% by mass, and is within the range between any two of the numerical values exemplified here. May be good.
  • the maleimide-based copolymer will be a chlorine-containing polymer.
  • the maleimide-based copolymer cannot be kneaded without melting, or the coloration of the chlorine-containing polymer-based resin composition and its molded product may become a problem due to the high yellowness (YI) of the maleimide-based copolymer. If it exceeds 90% by mass, the heat resistance of the chlorine-containing polymer resin composition may not be sufficiently improved.
  • vinyl cyanide-based monomer unit examples include acrylonitrile, methacrylonitrile, etacrylonitrile, and fumaronitrile. Among these, acrylonitrile is preferable from the viewpoint of imparting heat resistance to the hue and the chlorine-containing polymer resin composition.
  • the vinyl cyanide monomer may be used alone or in combination of two or more.
  • the maleimide-based copolymer according to the present invention has a total of 100 mass by mass of an aromatic vinyl-based monomer unit, a cyanide vinyl-based monomer unit, an unsaturated acid anhydride monomer unit, and a maleimide-based monomer unit. %,
  • the vinyl cyanide-based monomer unit is contained in an amount of 0.5 to 25% by mass, preferably 5 to 20% by mass, and more preferably 1 to 20% by mass. Specifically, for example, it is 0.5, 1, 5, 10, 15, 20, or 25% by mass, and may be within the range between any two of the numerical values exemplified here.
  • the amount of vinyl cyanide-based monomer unit is less than 0.5% by mass, the heat resistance of the chlorine-containing polymer-based resin composition may not be sufficiently improved, and if it exceeds 25% by mass, it is maleimide-based.
  • the yellowness (YI) of the copolymer may be high.
  • unsaturated acid anhydride monomer unit examples include maleic acid anhydride, itaconic acid anhydride, citraconic acid anhydride, aconitic acid anhydride and the like. .. Among these, maleic anhydride is preferable from the viewpoint of imparting heat resistance to the chlorine-containing polymer resin composition.
  • the unsaturated acid anhydride monomer unit may be used alone or in combination of two or more.
  • the maleimide-based copolymer according to the present invention has a total of 100 mass of aromatic vinyl-based monomer unit, cyanide vinyl-based monomer unit, unsaturated acid anhydride monomer unit and maleimide-based monomer unit. %,
  • the unsaturated acid anhydride monomer unit is contained in an amount of 0 to 10% by mass, preferably 0.3 to 5% by mass, and more preferably 0.5 to 5% by mass. Specifically, for example, 0, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10% by mass. It may be within the range between any two of the numerical values exemplified here. If the amount of the unsaturated acid anhydride monomer unit exceeds 10% by mass, the fluidity may decrease and the kneadability with the chlorine-containing polymer may decrease.
  • maleimide-based monomer unit examples of the maleimide-based monomer unit that can be used in the maleimide-based copolymer according to the present invention include N-alkylmaleimide such as N-methylmaleimide, N-butylmaleimide, and N-cyclohexylmaleimide, and N-phenyl. There are N-arylmaleimide such as maleimide, N-chlorphenylmaleimide, N-methylphenylmaleimide, N-methoxyphenylmaleimide, N-tribromophenylmaleimide and the like.
  • N-arylmaleimide is preferable, and N-phenylmaleimide is more preferable, from the viewpoint of imparting heat resistance to the chlorine-containing polymer resin composition.
  • the maleimide-based monomer may be used alone or in combination of two or more.
  • a copolymer obtained by copolymerizing a raw material composed of an unsaturated dicarboxylic acid monomer unit with another monomer is made into ammonia or a primary polymer. It may be imidized with an amine.
  • a raw material made of a maleimide-based monomer may be copolymerized with another monomer.
  • the maleimide-based copolymer according to the present invention has a total of 100 mass by mass of an aromatic vinyl-based monomer unit, a cyanide vinyl-based monomer unit, an unsaturated acid anhydride monomer unit, and a maleimide-based monomer unit. %,
  • the maleimide-based monomer unit is contained in an amount of 5 to 25% by mass, preferably 5% by mass or more and less than 25% by mass, more preferably 5 to 24% by mass, and further preferably 10 to 10% by mass. Contains 24% by mass. Specifically, for example, it is 5, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, or 25% by mass, and is a numerical value exemplified here. It may be within the range between any two of the above.
  • the amount of the maleimide-based monomer unit is less than 5% by mass, the heat resistance of the chlorine-containing polymer-based resin composition may not be sufficiently improved, and if it exceeds 25% by mass, the maleimide-based copolymer is formed. It may not melt with the chlorine-containing polymer and cannot be kneaded.
  • the maleimide-based copolymer according to the present invention comprises a copolymerizable monomer other than an aromatic vinyl monomer, a vinyl cyanide monomer, an unsaturated acid anhydride monomer unit and a maleimide monomer. Copolymerization may be carried out as long as the effect of the present invention is not impaired.
  • the monomer copolymerizable with the maleimide-based copolymer include acrylic acid ester monomers such as methyl acrylic acid ester, ethyl acrylic acid ester, and butyl acrylic acid ester, methyl methacrylate ester, and ethyl methacrylate ester.
  • Examples thereof include methacrylic acid ester monomers, vinyl carboxylic acid monomers such as acrylic acid and methacrylic acid, acrylic acid amides and methacrylic acid amides.
  • the monomer copolymerizable with the maleimide-based copolymer may be used alone or in combination of two or more. Such a monomer can be copolymerized as long as the effect of the present invention is not impaired, but it is preferably 20% by mass or less, preferably 10% by mass, from the viewpoint of imparting heat resistance to the chlorine-containing polymer resin composition. % Or less is more preferable.
  • the polymerization solution contains heat-resistant stabilizers such as hindered phenol-based compounds, lactone-based compounds, phosphorus-based compounds and sulfur-based compounds, and light-resistant stabilizers such as hindered amine-based compounds and benzotriazole-based compounds, as necessary.
  • heat-resistant stabilizers such as hindered phenol-based compounds, lactone-based compounds, phosphorus-based compounds and sulfur-based compounds
  • light-resistant stabilizers such as hindered amine-based compounds and benzotriazole-based compounds
  • Additives such as lubricants, plasticizers, colorants, antistatic agents, and mineral oils may be added. The amount added is preferably less than 0.2 parts by mass with respect to 100 parts by mass of all the monomer units. These additives may be used alone or in combination of two or more.
  • the melt viscosity of the maleimide-based copolymer in the present invention is 200 to 100,000 Pa ⁇ sec, preferably 200 to 70,000 Pa ⁇ sec, and more preferably 500 to 70,000 Pa ⁇ sec. Specifically, for example, it is 200, 500, 1000, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, 10000, 20000, 30000, 40,000, 50000, or 100,000 Pa ⁇ sec, and is a numerical value exemplified here. It may be within the range between any two of the above.
  • the heat resistance of the chlorine-containing polymer resin composition may not be sufficiently improved, and if it exceeds 100,000 Pa ⁇ sec, the maleimide-based copolymer of the mixed resin melts with the chlorine-containing polymer. It may not be possible to knead without kneading.
  • the melt viscosity of the maleimide-based copolymer can be adjusted by adjusting the blending ratio of the monomer units constituting the maleimide-based copolymer. For example, increasing the melt viscosity by increasing the content of vinyl cyanide-based monomer units in the maleimide-based copolymer or increasing the content of maleimide-based monomer units in the maleimide-based copolymer. Is possible. It is also possible to increase the melt viscosity by increasing the weight average molecular weight of the maleimide-based copolymer. These adjustment methods can be used together.
  • the weight average molecular weight of the maleimide-based copolymer in the present invention is 25,000 to 120,000, preferably 50,000 to 100,000. Specifically, for example, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9. It is 5, 10, 10.5, 11, 11.5, or 120,000, and may be within the range between any two of the numerical values exemplified here. If the weight average molecular weight is less than 25,000, the heat resistance of the chlorine-containing polymer resin composition may not be sufficiently improved, and if it exceeds 120,000, the chlorine-containing polymer resin composition may not be sufficiently improved during kneading. Torque may increase.
  • the weight average molecular weight is a polystyrene-equivalent value measured by gel permeation chromatography (GPC), and can be measured under the following conditions.
  • Measurement name SYSTEM-21 Shodex (manufactured by Showa Denko KK) Column: 3 PL gel MIXED-B (manufactured by Polymer Laboratories) in series Temperature: 40 ° C Detection: Differential Refractometer Solvent: Tetrahydrofuran Concentration: 2% by mass Calibration curve: Created using standard polystyrene (PS) (manufactured by Polymer Laboratories)
  • a method for obtaining a maleimide-based copolymer having a preferable weight average molecular weight (Mw) range of 25,000 to 120,000 in addition to the method for adjusting the polymerization temperature, the polymerization time, and the amount of the polymerization initiator added, , A method of adjusting the amount of the solvent added and the amount of the chain transfer agent added. In addition, a method of reducing the molecular weight of the obtained copolymer by decomposition is known.
  • the polymerization mode of the maleimide-based copolymer includes, for example, solution polymerization, bulk polymerization and the like.
  • Solution polymerization is preferable from the viewpoint that a maleimide-based copolymer having a more uniform copolymer composition can be obtained by polymerizing while performing addition or the like.
  • the solvent for solution polymerization is preferably non-polymerizable from the viewpoint that by-products are difficult to form and adverse effects are small.
  • 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 and chlorobenzene, N, N-dimethylformamide and dimethyl. It is sulfoxide, N-methyl-2-pyrrolidone, etc., and methyl ethyl ketone and methyl isobutyl ketone are preferable because of the ease of solvent removal at the time of volatilization recovery of the maleimide-based copolymer.
  • any of continuous polymerization type, batch type (batch type) and semi-batch type can be applied.
  • the method for producing the maleimide-based copolymer is not particularly limited, but it can be preferably 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 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, ethyl-3,3-di- (t-butylperoxy) butyrate can be used, and one of these Seeds or a combination of two or more may be used.
  • the amount of the polymerization initiator used is not particularly limited, but is preferably 0.1 to 1.5% by mass, more preferably 0.1 to 1.5% by mass with respect to 100% by mass of all the monomer units. It is 1.0% by mass.
  • the amount of the polymerization initiator used is 0.1% by mass or more, a sufficient polymerization rate can be obtained, which is preferable.
  • the amount of the polymerization initiator used is 1.5% by mass or less, the polymerization rate can be suppressed, so that reaction control becomes easy and it becomes easy to obtain a target molecular weight.
  • a chain transfer agent can be used in the production of the maleimide-based copolymer.
  • the chain transfer agent used is not particularly limited, and examples thereof include n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, ⁇ -methylstyrene dimer, ethyl thioglycolate, limonene, turpinolene and the like. be.
  • the amount of the chain transfer amount 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 with respect to 100% by mass of all the monomer units. Is preferable, and more preferably 0.1 to 0.5% by mass. When the amount of the chain transfer agent used is 0.01% by mass to 0.8% by mass, the target molecular weight can be easily obtained.
  • a method for introducing the maleimide monomer unit of the maleimide-based copolymer a method of copolymerizing a maleimide-based monomer, an aromatic vinyl monomer, a cyanide vinyl monomer (direct method), or an unsaturated method is used.
  • An unsaturated dicarboxylic acid anhydride is obtained by copolymerizing a dicarboxylic acid anhydride, an aromatic vinyl monomer, and a vinyl cyanide monomer in advance, and then reacting the unsaturated dicarboxylic acid anhydride group with ammonia or a primary amine.
  • post-imidization method of converting an acid anhydride group into a maleimide monomer unit. The post-imidization method is preferable because the amount of residual maleimide-based monomer in the copolymer is small.
  • the primary amines used in the postimidization method are, for example, methylamine, ethylamine, n-propylamine, iso-propylamine, n-butylamine, n-pentylamine, n-hexylamine, n-octylamine and cyclohexyl.
  • alkylamines such as amines and decylamines and aromatic amines such as chlor or brom-substituted alkylamines, aniline, toluidine and naphthylamines, of which aniline and cyclohexylamines are preferred.
  • These primary amines may be used alone or in combination of two or more.
  • the amount of the primary amine added is not particularly limited, but is preferably 0.7 to 1.1 molar equivalents, more preferably 0.85 to 1.05 mol, based on the unsaturated dicarboxylic acid anhydride group. Equivalent. When it is 0.7 molar equivalent or more with respect to the unsaturated dicarboxylic acid anhydride monomer unit in the maleimide-based copolymer, it is preferable because the thermal stability is good. Further, when the equivalent is 1.1 mol equivalent or less, the amount of the primary amine remaining in the maleimide-based copolymer is reduced, which is preferable.
  • a catalyst may be used when introducing the maleimide monomer unit by the postimidization method.
  • the catalyst can improve the dehydration ring closure reaction in the reaction of ammonia or a primary amine with an unsaturated dicarboxylic acid anhydride group, particularly in the reaction of converting an unsaturated dicarboxylic acid anhydride group to a maleimide group.
  • the type of catalyst is not particularly limited, but for example, a tertiary amine can be used.
  • the tertiary amine is not particularly limited, and examples thereof include trimethylamine, triethylamine, tripropylamine, tributylamine, N, N-dimethylaniline, N, N-diethylaniline and the like.
  • the amount of the tertiary amine added is not particularly limited, but is preferably 0.01 molar equivalent or more with respect to the unsaturated dicarboxylic acid anhydride group.
  • the temperature of the imidization reaction in the present invention is preferably 100 to 250 ° C, more preferably 120 to 200 ° C. When the temperature of the imidization reaction is 100 ° C. or higher, the reaction rate is sufficiently high, which is preferable from the viewpoint of productivity. When the temperature of the imidization reaction is 250 ° C. or lower, deterioration of physical properties due to thermal deterioration of the maleimide-based copolymer can be suppressed, which is preferable.
  • a method for removing volatile components such as a solvent used for solution polymerization and unreacted monomers from a solution after solution polymerization of a maleimide-based copolymer or a solution after completion of post-imidization is known.
  • Method can be adopted.
  • a vacuum devolatilization tank with a heater or a devolatilization extruder with a vent can be used.
  • the devolatile, molten maleimide-based copolymer is transferred to the granulation process, extruded into strands from a porous die, and processed into pellets by a cold-cut method, an aerial hot-cut method, or an underwater hot-cut method. Can be done.
  • the maleimide-based copolymer of the present invention is also pulverized into the form of a powder before use.
  • the crushing method is not particularly limited, and a known crushing technique can be used. Suitable crushers include a turbo mill type crusher, a turbo disc mill type crusher, a turbo cutter type crusher, a jet mill type crusher, an impact type crusher, a hammer type crusher, a vibration type crusher and the like. ..
  • the chlorine-containing polymer in the present invention is a polymer obtained by polymerizing a vinyl chloride monomer alone or a mixture of a vinyl chloride monomer and one or more types of monomers copolymerizable therewith, and such a polymer.
  • This is a chlorine-added polymer obtained by further adding chlorine to the polymer obtained in the above.
  • the chlorine-containing polymer may also contain a compound of the polymer thus obtained and the chlorine-added polymer.
  • copolymerizable monomers examples 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, and butyl malate and diethylma. Fumaric acid esters such as rates, vinyl ethers such as vinyl methyl ether, vinyl butyl ether and vinyl octyl ether, vinyl cyanide such as acrylonitrile and methacrylonitrile, ⁇ -olefins such as ethylene and propylene, styrene and ⁇ -methyl.
  • Styrenes such as styrene, vinyltoluene, t-butylstyrene, chlorostyrene and their substitutes, vinylidene halides other than vinyl chloride such as vinylidene chloride and vinyl bromide, vinyl halides, and phthalates such as diallylphthalate.
  • the chlorine-containing polymer is preferably polyvinyl chloride obtained by polymerizing a vinyl chloride monomer from the viewpoint of compatibility with a maleimide-based copolymer.
  • the average degree of polymerization of the chlorine-containing polymer is 680 to 1900, preferably 700 to 1700.
  • the maleimide-based copolymer can be uniformly dispersed, and when it is 1900 or less, the kneadability with the maleimide-based copolymer is excellent.
  • the polymerization method of the chlorine-containing polymer is not particularly limited, and conventionally known bulk polymerization, solution polymerization, emulsion polymerization and the like are used.
  • the blending ratio of the maleimide-based copolymer and the chlorine-containing polymer in the present invention is preferably 5 to 50% by mass of the maleimide-based copolymer and 50 to 95% by mass of the chlorine-containing polymer, and more preferably the maleimide-based copolymer.
  • the combined content is 5 to 30% by mass and the chlorine-containing polymer is 70 to 95% by mass.
  • the mixing ratio of the maleimide-based copolymer is 5% by mass or more, a sufficient heat resistance-imparting effect can be obtained, and when it is 50% by mass or less, deterioration of releasability during kneading can be suppressed.
  • the chlorine-containing polymer-based resin composition in the present invention may contain an additive as described below to the extent that the effect of the present invention is not impaired, but is substantially composed of a maleimide-based copolymer and a chlorine-containing polymer. It may be a thing. If necessary, a strengthening agent, a processability improving agent, a heat stabilizer, a lubricant, a plasticizer and the like can be added alone or in combination of two or more to the chlorine-containing polymer resin composition of the present invention. As other additives, a light-resistant stabilizer, an ultraviolet absorber, an antioxidant, a pigment, a dye and the like can be arbitrarily added.
  • the method for obtaining the chlorine-containing polymer-based resin composition according to the present invention by kneading and mixing the maleimide-based copolymer and the chlorine-containing polymer is not particularly limited, and a known melt-kneading technique can be used.
  • Suitable melt-kneading devices include single-screw extruders, meshing co-rotating or meshing non-directional rotating twin-screw extruders, screw extruders such as non- or incomplete meshing twin-screw extruders, and Banbury mixers. There are coniders and mixed rolls. Further, a plurality of these extruders can be used in combination.
  • the extruder is composed of a kneading section for melt-kneading a maleimide-based copolymer and a chlorine-containing polymer, and at least one devolatilization section.
  • the maleimide-based copolymer and the chlorine-containing polymer supplied to the extruder are first melted in the kneading section and kneaded into a uniform composition.
  • the kneading portion is configured by combining known mixing elements such as a kneading disc.
  • an element having an action of pushing the molten resin back to the upstream side in the downstream of the kneading portion to fill the kneaded portion examples include reverse lead full flight, reverse shift kneading, and seal ring.
  • a known method can be adopted as the molding method of the chlorine-containing polymer resin composition.
  • injection molding, sheet extrusion molding, vacuum forming, blow molding, foam molding, profile extrusion molding and the like can be mentioned.
  • the chlorine-containing polymer resin composition is usually heated to 170 to 200 ° C. and then processed, but it is preferably 190 to 200 ° C.
  • Molded products can be used for rain gutters, air conditioner piping covers, plant piping, pipes, fittings, sprinkler piping, window frames, sashes, industrial products, and the like.
  • the filling amount is 190 ° C. It is preferable that the value of the maximum torque measured under the conditions of 60.0 g and 60 rpm is 50 Nm or less.
  • maleimide-based copolymer (A-1) > 73 parts by mass of styrene, 18 parts by mass of acrylonitrile, 1 part by mass of maleic acid anhydride, 0.22 parts by mass of ⁇ -methylstyrene dimer, and 26 parts by mass of methylethylketone were charged in an autoclave equipped with a stirrer and having a volume of about 120 liters. After replacing the phase part with nitrogen gas, the temperature was raised to 92 ° C. over 40 minutes with stirring.
  • a solution of 7 parts by mass of maleic anhydride and 1.0 part by mass of t-butylperoxy-2-ethylhexanoate in 35 parts by mass of methyl ethyl ketone was added over 4.5 hours while maintaining the temperature at 92 ° C. after the temperature was raised. Was added continuously. 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. Then, 6 parts by mass of aniline and 0.1 part by mass of triethylamine were added to the polymerization solution, and the mixture was reacted at 140 ° C. for 7 hours.
  • the imidization reaction solution was put into a vent type screw extruder to remove volatile components to obtain a pellet-shaped maleimide-based copolymer A-1.
  • the analysis results of the obtained maleimide-based copolymer are shown in Table 1.
  • Sty is a styrene monomer unit
  • AN is an acrylonitrile monomer unit
  • MAH is a maleic anhydride monomer unit
  • NPMI is an N-phenylmaleimide monomer unit
  • PVC polyvinyl chloride. Indicates vinyl.
  • a solution of 9 parts by mass of maleic anhydride and 0.60 parts by mass of t-butylperoxy-2-ethylhexanoate in 47 parts by mass of methyl ethyl ketone was continuously prepared over 5 hours while maintaining 92 ° C. after the temperature was raised. Was added. 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. Then, 9 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 7 hours.
  • a solution prepared by dissolving 7 parts by mass of maleic anhydride and 0.80 parts by mass of t-butylperoxy-2-ethylhexanoate in 33 parts by mass of methyl ethyl ketone was continuously prepared over 6 hours while maintaining 92 ° C. after the temperature was raised. Was 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. Then, 5 parts by mass of aniline and 0.1 part by mass of triethylamine were added to the polymerization solution, and the mixture was reacted at 140 ° C. for 7 hours.
  • maleimide-based copolymer (A-5) 25 parts by mass of styrene, 26 parts by mass of acrylonitrile, 2 parts by mass of maleic acid anhydride, 0.53 parts by mass of ⁇ -methylstyrene dimer, and 30 parts by mass of methylethylketone are charged in an autoclave equipped with a stirrer and having a volume of about 120 liters. After replacing the phase part with nitrogen gas, the temperature was raised to 92 ° C. over 40 minutes with stirring.
  • maleimide-based copolymer (A-6) 23 parts by mass of styrene, 26 parts by mass of acrylonitrile, 2 parts by mass of maleic acid anhydride, 0.32 parts by mass of ⁇ -methylstyrene dimer, and 32 parts by mass of methylethylketone were charged into an autoclave equipped with a stirrer and having a volume of about 120 liters. After replacing the phase part with nitrogen gas, the temperature was raised to 92 ° C. over 40 minutes with stirring.
  • a solution prepared by dissolving 4 parts by mass of maleic anhydride and 1.0 part by mass of t-butylperoxy-2-ethylhexanoate in 18 parts by mass of methyl ethyl ketone was added over 7.5 hours while maintaining 92 ° C. after the temperature was raised. Was added continuously. 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. Then, 3 parts by mass of aniline and 0.1 part by mass of triethylamine were added to the polymerization solution, and the mixture was reacted at 140 ° C. for 7 hours.
  • a solution prepared by dissolving 11 parts by mass of maleic anhydride and 1.20 parts by mass of t-butylperoxy-2-ethylhexanoate in 56 parts by mass of methyl ethyl ketone was added over 8.5 hours while maintaining the temperature at 92 ° C. after the temperature was raised. Was added continuously. 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. Then, 9 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 7 hours.
  • a solution of 13 parts by mass of maleic anhydride and 0.44 parts by mass of t-butylperoxy-2-ethylhexanoate in 69 parts by mass of methyl ethyl ketone was continuously prepared over 4 hours while maintaining 92 ° C. after the temperature was raised. Was added. Further, after the addition of maleic anhydride was completed, a solution prepared by dissolving 0.16 parts by mass of t-butylperoxy-2-ethylhexanoate in 1 part by mass of methyl ethyl ketone was continuously added over 1.5 hours. 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.
  • ⁇ Production example of maleimide-based copolymer (B-6)> 24 parts by mass of styrene, 24 parts by mass of acrylonitrile, 2 parts by mass of maleic acid anhydride, 0.53 parts by mass of ⁇ -methylstyrene dimer, and 33 parts by mass of methylethylketone were charged in an autoclave equipped with a stirrer and having a volume of about 120 liters. After replacing the phase part with nitrogen gas, the temperature was raised to 92 ° C. over 40 minutes with stirring.
  • a solution of 9 parts by mass of maleic anhydride and 0.60 parts by mass of t-butylperoxy-2-ethylhexanoate in 47 parts by mass of methyl ethyl ketone was continuously prepared over 5 hours while maintaining 92 ° C. after the temperature was raised. Was added. 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. Then, 9 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 7 hours.
  • a solution of 9 parts by mass of maleic anhydride and 0.60 parts by mass of t-butylperoxy-2-ethylhexanoate in 47 parts by mass of methyl ethyl ketone was continuously prepared over 5 hours while maintaining 92 ° C. after the temperature was raised. Was added. 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. Then, 9 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 7 hours.
  • Chlorine-containing polymer resin composition (Raw materials used) The raw materials used in each example and each comparative example are shown below.
  • Maleimide-based copolymer-(A-1 to A-6, B-1 to B-10) obtained according to the above-mentioned production example were used.
  • Examples 1 to 6 and Comparative Examples 1 to 12 (kneading and mixing of a maleimide-based copolymer and a chlorine-containing polymer)
  • a generally commercially available chlorine-containing polymer (product name: TH-1000) in which maleimide-based copolymers A-1 to A-6 and B-1 to B-12 are mixed with a stabilizer and a lubricant in advance with a Henshell mixer. , Taiyo PVC) is blended in the blending ratios shown in Tables 1 and 2, and then roll sheets are prepared using test rolls ( ⁇ 6 x L15 test rolls, manufactured by Kansai Roll Co., Ltd.), and the roll sheets are stacked. A test piece was prepared by press molding and cutting or punching, and each physical property value was measured. The results are shown in Tables 1 and 2.
  • composition analysis The composition analysis of each monomer unit was measured by the C-13 NMR method under the measurement conditions described below.
  • the weight average molecular weight is a polystyrene-equivalent value measured by gel permeation chromatography (GPC), and was measured under the following conditions. Measurement name: SYSTEM-21 Shodex (manufactured by Showa Denko KK) Column: 3 PL gel MIXED-B (manufactured by Polymer Laboratories) in series Temperature: 40 ° C Detection: Differential Refractometer Solvent: Tetrahydrofuran Concentration: 2% by mass Calibration curve: Created using standard polystyrene (PS) (manufactured by Polymer Laboratories)
  • the measuring machine used was a capillary rheometer 1D manufactured by Toyo Seiki Seisakusho Co., Ltd.
  • the Vicat softening point was measured by the 50 method (load 50 N, heating rate 50 ° C./hour) based on JIS K7206: 1999, using a test piece having a size of 20 mm ⁇ 20 mm and a thickness of 4 mm.
  • As the measuring machine an HDT & VSPT test device manufactured by Toyo Seiki Seisakusho Co., Ltd. was used.
  • the maximum torque of each Example and Comparative Example was measured as follows. 20 parts by mass of the maleimide-based polymer of Examples and Comparative Examples was added to 80 parts by mass of a chlorine-containing polymer (TH-1000, manufactured by Taiyo PVC Co., Ltd.) in which additives such as stabilizers and lubricants were added in advance and mixed with a Henshell mixer. I added a part.
  • TH-1000 manufactured by Taiyo PVC Co., Ltd.
  • melt-kneading of the maleimide-based copolymer and the chlorine-containing polymer a lab-plast mill (4C150 type, mixer model R60, manufactured by Toyo Seiki Seisakusho Co., Ltd.) was used, and the filling amount was 60.0 g, the temperature was 190 ° C., and the rotation speed was 60 rpm.
  • the maximum torque during kneading (kneading torque, unit: Nm) was measured under the conditions. When the value of the maximum torque is low, it is advantageous for melt-kneading, so that extrusion molding can be suitably performed.
  • Example 1 to 6 using the chlorine-containing polymer-based resin composition using the maleimide-based copolymer according to the present invention the heat resistance of the chlorine-containing polymer was sufficiently improved.
  • the yellowness of the maleimide-based copolymer used is controlled to be low, and coloring in the resin composition and its molded product can be suppressed.
  • the maximum torque at the time of melt-kneading the maleimide-based copolymer and the chlorine-containing polymer was suppressed to a low level. It is expected that extrusion molding of molded products can be carried out without problems.
  • a chlorine-containing polymer-based resin composition in which coloring is suppressed while improving the heat resistance of the chlorine-containing polymer, and chlorine containing a maleimide-based copolymer and a chlorine-containing polymer.
  • a polymer-based resin composition and a molded product thereof are provided, and are suitably used for molded products that require heat resistance and appearance performance, such as raindrops and pipe covers for air conditioners.
  • the chlorine-containing polymer resin composition according to the present invention is suitably used for extrusion molding.

Abstract

The present invention addresses the problem of providing: a maleimide copolymer from which it is possible to obtain a chlorine-containing polymer resin composition, in which coloration of the composition is suppressed and the heat resistance of the chlorine-containing polymer is improved; a chlorine-containing polymer resin composition including a maleimide copolymer and a chlorine-containing polymer; and a molded body of said chlorine-containing polymer resin composition. Furthermore, provide is a chlorine-containing polymer resin composition with excellent extrusion molding properties. The present invention provides a maleimide copolymer for chlorine-containing polymers which has 50 to 90 mass% of aromatic vinyl monomer units, 0.5 to 25 mass% of vinyl cyanide monomer units, 0 to 10 mass% of unsaturated acid anhydride monomer units, and 5 to 25 mass% of maleimide monomer units when the total of the aromatic vinyl monomer units, the vinyl cyanide monomer units, the unsaturated acid anhydride monomer units, and the maleimide monomer units is 100 mass%. The melt viscosity of the maleimide copolymer as measured under conditions of 190℃ and a shear rate of 100/sec, is 200 to 100,000 Pa sec. and the weight average molecular weight of the maleimide copolymer is 2.5 to 120,000.

Description

マレイミド系共重合体、及びマレイミド系共重合体と塩素含有ポリマーを含む塩素含有ポリマー系樹脂組成物Maleimide-based copolymer, and chlorine-containing polymer-based resin composition containing maleimide-based copolymer and chlorine-containing polymer.
　本発明は、マレイミド系共重合体、及びマレイミド系共重合体と塩素含有ポリマーを含む塩素含有ポリマー系樹脂組成物に関するものである。 The present invention relates to a maleimide-based copolymer and a chlorine-containing polymer-based resin composition containing a maleimide-based copolymer and a chlorine-containing polymer.
　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（熱軟化温度）に欠ける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。
　塩素含有ポリマー系樹脂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塩素含有ポリマーと混合する方法（特許文献１、２）が知られている。 Chlorine-containing polymer resins are inexpensive and have excellent chemical, physical, and mechanical properties, so they are mass-produced and used in a variety of applications.
However, the chlorine-containing polymer has a drawback of lacking heat resistance (heat softening temperature), and is measured by the 50 method (load 50 N, heating rate 50 ° C./hour) based on, for example, JIS K7206: 1999. The softening temperature is around 82 ° C., and the softening temperature is further lowered by the stabilizer and the plasticizer usually blended during the molding process.
As a method for improving the heat resistance of the chlorine-containing polymer resin, a method of mixing the resin imparting heat resistance with the chlorine-containing polymer (Patent Documents 1 and 2) is known.
特許０６４７５５０１Patent 06475501 特開２００６－２６５３７３JP 2006-265373
　本発明は、塩素含有ポリマーの耐熱性を向上しつつ、着色が抑えられた塩素含有ポリマー系樹脂組成物を得ることができるマレイミド系共重合体、マレイミド系共重合体と塩素含有ポリマーを含む塩素含有ポリマー系樹脂組成物及びその成形体を提供しようとするものである。さらに、押出成形性に優れた塩素含有ポリマー系樹脂組成物を提供しようとするものである。 INDUSTRIAL APPLICABILITY The present invention is a maleimide-based copolymer capable of obtaining a chlorine-containing polymer-based resin composition in which coloring is suppressed while improving the heat resistance of the chlorine-containing polymer, and chlorine containing a maleimide-based copolymer and a chlorine-containing polymer. An object of the present invention is to provide a polymer-based resin composition containing a compound and a molded product thereof. Further, it is an object of the present invention to provide a chlorine-containing polymer-based resin composition having excellent extrusion moldability.
　本発明者らの検討の結果、特定の単量体単位組成、特定の範囲の溶融粘度、及び特定の範囲の重量平均分子量を有し、黄色度を低く制御したマレイミド系共重合体を採用すれば、塩素含有ポリマーに耐熱性を付与できるとともに、樹脂組成物及びその成形体における着色を抑えることができることを見出した。さらに、当該樹脂組成物の押出成形性が良好であることを見出した。
　即ち、本発明は、
（１）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、不飽和酸無水物単量体単位及びマレイミド系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５０～９０質量％と、前記シアン化ビニル系単量体単位０．５～２５質量％と、前記不飽和酸無水物単量体単位０～１０質量％と、前記マレイミド系単量体単位５～２５質量％とを有し、１９０℃、せん断速度１００／ｓｅｃの条件で測定した溶融粘度が２００～１０００００Ｐａ・ｓｅｃであり、重量平均分子量が２．５～１２万である、塩素含有ポリマー用マレイミド系共重合体、
（２）（１）に記載のマレイミド系共重合体５～５０質量％と、塩素含有ポリマー５０～９５質量％と、を含有する、塩素含有ポリマー系樹脂組成物、
（３）前記溶融粘度が２００～７００００Ｐａ・ｓｅｃである、（２）に記載の塩素含有ポリマー系樹脂組成物、
（４）前記マレイミド系共重合体の重量平均分子量が５～１０万である、（２）又は（３）に記載の塩素含有ポリマー系樹脂組成物、
（５）前記マレイミド系共重合体が、芳香族ビニル系単量体単位を５０～８０質量％有する、（２）～（４）のいずれか１つに記載の塩素含有ポリマー系樹脂組成物、
（６）前記マレイミド系共重合体が、シアン化ビニル系単量体単位を５～２０質量％有する、（２）～（５）のいずれか１つに記載の塩素含有ポリマー系樹脂組成物、
（７）前記マレイミド系共重合体が、不飽和酸無水物単量体単位を０．３～５質量％有する、（２）～（６）のいずれか１つに記載の塩素含有ポリマー系樹脂組成物、
（８）前記マレイミド系共重合体が、マレイミド系単量体単位を５～２４質量％有する、（２）～（７）のいずれか１つに記載の塩素含有ポリマー系樹脂組成物、
（９）前記マレイミド系単量体単位がＮ－アリールマレイミドである、（２）～（８）のいずれか１つに記載の塩素含有ポリマー系樹脂組成物、
（１０）（２）～（９）のいずれか１つに記載の塩素含有ポリマー系樹脂組成物から成形されてなることを特徴とする成形体、
に関する。 As a result of the studies by the present inventors, a maleimide-based copolymer having a specific monomer unit composition, a specific range of melt viscosities, and a specific range of weight average molecular weight and having a low yellowness is adopted. For example, it has been found that heat resistance can be imparted to the chlorine-containing polymer and coloring in the resin composition and its molded product can be suppressed. Furthermore, they have found that the resin composition has good extrusion moldability.
That is, the present invention
(1) The fragrance when the total of the aromatic vinyl-based monomer unit, the cyanide vinyl-based monomer unit, the unsaturated acid anhydride monomer unit, and the maleimide-based monomer unit is 100% by mass. The group vinyl-based monomer unit 50 to 90% by mass, the cyanide vinyl-based monomer unit 0.5 to 25% by mass, the unsaturated acid anhydride monomer unit 0 to 10% by mass, and the above. It has a maleimide-based monomer unit of 5 to 25% by mass, has a melt viscosity of 200 to 100,000 Pa · sec measured under the conditions of 190 ° C. and a shear rate of 100 / sec, and has a weight average molecular weight of 250,000 to 120,000. Maleimide-based copolymer for chlorine-containing polymers,
(2) A chlorine-containing polymer-based resin composition containing 5 to 50% by mass of the maleimide-based copolymer and 50 to 95% by mass of the chlorine-containing polymer according to (1).
(3) The chlorine-containing polymer-based resin composition according to (2), wherein the melt viscosity is 200 to 70,000 Pa · sec.
(4) The chlorine-containing polymer-based resin composition according to (2) or (3), wherein the maleimide-based copolymer has a weight average molecular weight of 50,000 to 100,000.
(5) The chlorine-containing polymer-based resin composition according to any one of (2) to (4), wherein the maleimide-based copolymer has 50 to 80% by mass of an aromatic vinyl-based monomer unit.
(6) The chlorine-containing polymer-based resin composition according to any one of (2) to (5), wherein the maleimide-based copolymer has 5 to 20% by mass of vinyl cyanide-based monomer units.
(7) The chlorine-containing polymer-based resin according to any one of (2) to (6), wherein the maleimide-based copolymer has 0.3 to 5% by mass of an unsaturated acid anhydride monomer unit. Composition,
(8) The chlorine-containing polymer-based resin composition according to any one of (2) to (7), wherein the maleimide-based copolymer has 5 to 24% by mass of a maleimide-based monomer unit.
(9) The chlorine-containing polymer-based resin composition according to any one of (2) to (8), wherein the maleimide-based monomer unit is N-arylmaleimide.
(10) A molded product, which is formed from the chlorine-containing polymer-based resin composition according to any one of (2) to (9).
Regarding.
　本発明のマレイミド系共重合体を採用すれば、塩素含有ポリマーに耐熱性を付与できるとともに、樹脂組成物及びその成形体における着色を抑えることができる。このため、耐熱性が要求される用途や、良好な外観が要求される用途に好適に利用される。さらに、混練性にも優れているため、押出成形にも好適に利用される。 If the maleimide-based copolymer of the present invention is adopted, heat resistance can be imparted to the chlorine-containing polymer, and coloring in the resin composition and its molded body can be suppressed. Therefore, it is suitably used for applications that require heat resistance and applications that require good appearance. Further, since it is excellent in kneading property, it is suitably used for extrusion molding.
＜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 specification of the present application, the description "A to B" means that it is A or more and B or less.
　以下、本発明の実施形態について、詳細に説明する。また、各実施形態はそれぞれ互いに組み合わせることが可能である。 Hereinafter, embodiments of the present invention will be described in detail. Moreover, each embodiment can be combined with each other.
（１．マレイミド系共重合体に含有される単量体単位）
　本発明におけるマレイミド系共重合体は、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、不飽和酸無水物単量体単位及びマレイミド系単量体単位を含有する。マレイミド系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。 (1. Monomer unit contained in maleimide-based copolymer)
The maleimide-based copolymer in the present invention contains an aromatic vinyl-based monomer unit, a cyanide vinyl-based monomer unit, an unsaturated acid anhydride monomer unit, and a maleimide-based monomer unit. The monomer unit contained in the maleimide-based copolymer will be described below.
（１－１．芳香族ビニル系単量体単位）
　本発明にかかるマレイミド系共重合体に用いることのできる芳香族ビニル単量体としては、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。これらの中でも色相を向上させる効果の高いスチレンが好ましい。スチレン系単量体は、単独でも良いが２種類以上を併用しても良い。 (1-1. Aromatic vinyl-based monomer unit)
Examples of the aromatic vinyl monomer that can be used in the maleimide-based copolymer according to the present invention include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, and ethyl. Examples thereof include styrene, p-tert-butyl styrene, α-methyl styrene, α-methyl-p-methyl styrene and the like. Among these, styrene, which has a high effect of improving hue, is preferable. The styrene-based monomer may be used alone or in combination of two or more.
　本発明にかかるマレイミド系共重合体は、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、不飽和酸無水物単量体単位及びマレイミド系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５０～９０質量％含有し、好ましくは５０～８０質量％含有し、さらに好ましくは６０～７０質量％含有する。具体的には例えば、５０、４５、５０、５５、６０、６５、７０、７５、８０、８５、又は９０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が５０質量％に満たないとマレイミド系共重合体に含有される他の単量体成分が相対的に増える結果として、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場合や、マレイミド系共重合体の黄色度（ＹＩ）が高くなることに起因して塩素含有ポリマー系樹脂組成物及びその成形体の着色が問題となる場合があり、９０質量％を超えると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ない場合がある。 The maleimide-based copolymer according to the present invention has a total of 100 mass by mass of an aromatic vinyl-based monomer unit, a cyanide vinyl-based monomer unit, an unsaturated acid anhydride monomer unit, and a maleimide-based monomer unit. %, The aromatic vinyl-based monomer unit is contained in an amount of 50 to 90% by mass, preferably 50 to 80% by mass, and more preferably 60 to 70% by mass. Specifically, for example, it is 50, 45, 50, 55, 60, 65, 70, 75, 80, 85, or 90% by mass, and is within the range between any two of the numerical values exemplified here. May be good. If the amount of the aromatic vinyl-based monomer unit is less than 50% by mass, the other monomer components contained in the maleimide-based copolymer will increase relatively, and as a result, the maleimide-based copolymer will be a chlorine-containing polymer. In some cases, the maleimide-based copolymer cannot be kneaded without melting, or the coloration of the chlorine-containing polymer-based resin composition and its molded product may become a problem due to the high yellowness (YI) of the maleimide-based copolymer. If it exceeds 90% by mass, the heat resistance of the chlorine-containing polymer resin composition may not be sufficiently improved.
（１－２．シアン化ビニル系単量体単位）
　本発明にかかるマレイミド系共重合体に用いることのできるシアン化ビニル系単量体単位としては、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。シアン化ビニル単量体は単独でも良いが２種類以上を併用しても良い。 (1-2. Vinyl cyanide-based monomer unit)
Examples of the vinyl cyanide-based monomer unit that can be used in the maleimide-based copolymer according to the present invention include acrylonitrile, methacrylonitrile, etacrylonitrile, and fumaronitrile. Among these, acrylonitrile is preferable from the viewpoint of imparting heat resistance to the hue and the chlorine-containing polymer resin composition. The vinyl cyanide monomer may be used alone or in combination of two or more.
　本発明にかかるマレイミド系共重合体は、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、不飽和酸無水物単量体単位及びマレイミド系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０．５～２５質量％含有し、好ましくは５～２０質量％含有し、さらに好ましくは１～２０質量％含有する。具体的には例えば、０．５、１、５、１０、１５、２０、又は２５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が０．５質量％に満たないと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ない場合があり、２５質量％を越えるとマレイミド系共重合体の黄色度（ＹＩ）が高くなる場合がある。 The maleimide-based copolymer according to the present invention has a total of 100 mass by mass of an aromatic vinyl-based monomer unit, a cyanide vinyl-based monomer unit, an unsaturated acid anhydride monomer unit, and a maleimide-based monomer unit. %, The vinyl cyanide-based monomer unit is contained in an amount of 0.5 to 25% by mass, preferably 5 to 20% by mass, and more preferably 1 to 20% by mass. Specifically, for example, it is 0.5, 1, 5, 10, 15, 20, or 25% by mass, and may be within the range between any two of the numerical values exemplified here. If the amount of vinyl cyanide-based monomer unit is less than 0.5% by mass, the heat resistance of the chlorine-containing polymer-based resin composition may not be sufficiently improved, and if it exceeds 25% by mass, it is maleimide-based. The yellowness (YI) of the copolymer may be high.
（１－３．不飽和酸無水物単量体単位）
　本発明にかかるマレイミド系共重合体に用いることのできる不飽和酸無水物単量体単位としては、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単位は単独でも良いが２種類以上を併用しても良い。 (1-3. Unsaturated acid anhydride monomer unit)
Examples of the unsaturated acid anhydride monomer unit that can be used in the maleimide-based copolymer according to the present invention include maleic acid anhydride, itaconic acid anhydride, citraconic acid anhydride, aconitic acid anhydride and the like. .. Among these, maleic anhydride is preferable from the viewpoint of imparting heat resistance to the chlorine-containing polymer resin composition. The unsaturated acid anhydride monomer unit may be used alone or in combination of two or more.
　本発明にかかるマレイミド系共重合体は、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、不飽和酸無水物単量体単位及びマレイミド系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％含有し、好ましくは０．３～５質量％含有し、さらに好ましくは０．５～５質量％含有する。具体的には例えば、０、０．５、０．６、０．７、０．８、０．９、１、２、３、４、５、６、７、８、９、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が１０質量％を越えると流動性が低下し、塩素含有ポリマーとの混練性が低下する場合がある。 The maleimide-based copolymer according to the present invention has a total of 100 mass of aromatic vinyl-based monomer unit, cyanide vinyl-based monomer unit, unsaturated acid anhydride monomer unit and maleimide-based monomer unit. %, The unsaturated acid anhydride monomer unit is contained in an amount of 0 to 10% by mass, preferably 0.3 to 5% by mass, and more preferably 0.5 to 5% by mass. Specifically, for example, 0, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10% by mass. It may be within the range between any two of the numerical values exemplified here. If the amount of the unsaturated acid anhydride monomer unit exceeds 10% by mass, the fluidity may decrease and the kneadability with the chlorine-containing polymer may decrease.
（１－４．マレイミド系単量体単位）
　本発明にかかるマレイミド系共重合体に用いることのできるマレイミド系単量体単位としては、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。
　マレイミド系共重合体にマレイミド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単位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。 (1-4. Maleimide-based monomer unit)
Examples of the maleimide-based monomer unit that can be used in the maleimide-based copolymer according to the present invention include N-alkylmaleimide such as N-methylmaleimide, N-butylmaleimide, and N-cyclohexylmaleimide, and N-phenyl. There are N-arylmaleimide such as maleimide, N-chlorphenylmaleimide, N-methylphenylmaleimide, N-methoxyphenylmaleimide, N-tribromophenylmaleimide and the like. Among these, N-arylmaleimide is preferable, and N-phenylmaleimide is more preferable, from the viewpoint of imparting heat resistance to the chlorine-containing polymer resin composition. The maleimide-based monomer may be used alone or in combination of two or more.
In order to contain a maleimide monomer unit in a maleimide-based copolymer, for example, a copolymer obtained by copolymerizing a raw material composed of an unsaturated dicarboxylic acid monomer unit with another monomer is made into ammonia or a primary polymer. It may be imidized with an amine. Alternatively, a raw material made of a maleimide-based monomer may be copolymerized with another monomer.
　本発明にかかるマレイミド系共重合体は、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、不飽和酸無水物単量体単位及びマレイミド系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５～２５質量％含有し、好ましくは５質量％以上且つ２５質量％未満含有し、より好ましくは５～２４質量％含有し、さらに好ましくは１０～２４質量％含有する。具体的には例えば、５、１０、１１、１２、１３、１４、１５、１６、１７、１８、１９、２０、２１、２２、２３、２４、又は２５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が５質量％に満たないと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ない場合があり、２５質量％を超えると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場合がある。 The maleimide-based copolymer according to the present invention has a total of 100 mass by mass of an aromatic vinyl-based monomer unit, a cyanide vinyl-based monomer unit, an unsaturated acid anhydride monomer unit, and a maleimide-based monomer unit. %, The maleimide-based monomer unit is contained in an amount of 5 to 25% by mass, preferably 5% by mass or more and less than 25% by mass, more preferably 5 to 24% by mass, and further preferably 10 to 10% by mass. Contains 24% by mass. Specifically, for example, it is 5, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, or 25% by mass, and is a numerical value exemplified here. It may be within the range between any two of the above. If the amount of the maleimide-based monomer unit is less than 5% by mass, the heat resistance of the chlorine-containing polymer-based resin composition may not be sufficiently improved, and if it exceeds 25% by mass, the maleimide-based copolymer is formed. It may not melt with the chlorine-containing polymer and cannot be kneaded.
（１－５．共重合可能な単量体）
　本発明にかかるマレイミド系共重合体は、芳香族ビニル単量体、シアン化ビニル単量体、不飽和酸無水物単量体単位及びマレイミド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。マレイミド系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。マレイミド系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。 (1-5. Copolymerizable monomer)
The maleimide-based copolymer according to the present invention comprises a copolymerizable monomer other than an aromatic vinyl monomer, a vinyl cyanide monomer, an unsaturated acid anhydride monomer unit and a maleimide monomer. Copolymerization may be carried out as long as the effect of the present invention is not impaired. Examples of the monomer copolymerizable with the maleimide-based copolymer include acrylic acid ester monomers such as methyl acrylic acid ester, ethyl acrylic acid ester, and butyl acrylic acid ester, methyl methacrylate ester, and ethyl methacrylate ester. Examples thereof include methacrylic acid ester monomers, vinyl carboxylic acid monomers such as acrylic acid and methacrylic acid, acrylic acid amides and methacrylic acid amides. The monomer copolymerizable with the maleimide-based copolymer may be used alone or in combination of two or more.
Such a monomer can be copolymerized as long as the effect of the present invention is not impaired, but it is preferably 20% by mass or less, preferably 10% by mass, from the viewpoint of imparting heat resistance to the chlorine-containing polymer resin composition. % Or less is more preferable.
（１－６．添加剤）
　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耐光安定剤、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。 (1-6. Additives)
After completion of the polymerization, the polymerization solution contains heat-resistant stabilizers such as hindered phenol-based compounds, lactone-based compounds, phosphorus-based compounds and sulfur-based compounds, and light-resistant stabilizers such as hindered amine-based compounds and benzotriazole-based compounds, as necessary. Additives such as lubricants, plasticizers, colorants, antistatic agents, and mineral oils may be added. The amount added is preferably less than 0.2 parts by mass with respect to 100 parts by mass of all the monomer units. These additives may be used alone or in combination of two or more.
（２．マレイミド系共重合体の物性）
（２－１．マレイミド系共重合体の溶融粘度）
　本発明におけるマレイミド系共重合体の溶融粘度は２００～１０００００Ｐａ・ｓｅｃであり、好ましくは２００～７００００Ｐａ・ｓｅｃ、さらに好ましくは５００～７００００Ｐａ・ｓｅｃである。具体的には例えば、２００、５００、１０００、２０００、３０００、４０００、５０００、６０００、７０００、８０００、９０００、１００００、２００００、３００００、４００００、５００００、又は１０００００Ｐａ・ｓｅｃ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。２００Ｐａ・ｓｅｃに満たないと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ない場合があり、１０００００Ｐａ・ｓｅｃを超えると混合樹脂の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することが不可能となる場合がある。
　溶融粘度は、株式会社東洋精機製作所製キャピラリーレオメータ１Ｄを用いて、Ｌ＝４０ｍｍ、Ｄ＝１ｍｍのキャピラリーダイで測定した。 (2. Physical characteristics of maleimide-based copolymer)
(2-1. Melt viscosity of maleimide-based copolymer)
The melt viscosity of the maleimide-based copolymer in the present invention is 200 to 100,000 Pa · sec, preferably 200 to 70,000 Pa · sec, and more preferably 500 to 70,000 Pa · sec. Specifically, for example, it is 200, 500, 1000, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, 10000, 20000, 30000, 40,000, 50000, or 100,000 Pa · sec, and is a numerical value exemplified here. It may be within the range between any two of the above. If it is less than 200 Pa · sec, the heat resistance of the chlorine-containing polymer resin composition may not be sufficiently improved, and if it exceeds 100,000 Pa · sec, the maleimide-based copolymer of the mixed resin melts with the chlorine-containing polymer. It may not be possible to knead without kneading.
The melt viscosity was measured with a capillary rheometer 1D manufactured by Toyo Seiki Seisakusho Co., Ltd. with a capillary die having L = 40 mm and D = 1 mm.
　マレイミド系共重合体の溶融粘度は、マレイミド系共重合体を構成する単量体単位の配合比の調整により調整することが可能である。例えば、マレイミド系共重合体中のシアン化ビニル系単量体単位の含有量を増やしたり、マレイミド系共重合体中のマレイミド系単量体単位の含有量を増やすことにより溶融粘度を高くすることが可能である。また、マレイミド系共重合体の重量平均分子量を大きくすることによっても溶融粘度を高くすることが可能である。これらの調整方法は、併用することが可能である。 The melt viscosity of the maleimide-based copolymer can be adjusted by adjusting the blending ratio of the monomer units constituting the maleimide-based copolymer. For example, increasing the melt viscosity by increasing the content of vinyl cyanide-based monomer units in the maleimide-based copolymer or increasing the content of maleimide-based monomer units in the maleimide-based copolymer. Is possible. It is also possible to increase the melt viscosity by increasing the weight average molecular weight of the maleimide-based copolymer. These adjustment methods can be used together.
（２－２．マレイミド系共重合体の重量平均分子量）
　本発明におけるマレイミド系共重合体の重量平均分子量は、２．５万～１２万であり、好ましくは５万～１０万である。具体的には例えば、２．５、３、３．５、４、４．５、５、５．５、６、６．５、７、７．５、８、８．５、９、９．５、１０、１０．５、１１、１１．５、又は１２万であり、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。重量平均分子量が２．５万に満たないと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ない場合があり、１２万を超えると塩素含有ポリマー系樹脂組成物の混練時のトルクが上昇する場合がある。

　重量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）にて測定されるポリスチレン換算の値であり、以下の条件で測定できる。
　測定名：ＳＹＳＴＥＭ－２１　Ｓｈｏｄｅｘ（昭和電工株式会社製）
　カラム：ＰＬ　ｇｅｌ　ＭＩＸＥＤ－Ｂ（ポリマーラボラトリーズ社製）を３本直列
　温度：４０℃
　検出：示差屈折率
　溶媒：テトラヒドロフラン
　濃度：２質量％
　検量線：標準ポリスチレン（ＰＳ）（ポリマーラボラトリーズ社製）を用いて作成 (2-2. Weight average molecular weight of maleimide-based copolymer)
The weight average molecular weight of the maleimide-based copolymer in the present invention is 25,000 to 120,000, preferably 50,000 to 100,000. Specifically, for example, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9. It is 5, 10, 10.5, 11, 11.5, or 120,000, and may be within the range between any two of the numerical values exemplified here. If the weight average molecular weight is less than 25,000, the heat resistance of the chlorine-containing polymer resin composition may not be sufficiently improved, and if it exceeds 120,000, the chlorine-containing polymer resin composition may not be sufficiently improved during kneading. Torque may increase.

The weight average molecular weight is a polystyrene-equivalent value measured by gel permeation chromatography (GPC), and can be measured under the following conditions.
Measurement name: SYSTEM-21 Shodex (manufactured by Showa Denko KK)
Column: 3 PL gel MIXED-B (manufactured by Polymer Laboratories) in series Temperature: 40 ° C
Detection: Differential Refractometer Solvent: Tetrahydrofuran Concentration: 2% by mass
Calibration curve: Created using standard polystyrene (PS) (manufactured by Polymer Laboratories)
　好ましい重量平均分子量（Ｍｗ）の範囲である２．５万～１２万であるマレイミド系共重合体を得る方法としては、重合温度、重合時間、および重合開始剤添加量の調整する方法に加えて、溶剤の添加量および連鎖移動剤の添加量を調整する方法が挙げられる。他にも、得られた共重合体を分解により低分子量化する方法が知られている。 As a method for obtaining a maleimide-based copolymer having a preferable weight average molecular weight (Mw) range of 25,000 to 120,000, in addition to the method for adjusting the polymerization temperature, the polymerization time, and the amount of the polymerization initiator added, , A method of adjusting the amount of the solvent added and the amount of the chain transfer agent added. In addition, a method of reducing the molecular weight of the obtained copolymer by decomposition is known.
（３．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マレイミド系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、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。 (3. Production of maleimide-based copolymer)
The polymerization mode of the maleimide-based copolymer includes, for example, solution polymerization, bulk polymerization and the like. Solution polymerization is preferable from the viewpoint that a maleimide-based copolymer having a more uniform copolymer composition can be obtained by polymerizing while performing addition or the like. The solvent for solution polymerization is preferably non-polymerizable from the viewpoint that by-products are difficult to form and adverse effects are small. 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 and chlorobenzene, N, N-dimethylformamide and dimethyl. It is sulfoxide, N-methyl-2-pyrrolidone, etc., and methyl ethyl ketone and methyl isobutyl ketone are preferable because of the ease of solvent removal at the time of volatilization recovery of the maleimide-based copolymer. As the polymerization process, any of continuous polymerization type, batch type (batch type) and semi-batch type can be applied.
　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-based copolymer is not particularly limited, but it can be preferably 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 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, ethyl-3,3-di- (t-butylperoxy) butyrate can be used, and one of these Seeds or a combination of two or more may be used. From the viewpoint of controlling the reaction rate of polymerization and the polymerization rate, 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 is preferably 0.1 to 1.5% by mass, more preferably 0.1 to 1.5% by mass with respect to 100% by mass of all the monomer units. It is 1.0% by mass. When the amount of the polymerization initiator used is 0.1% by mass or more, a sufficient polymerization rate can be obtained, which is preferable. When the amount of the polymerization initiator used is 1.5% by mass or less, the polymerization rate can be suppressed, so that reaction control becomes easy and it becomes easy to obtain a 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 the maleimide-based copolymer. The chain transfer agent used is not particularly limited, and examples thereof include n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, α-methylstyrene dimer, ethyl thioglycolate, limonene, turpinolene and the like. be. The amount of the chain transfer amount 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 with respect to 100% by mass of all the monomer units. Is preferable, and more preferably 0.1 to 0.5% by mass. When the amount of the 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のマレイミド単量体単位の導入方法としては、マレイミド系単量体、芳香族ビニル単量体、シアン化ビニル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、芳香族ビニル単量体、シアン化ビニル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。 As a method for introducing the maleimide monomer unit of the maleimide-based copolymer, a method of copolymerizing a maleimide-based monomer, an aromatic vinyl monomer, a cyanide vinyl monomer (direct method), or an unsaturated method is used. An unsaturated dicarboxylic acid anhydride is obtained by copolymerizing a dicarboxylic acid anhydride, an aromatic vinyl monomer, and a vinyl cyanide monomer in advance, and then reacting the unsaturated dicarboxylic acid anhydride group with ammonia or a primary amine. There is a method (post-imidization method) of converting an acid anhydride group into a maleimide monomer unit. The post-imidization method is preferable because the amount of residual maleimide-based monomer in the copolymer is small.
　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、マレイミド系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 postimidization method are, for example, methylamine, ethylamine, n-propylamine, iso-propylamine, n-butylamine, n-pentylamine, n-hexylamine, n-octylamine and cyclohexyl. There are alkylamines such as amines and decylamines and aromatic amines such as chlor or brom-substituted alkylamines, aniline, toluidine and naphthylamines, of which aniline and cyclohexylamines are preferred. These primary amines may be used alone or in combination of two or more. The amount of the primary amine added is not particularly limited, but is preferably 0.7 to 1.1 molar equivalents, more preferably 0.85 to 1.05 mol, based on the unsaturated dicarboxylic acid anhydride group. Equivalent. When it is 0.7 molar equivalent or more with respect to the unsaturated dicarboxylic acid anhydride monomer unit in the maleimide-based copolymer, it is preferable because the thermal stability is good. Further, when the equivalent is 1.1 mol equivalent or less, the amount of the primary amine remaining in the maleimide-based copolymer is reduced, which is preferable.
　マレイミド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℃以下であればマレイミド系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 postimidization method. The catalyst can improve the dehydration ring closure reaction in the reaction of ammonia or a primary amine with an unsaturated dicarboxylic acid anhydride group, particularly in the reaction of converting an unsaturated dicarboxylic acid anhydride group to a maleimide group. The type of catalyst is not particularly limited, but for example, a tertiary amine can be used. The tertiary amine is not particularly limited, and examples thereof include trimethylamine, triethylamine, tripropylamine, tributylamine, N, N-dimethylaniline, N, N-diethylaniline and the like. The amount of the tertiary amine added is not particularly limited, but is preferably 0.01 molar equivalent or more with respect to the unsaturated dicarboxylic acid anhydride group. The temperature of the imidization reaction in the present invention is preferably 100 to 250 ° C, more preferably 120 to 200 ° C. When the temperature of the imidization reaction is 100 ° C. or higher, the reaction rate is sufficiently high, which is preferable from the viewpoint of productivity. When the temperature of the imidization reaction is 250 ° C. or lower, deterioration of physical properties due to thermal deterioration of the maleimide-based copolymer can be suppressed, which is preferable.
　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。
　塩素含有ポリマーがパウダー形状である場合は、本発明のマレイミド系共重合体もパウダー形状に粉砕して使用した方が好ましい。粉砕方法としては、特に限定はなく、公知の粉砕技術を用いることが出来る。好適に使用できる粉砕装置としては、ターボミル式粉砕機、ターボディスクミル式粉砕機、ターボカッター式粉砕機、ジェットミル式粉砕機、衝撃式粉砕機、ハンマー式粉砕機、振動式粉砕機等がある。 A method (devolatile method) for removing volatile components such as a solvent used for solution polymerization and unreacted monomers from a solution after solution polymerization of a maleimide-based copolymer or a solution after completion of post-imidization is known. Method can be adopted. For example, a vacuum devolatilization tank with a heater or a devolatilization extruder with a vent can be used. The devolatile, molten maleimide-based copolymer is transferred to the granulation process, extruded into strands from a porous die, and processed into pellets by a cold-cut method, an aerial hot-cut method, or an underwater hot-cut method. Can be done.
When the chlorine-containing polymer is in the form of a powder, it is preferable that the maleimide-based copolymer of the present invention is also pulverized into the form of a powder before use. The crushing method is not particularly limited, and a known crushing technique can be used. Suitable crushers include a turbo mill type crusher, a turbo disc mill type crusher, a turbo cutter type crusher, a jet mill type crusher, an impact type crusher, a hammer type crusher, a vibration type crusher and the like. ..
（４．塩素含有ポリマー）
　本発明におけ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、マレイミド系共重合体との親和性の観点から、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。 (4. Chlorine-containing polymer)
The chlorine-containing polymer in the present invention is a polymer obtained by polymerizing a vinyl chloride monomer alone or a mixture of a vinyl chloride monomer and one or more types of monomers copolymerizable therewith, and such a polymer. This is a chlorine-added polymer obtained by further adding chlorine to the polymer obtained in the above. Further, the chlorine-containing polymer may also contain a compound of the polymer thus obtained and the chlorine-added polymer. Examples of 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, and butyl malate and diethylma. Fumaric acid esters such as rates, vinyl ethers such as vinyl methyl ether, vinyl butyl ether and vinyl octyl ether, vinyl cyanide such as acrylonitrile and methacrylonitrile, α-olefins such as ethylene and propylene, styrene and α-methyl. Styrenes such as styrene, vinyltoluene, t-butylstyrene, chlorostyrene and their substitutes, vinylidene halides other than vinyl chloride such as vinylidene chloride and vinyl bromide, vinyl halides, and phthalates such as diallylphthalate. Can be mentioned.
The chlorine-containing polymer is preferably polyvinyl chloride obtained by polymerizing a vinyl chloride monomer from the viewpoint of compatibility with a maleimide-based copolymer.
　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 680 to 1900, preferably 700 to 1700. When the average degree of polymerization is 680 or more, the maleimide-based copolymer can be uniformly dispersed, and when it is 1900 or less, the kneadability with the maleimide-based copolymer is excellent.
（４－１．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。 (4-1. Manufacture of chlorine-containing polymer)
The polymerization method of the chlorine-containing polymer is not particularly limited, and conventionally known bulk polymerization, solution polymerization, emulsion polymerization and the like are used.
（５．マレイミド系共重合体と塩素含有ポリマーを含有する塩素含有ポリマー系樹脂組成物）
　本発明におけるマレイミド系共重合体と塩素含有ポリマーの配合割合は、マレイミド系共重合体５～５０質量％、塩素含有ポリマー５０～９５質量％であることが好ましく、さらに好ましくは、マレイミド系共重合体５～３０質量％、塩素含有ポリマー７０～９５質量％である。マレイミド系共重合体の配合割合を５質量％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％以下とすることで混練時の離型性悪化が抑えられる。 (5. Chlorine-containing polymer-based resin composition containing a maleimide-based copolymer and a chlorine-containing polymer)
The blending ratio of the maleimide-based copolymer and the chlorine-containing polymer in the present invention is preferably 5 to 50% by mass of the maleimide-based copolymer and 50 to 95% by mass of the chlorine-containing polymer, and more preferably the maleimide-based copolymer. The combined content is 5 to 30% by mass and the chlorine-containing polymer is 70 to 95% by mass. When the mixing ratio of the maleimide-based copolymer is 5% by mass or more, a sufficient heat resistance-imparting effect can be obtained, and when it is 50% by mass or less, deterioration of releasability during kneading can be suppressed.
（５－１．塩素含有ポリマー系樹脂組成物の添加剤）
　本発明における塩素含有ポリマー系樹脂組成物は、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、実質的にマレイミド系共重合体と塩素含有ポリマーからなるものでも良い。
　本発明の塩素含有ポリマー系樹脂組成物に、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、耐光安定剤、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。 (5-1. Additives for chlorine-containing polymer resin composition)
The chlorine-containing polymer-based resin composition in the present invention may contain an additive as described below to the extent that the effect of the present invention is not impaired, but is substantially composed of a maleimide-based copolymer and a chlorine-containing polymer. It may be a thing.
If necessary, a strengthening agent, a processability improving agent, a heat stabilizer, a lubricant, a plasticizer and the like can be added alone or in combination of two or more to the chlorine-containing polymer resin composition of the present invention.
As other additives, a light-resistant stabilizer, an ultraviolet absorber, an antioxidant, a pigment, a dye and the like can be arbitrarily added.
（５－２．塩素含有ポリマー系樹脂組成物の製造）
　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本発明にかかる塩素含有ポリマー系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。 (5-2. Production of chlorine-containing polymer resin composition)
The method for obtaining the chlorine-containing polymer-based resin composition according to the present invention by kneading and mixing the maleimide-based copolymer and the chlorine-containing polymer is not particularly limited, and a known melt-kneading technique can be used. Suitable melt-kneading devices include single-screw extruders, meshing co-rotating or meshing non-directional rotating twin-screw extruders, screw extruders such as non- or incomplete meshing twin-screw extruders, and Banbury mixers. There are coniders and mixed rolls. Further, a plurality of these extruders can be used in combination.
　押出機は、マレイミド系共重合体と塩素含有ポリマーを溶融混練するための混練部と少なくとも１つの脱揮部から構成される。押出機に供給されたマレイミド系共重合体と塩素含有ポリマーは、まず、混練部にて溶融され、均一な組成に混練される。混練部は、ニーディングディスク等の公知のミキシングエレメントを組合せて構成される。混練部の下流には、上流側に溶融樹脂を押し戻す作用を有するエレメントを使用し、混練部を充満状態にすることが混練性の観点から好ましい。当該エレメントとしては、例えば、逆リードフルフライト、逆ずらしニーディング、シールリングなどが挙げられる。 The extruder is composed of a kneading section for melt-kneading a maleimide-based copolymer and a chlorine-containing polymer, and at least one devolatilization section. The maleimide-based copolymer and the chlorine-containing polymer supplied to the extruder are first melted in the kneading section and kneaded into a uniform composition. The kneading portion is configured by combining known mixing elements such as a kneading disc. From the viewpoint of kneading property, it is preferable to use an element having an action of pushing the molten resin back to the upstream side in the downstream of the kneading portion to fill the kneaded portion. Examples of the element include reverse lead full flight, reverse shift kneading, and seal ring.
　塩素含有ポリマー系樹脂組成物の成形方法は、公知の方法が採用できる。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。成形品は、雨どい、エアコンの配管カバー、プラント配管、パイプ、継手、スプリンクラー配管、窓枠、サッシ、工業製品等に用いることができる。 A known method can be adopted as the molding method of the chlorine-containing polymer resin composition. For example, injection molding, sheet extrusion molding, vacuum forming, blow molding, foam molding, profile extrusion molding and the like can be mentioned. At the time of molding, the chlorine-containing polymer resin composition is usually heated to 170 to 200 ° C. and then processed, but it is preferably 190 to 200 ° C. Molded products can be used for rain gutters, air conditioner piping covers, plant piping, pipes, fittings, sprinkler piping, window frames, sashes, industrial products, and the like.
（５－３．塩素含有ポリマー系樹脂組成物の溶融混練時の最大トルク）
　塩素含有ポリマー系樹脂組成物の押出成形を行う際、塩素含有ポリマー系樹脂組成物の溶融混練時の最大トルクを低く抑えることが溶融混練において有利である。指標としては、例えば、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２０質量部加えて溶融混練を行う際の最大トルクを用いることができる。　溶融混練を行う際の最大トルクの好ましい範囲は、実際の押出成形の条件によって代わり得るが、例えば、株式会社東洋精機製作所のラボプラストミル（４Ｃ１５０、ミキサータイプＲ６０）を用いて１９０℃、充填量６０．０ｇ、６０ｒｐｍの条件で測定した最大トルクの値が５０Ｎ・ｍ以下であることが好ましい。 (5-3. Maximum torque during melt-kneading of chlorine-containing polymer resin composition)
When the chlorine-containing polymer resin composition is extruded, it is advantageous in the melt kneading to keep the maximum torque of the chlorine-containing polymer resin composition during melt kneading low. As an index, for example, the maximum torque when 20 parts by mass of a maleimide-based copolymer is added to 100 parts by mass of a chlorine-containing polymer and melt-kneading can be used can be used. The preferable range of the maximum torque for melt-kneading can be changed depending on the actual extrusion molding conditions. For example, using a lab plast mill (4C150, mixer type R60) manufactured by Toyo Seiki Seisakusho Co., Ltd., the filling amount is 190 ° C. It is preferable that the value of the maximum torque measured under the conditions of 60.0 g and 60 rpm is 50 Nm or less.
　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, the detailed contents will be described with reference to Examples, but the present invention is not limited to the following Examples.
　＜マレイミド系共重合体（Ａ－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７３質量部、アクリロニトリル１８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０．２２質量部、メチルエチルケトン２６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７質量部とｔ－ブチルパーオキシ－２－エチルヘキサノエート１．０質量部をメチルエチルケトン３５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６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マレイミド系共重合体Ａ－１を得た。得られたマレイミド系共重合体の分析結果を表１に示す。表１及び表２中、Ｓｔｙはスチレン単量体単位、ＡＮはアクリロニトリル単量体単位、ＭＡＨはマレイン酸無水物単量体単位、ＮＰＭＩはＮ－フェニルマレイミド単量体単位を、ＰＶＣはポリ塩化ビニルを示す。 <Production example of maleimide-based copolymer (A-1)>
73 parts by mass of styrene, 18 parts by mass of acrylonitrile, 1 part by mass of maleic acid anhydride, 0.22 parts by mass of α-methylstyrene dimer, and 26 parts by mass of methylethylketone were charged in an autoclave equipped with a stirrer and having a volume of about 120 liters. After replacing the phase part with nitrogen gas, the temperature was raised to 92 ° C. over 40 minutes with stirring. A solution of 7 parts by mass of maleic anhydride and 1.0 part by mass of t-butylperoxy-2-ethylhexanoate in 35 parts by mass of methyl ethyl ketone was added over 4.5 hours while maintaining the temperature at 92 ° C. after the temperature was raised. Was added continuously. 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. Then, 6 parts by mass of aniline and 0.1 part by mass of triethylamine were added to the polymerization solution, and the mixture was reacted at 140 ° C. for 7 hours. After the reaction was completed, the imidization reaction solution was put into a vent type screw extruder to remove volatile components to obtain a pellet-shaped maleimide-based copolymer A-1. The analysis results of the obtained maleimide-based copolymer are shown in Table 1. In Tables 1 and 2, Sty is a styrene monomer unit, AN is an acrylonitrile monomer unit, MAH is a maleic anhydride monomer unit, NPMI is an N-phenylmaleimide monomer unit, and PVC is polyvinyl chloride. Indicates vinyl.
　＜マレイミド系共重合体（Ａ－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６４質量部、アクリロニトリル２０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０．５質量部、メチルエチルケトン３１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１４質量部とｔ－ブチルパーオキシ－２－エチルヘキサノエート０．６０質量部をメチルエチルケトン６９質量部に溶解した溶液を５．５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マレイミド系共重合体Ａ－２を得た。得られたマレイミド系共重合体の分析結果を表１に示す。 <Production example of maleimide-based copolymer (A-2)>
In an autoclave with a volume of about 120 liters equipped with a stirrer, 64 parts by mass of styrene, 20 parts by mass of acrylonitrile, 2 parts by mass of maleic acid anhydride, 0.5 parts by mass of α-methylstyrene dimer, and 31 parts by mass of methylethylketone were charged. After replacing the phase part with nitrogen gas, the temperature was raised to 92 ° C. over 40 minutes with stirring. A solution of 14 parts by mass of maleic anhydride and 0.60 parts by mass of t-butylperoxy-2-ethylhexanoate in 69 parts by mass of methyl ethyl ketone was added over 5.5 hours while maintaining 92 ° C. after the temperature was raised. Was added continuously. 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. Then, 12 parts by mass of aniline and 0.2 part by mass of triethylamine were added to the polymerization solution, and the mixture was reacted at 140 ° C. for 7 hours. After the reaction was completed, the imidization reaction solution was put into a vent type screw extruder to remove volatile components to obtain a pellet-shaped maleimide-based copolymer A-2. The analysis results of the obtained maleimide-based copolymer are shown in Table 1.
　＜マレイミド系共重合体（Ａ－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７９質量部、アクリロニトリル９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０．５２質量部、メチルエチルケトン３３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０．６０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、１．５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９質量部、トリエチルアミン０．２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マレイミド系共重合体Ａ－３を得た。得られたマレイミド系共重合体の分析結果を表１に示す。 <Production example of maleimide-based copolymer (A-3)>
In an autoclave with a volume of about 120 liters equipped with a stirrer, 79 parts by mass of styrene, 9 parts by mass of acrylonitrile, 2 parts by mass of maleic acid anhydride, 0.52 parts by mass of α-methylstyrene dimer, and 33 parts by mass of methylethylketone were charged. After replacing the phase part with nitrogen gas, the temperature was raised to 92 ° C. over 40 minutes with stirring. A solution of 9 parts by mass of maleic anhydride and 0.60 parts by mass of t-butylperoxy-2-ethylhexanoate in 47 parts by mass of methyl ethyl ketone was continuously prepared over 5 hours while maintaining 92 ° C. after the temperature was raised. Was added. 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. Then, 9 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 7 hours. After the reaction was completed, the imidization reaction solution was put into a vent type screw extruder to remove volatile components to obtain a pellet-shaped maleimide-based copolymer A-3. The analysis results of the obtained maleimide-based copolymer are shown in Table 1.
　＜マレイミド系共重合体（Ａ－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８５質量部、アクリロニトリル７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０．７２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７質量部とｔ－ブチルパーオキシ－２－エチルヘキサノエート０．８０質量部をメチルエチルケトン３３質量部に溶解した溶液を６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マレイミド系共重合体Ａ－４を得た。得られたマレイミド系共重合体の分析結果を表１に示す。 <Production example of maleimide-based copolymer (A-4)>
In an autoclave with a volume of about 120 liters equipped with a stirrer, 85 parts by mass of styrene, 7 parts by mass of acrylonitrile, 1 part by mass of maleic acid anhydride, 0.72 parts by mass of α-methylstyrene dimer, and 30 parts by mass of methylethylketone were charged. After replacing the phase part with nitrogen gas, the temperature was raised to 92 ° C. over 40 minutes with stirring. A solution prepared by dissolving 7 parts by mass of maleic anhydride and 0.80 parts by mass of t-butylperoxy-2-ethylhexanoate in 33 parts by mass of methyl ethyl ketone was continuously prepared over 6 hours while maintaining 92 ° C. after the temperature was raised. Was 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. Then, 5 parts by mass of aniline and 0.1 part by mass of triethylamine were added to the polymerization solution, and the mixture was reacted at 140 ° C. for 7 hours. After the reaction was completed, the imidization reaction solution was put into a vent type screw extruder to remove volatile components to obtain a pellet-shaped maleimide-based copolymer A-4. The analysis results of the obtained maleimide-based copolymer are shown in Table 1.
　＜マレイミド系共重合体（Ａ－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２５質量部、アクリロニトリル２６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０．５３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、スチレン３４質量部及びマレイン酸無水物１３質量部とｔ－ブチルパーオキシ－２－エチルヘキサノエート０．２２質量部をメチルエチルケトン６７質量部に溶解した溶液を３時間かけて連続的に添加した。更にマレイン酸無水物添加終了後、ｔ－ブチルパーオキシ－２－エチルヘキサノエート０．１８質量部をメチルエチルケトン１質量部に溶解した溶液を２．５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マレイミド系共重合体Ａ－５を得た。得られたマレイミド系共重合体の分析結果を表１に示す。 <Production example of maleimide-based copolymer (A-5)>
25 parts by mass of styrene, 26 parts by mass of acrylonitrile, 2 parts by mass of maleic acid anhydride, 0.53 parts by mass of α-methylstyrene dimer, and 30 parts by mass of methylethylketone are charged in an autoclave equipped with a stirrer and having a volume of about 120 liters. After replacing the phase part with nitrogen gas, the temperature was raised to 92 ° C. over 40 minutes with stirring. A solution prepared by dissolving 34 parts by mass of styrene, 13 parts by mass of maleic anhydride and 0.22 parts by mass of t-butylperoxy-2-ethylhexanoate in 67 parts by mass of methyl ethyl ketone while maintaining 92 ° C. after raising the temperature. It was added continuously over 3 hours. Further, after the addition of maleic anhydride was completed, a solution prepared by dissolving 0.18 parts by mass of t-butylperoxy-2-ethylhexanoate in 1 part by mass of methyl ethyl ketone was continuously added over 2.5 hours. 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. Then, 12 parts by mass of aniline and 0.2 part by mass of triethylamine were added to the polymerization solution, and the mixture was reacted at 140 ° C. for 7 hours. After the reaction was completed, the imidization reaction solution was put into a vent type screw extruder to remove volatile components to obtain a pellet-shaped maleimide-based copolymer A-5. The analysis results of the obtained maleimide-based copolymer are shown in Table 1.
　＜マレイミド系共重合体（Ａ－６）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２３質量部、アクリロニトリル２６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０．３２質量部、メチルエチルケトン３２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、スチレン３３質量部及びマレイン酸無水物１６質量部とｔ－ブチルパーオキシ－２－エチルヘキサノエート０．２２質量部をメチルエチルケトン８１質量部に溶解した溶液を３時間かけて連続的に添加した。更にマレイン酸無水物添加終了後、ｔ－ブチルパーオキシ－２－エチルヘキサノエート０．１８質量部をメチルエチルケトン１質量部に溶解した溶液を２．５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１４質量部、トリエチルアミン０．３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マレイミド系共重合体Ａ－６を得た。得られたマレイミド系共重合体の分析結果を表１に示す。 <Production example of maleimide-based copolymer (A-6)>
23 parts by mass of styrene, 26 parts by mass of acrylonitrile, 2 parts by mass of maleic acid anhydride, 0.32 parts by mass of α-methylstyrene dimer, and 32 parts by mass of methylethylketone were charged into an autoclave equipped with a stirrer and having a volume of about 120 liters. After replacing the phase part with nitrogen gas, the temperature was raised to 92 ° C. over 40 minutes with stirring. A solution prepared by dissolving 33 parts by mass of styrene, 16 parts by mass of maleic anhydride and 0.22 parts by mass of t-butylperoxy-2-ethylhexanoate in 81 parts by mass of methyl ethyl ketone while maintaining 92 ° C. after raising the temperature. It was added continuously over 3 hours. Further, after the addition of maleic anhydride was completed, a solution prepared by dissolving 0.18 parts by mass of t-butylperoxy-2-ethylhexanoate in 1 part by mass of methyl ethyl ketone was continuously added over 2.5 hours. 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. Then, 14 parts by mass of aniline and 0.3 parts by mass of triethylamine were added to the polymerization solution, and the mixture was reacted at 140 ° C. for 7 hours. After the reaction was completed, the imidization reaction solution was put into a vent type screw extruder to remove volatile components to obtain a pellet-shaped maleimide-based copolymer A-6. The analysis results of the obtained maleimide-based copolymer are shown in Table 1.
　＜マレイミド系共重合体（Ｂ－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９４質量部、アクリロニトリル２
質量部、マレイン酸無水物０．４質量部、α－メチルスチレンダイマーを０．５８質量部、メチルエチルケトン２８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１．０質量部をメチルエチルケトン１８質量部に溶解した溶液を７．５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３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マレイミド系共重合体Ｂ－１を得た。得られたマレイミド系共重合体の分析結果を表２に示す。 <Production example of maleimide-based copolymer (B-1)>
94 parts by mass of styrene, acrylonitrile 2 in an autoclave with a volume of about 120 liters equipped with a stirrer
Add 0.4 parts by mass of maleic acid anhydride, 0.58 parts by mass of α-methylstyrene dimer, and 28 parts by mass of methyl ethyl ketone, replace the gas phase part with nitrogen gas, and then stir for 40 minutes. The temperature was raised to 92 ° C. A solution prepared by dissolving 4 parts by mass of maleic anhydride and 1.0 part by mass of t-butylperoxy-2-ethylhexanoate in 18 parts by mass of methyl ethyl ketone was added over 7.5 hours while maintaining 92 ° C. after the temperature was raised. Was added continuously. 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. Then, 3 parts by mass of aniline and 0.1 part by mass of triethylamine were added to the polymerization solution, and the mixture was reacted at 140 ° C. for 7 hours. After the reaction was completed, the imidization reaction solution was put into a vent type screw extruder to remove volatile components to obtain a pellet-shaped maleimide-based copolymer B-1. The analysis results of the obtained maleimide-based copolymer are shown in Table 2.
　＜マレイミド系共重合体（Ｂ－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８８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０．４８質量部、メチルエチルケトン２９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１１質量部とｔ－ブチルパーオキシ－２－エチルヘキサノエート１．２０質量部をメチルエチルケトン５６質量部に溶解した溶液を８．５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９質量部、トリエチルアミン０．２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マレイミド系共重合体Ｂ－２を得た。得られたマレイミド系共重合体の分析結果を表２に示す。 <Production example of maleimide-based copolymer (B-2)>
88 parts by mass of styrene, 1 part by mass of maleic acid anhydride, 0.48 parts by mass of α-methylstyrene dimer, and 29 parts by mass of methylethylketone were charged in an autoclave equipped with a stirrer and having a volume of about 120 liters. After replacement with, the temperature was raised to 92 ° C. over 40 minutes with stirring. A solution prepared by dissolving 11 parts by mass of maleic anhydride and 1.20 parts by mass of t-butylperoxy-2-ethylhexanoate in 56 parts by mass of methyl ethyl ketone was added over 8.5 hours while maintaining the temperature at 92 ° C. after the temperature was raised. Was added continuously. 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. Then, 9 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 7 hours. After the reaction was completed, the imidization reaction solution was put into a vent type screw extruder to remove volatile components to obtain a pellet-shaped maleimide-based copolymer B-2. The analysis results of the obtained maleimide-based copolymer are shown in Table 2.
　＜マレイミド系共重合体（Ｂ－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２７質量部、アクリロニトリル３３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０．１１質量部、メチルエチルケトン２４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、スチレン３１質量部及びマレイン酸無水物７質量部とｔ－ブチルパーオキシ－２－エチルヘキサノエート０．３８質量部をメチルエチルケトン３７質量部に溶解した溶液を３．５時間かけて連続的に添加した。更にマレイン酸無水物添加終了後、ｔ－ブチルパーオキシ－２－エチルヘキサノエート０．２２質量部をメチルエチルケトン２質量部に溶解した溶液を２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６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マレイミド系共重合体Ｂ－３を得た。得られたマレイミド系共重合体の分析結果を表２に示す。 <Production example of maleimide-based copolymer (B-3)>
27 parts by mass of styrene, 33 parts by mass of acrylonitrile, 2 parts by mass of maleic acid anhydride, 0.11 part by mass of α-methylstyrene dimer and 24 parts by mass of methylethylketone were charged in an autoclave equipped with a stirrer and having a volume of about 120 liters. After replacing the phase part with nitrogen gas, the temperature was raised to 92 ° C. over 40 minutes with stirring. A solution prepared by dissolving 31 parts by mass of styrene, 7 parts by mass of maleic anhydride and 0.38 parts by mass of t-butylperoxy-2-ethylhexanoate in 37 parts by mass of methyl ethyl ketone while maintaining 92 ° C. after raising the temperature. It was added continuously over 3.5 hours. Further, after the addition of maleic anhydride was completed, a solution prepared by dissolving 0.22 parts by mass of t-butylperoxy-2-ethylhexanoate in 2 parts by mass of methyl ethyl ketone was continuously added over 2 hours. 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. Then, 6 parts by mass of aniline and 0.1 part by mass of triethylamine were added to the polymerization solution, and the mixture was reacted at 140 ° C. for 7 hours. After the reaction was completed, the imidization reaction solution was put into a vent type screw extruder to remove volatile components to obtain a pellet-shaped maleimide-based copolymer B-3. The analysis results of the obtained maleimide-based copolymer are shown in Table 2.
　＜マレイミド系共重合体（Ｂ－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６３質量部、アクリロニトリル２２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０．５９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１３質量部とｔ－ブチルパーオキシ－２－エチルヘキサノエート０．４４質量部をメチルエチルケトン６９質量部に溶解した溶液を４時間かけて連続的に添加した。更にマレイン酸無水物添加終了後、ｔ－ブチルパーオキシ－２－エチルヘキサノエート０．１６質量部をメチルエチルケトン１質量部に溶解した溶液を１．５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３質量部、トリエチルアミン０．２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マレイミド系共重合体Ｂ－４を得た。得られたマレイミド系共重合体の分析結果を表２に示す。 <Production example of maleimide-based copolymer (B-4)>
In an autoclave with a volume of about 120 liters equipped with a stirrer, 63 parts by mass of styrene, 22 parts by mass of acrylonitrile, 2 parts by mass of maleic acid anhydride, 0.59 parts by mass of α-methylstyrene dimer, and 30 parts by mass of methylethylketone were charged. After replacing the phase part with nitrogen gas, the temperature was raised to 92 ° C. over 40 minutes with stirring. A solution of 13 parts by mass of maleic anhydride and 0.44 parts by mass of t-butylperoxy-2-ethylhexanoate in 69 parts by mass of methyl ethyl ketone was continuously prepared over 4 hours while maintaining 92 ° C. after the temperature was raised. Was added. Further, after the addition of maleic anhydride was completed, a solution prepared by dissolving 0.16 parts by mass of t-butylperoxy-2-ethylhexanoate in 1 part by mass of methyl ethyl ketone was continuously added over 1.5 hours. 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. Then, 3 parts by mass of aniline and 0.2 part by mass of triethylamine were added to the polymerization solution, and the mixture was reacted at 140 ° C. for 7 hours. After the reaction was completed, the imidization reaction solution was put into a vent type screw extruder to remove volatile components to obtain a pellet-shaped maleimide-based copolymer B-4. The analysis results of the obtained maleimide-based copolymer are shown in Table 2.
　＜マレイミド系共重合体（Ｂ－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１９質量部、マレイン酸無水物１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３質量部とｔ－ブチルパーオキシ－２－エチルヘキサノエート０．８２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４．５時間かけて連続的に添加した。更にマレイン酸無水物添加終了後、ｔ－ブチルパーオキシ－２－エチルヘキサノエート０．１８質量部をメチルエチルケトン１質量部に溶解した溶液を１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２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マレイミド系共重合体Ｂ－５を得た。得られたマレイミド系共重合体の分析結果を表２に示す。 <Production example of maleimide-based copolymer (B-5)>
77 parts by mass of styrene, 19 parts by mass of acrylonitrile, 1 part by mass of maleic acid anhydride, and 25 parts by mass of methyl ethyl ketone were charged in an autoclave having a volume of about 120 liters equipped with a stirrer, and the gas phase part was replaced with nitrogen gas and then stirred. The temperature was raised to 92 ° C. over 40 minutes. After raising the temperature, while maintaining 92 ° C., a solution of 3 parts by mass of maleic anhydride and 0.82 parts by mass of t-butylperoxy-2-ethylhexanoate in 23 parts by mass of methyl ethyl ketone was added over 4.5 hours. Was added continuously. Further, after the addition of maleic anhydride was completed, a solution prepared by dissolving 0.18 parts by mass of t-butylperoxy-2-ethylhexanoate in 1 part by mass of methyl ethyl ketone was continuously added over 1 hour. 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. Then, 2 parts by mass of aniline and 0.1 part by mass of triethylamine were added to the polymerization solution, and the mixture was reacted at 140 ° C. for 7 hours. After the reaction was completed, the imidization reaction solution was put into a vent type screw extruder to remove volatile components to obtain a pellet-shaped maleimide-based copolymer B-5. The analysis results of the obtained maleimide-based copolymer are shown in Table 2.
　＜マレイミド系共重合体（Ｂ－６）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２４質量部、アクリロニトリル２４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０．５３質量部、メチルエチルケトン３３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、スチレン３３質量部及びマレイン酸無水物１７質量部とｔ－ブチルパーオキシ－２－エチルヘキサノエート０．２２質量部をメチルエチルケトン８５質量部に溶解した溶液を３時間かけて連続的に添加した。更にマレイン酸無水物添加終了後、ｔ－ブチルパーオキシ－２－エチルヘキサノエート０．１８質量部をメチルエチルケトン１質量部に溶解した溶液を２．５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１６質量部、トリエチルアミン０．３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マレイミド系共重合体Ｂ－６を得た。得られたマレイミド系共重合体の分析結果を表２に示す。
<Production example of maleimide-based copolymer (B-6)>
24 parts by mass of styrene, 24 parts by mass of acrylonitrile, 2 parts by mass of maleic acid anhydride, 0.53 parts by mass of α-methylstyrene dimer, and 33 parts by mass of methylethylketone were charged in an autoclave equipped with a stirrer and having a volume of about 120 liters. After replacing the phase part with nitrogen gas, the temperature was raised to 92 ° C. over 40 minutes with stirring. A solution prepared by dissolving 33 parts by mass of styrene, 17 parts by mass of maleic anhydride and 0.22 parts by mass of t-butylperoxy-2-ethylhexanoate in 85 parts by mass of methyl ethyl ketone while maintaining 92 ° C. after raising the temperature. It was added continuously over 3 hours. Further, after the addition of maleic anhydride was completed, a solution prepared by dissolving 0.18 parts by mass of t-butylperoxy-2-ethylhexanoate in 1 part by mass of methyl ethyl ketone was continuously added over 2.5 hours. 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. Then, 16 parts by mass of aniline and 0.3 parts by mass of triethylamine were added to the polymerization solution, and the mixture was reacted at 140 ° C. for 7 hours. After the reaction was completed, the imidization reaction solution was put into a vent type screw extruder to remove volatile components to obtain a pellet-shaped maleimide-based copolymer B-6. The analysis results of the obtained maleimide-based copolymer are shown in Table 2.
　＜マレイミド系共重合体（Ｂ－７）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２２質量部、アクリロニトリル１０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０．４５質量部、メチルエチルケトン３９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、スチレン４１質量部及びマレイン酸無水物２３質量部とｔ－ブチルパーオキシ－２－エチルヘキサノエート０．４２質量部をメチルエチルケトン１１６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２３質量部、トリエチルアミン０．４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マレイミド系共重合体Ｂ－７を得た。得られたマレイミド系共重合体の分析結果を表２に示す。 <Production example of maleimide-based copolymer (B-7)>
In an autoclave with a volume of about 120 liters equipped with a stirrer, 22 parts by mass of styrene, 10 parts by mass of acrylonitrile, 3 parts by mass of maleic acid anhydride, 0.45 parts by mass of α-methylstyrene dimer, and 39 parts by mass of methylethylketone were charged. After replacing the phase part with nitrogen gas, the temperature was raised to 92 ° C. over 40 minutes with stirring. A solution prepared by dissolving 41 parts by mass of styrene, 23 parts by mass of maleic anhydride and 0.42 parts by mass of t-butylperoxy-2-ethylhexanoate in 116 parts by mass of methyl ethyl ketone while maintaining 92 ° C. after raising the temperature. It was added continuously over 5 hours. 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. Then, 23 parts by mass of aniline and 0.4 parts by mass of triethylamine were added to the polymerization solution, and the mixture was reacted at 140 ° C. for 7 hours. After the reaction was completed, the imidization reaction solution was put into a vent type screw extruder to remove volatile components to obtain a pellet-shaped maleimide-based copolymer B-7. The analysis results of the obtained maleimide-based copolymer are shown in Table 2.
　＜マレイミド系共重合体（Ｂ－８）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７９質量部、アクリロニトリル９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１．００質量部、メチルエチルケトン３３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０．６０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、１．５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９質量部、トリエチルアミン０．２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マレイミド系共重合体Ｂ－８を得た。得られたマレイミド系共重合体の分析結果を表２に示す。 <Production example of maleimide-based copolymer (B-8)>
In an autoclave with a volume of about 120 liters equipped with a stirrer, 79 parts by mass of styrene, 9 parts by mass of acrylonitrile, 2 parts by mass of maleic acid anhydride, 1.00 parts by mass of α-methylstyrene dimer, and 33 parts by mass of methylethylketone were charged. After replacing the phase part with nitrogen gas, the temperature was raised to 92 ° C. over 40 minutes with stirring. A solution of 9 parts by mass of maleic anhydride and 0.60 parts by mass of t-butylperoxy-2-ethylhexanoate in 47 parts by mass of methyl ethyl ketone was continuously prepared over 5 hours while maintaining 92 ° C. after the temperature was raised. Was added. 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. Then, 9 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 7 hours. After the reaction was completed, the imidization reaction solution was put into a vent type screw extruder to remove volatile components to obtain a pellet-shaped maleimide-based copolymer B-8. The analysis results of the obtained maleimide-based copolymer are shown in Table 2.
　＜マレイミド系共重合体（Ｂ－９）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７９質量部、アクリロニトリル９質量部、マレイン酸無水物２質量部、メチルエチルケトン３３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０．６０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、１．５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９質量部、トリエチルアミン０．２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マレイミド系共重合体Ｂ－９を得た。得られたマレイミド系共重合体の分析結果を表２に示す。 <Production example of maleimide-based copolymer (B-9)>
79 parts by mass of styrene, 9 parts by mass of acrylonitrile, 2 parts by mass of maleic acid anhydride, and 33 parts by mass of methyl ethyl ketone were charged in an autoclave having a volume of about 120 liters equipped with a stirrer, and the gas phase part was replaced with nitrogen gas and then stirred. The temperature was raised to 92 ° C. over 40 minutes. A solution of 9 parts by mass of maleic anhydride and 0.60 parts by mass of t-butylperoxy-2-ethylhexanoate in 47 parts by mass of methyl ethyl ketone was continuously prepared over 5 hours while maintaining 92 ° C. after the temperature was raised. Was added. 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. Then, 9 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 7 hours. After the reaction was completed, the imidization reaction solution was put into a vent type screw extruder to remove volatile components to obtain a pellet-shaped maleimide-based copolymer B-9. The analysis results of the obtained maleimide-based copolymer are shown in Table 2.
　＜マレイミド系共重合体（Ｂ－１０）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８４質量部、アクリロニトリル１２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０．５７質量部、メチルエチルケトン２６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３質量部とｔ－ブチルパーオキシ－２－エチルヘキサノエート０．８２質量部をメチルエチルケトン２４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。更にマレイン酸無水物添加終了後、ｔ－ブチルパーオキシ－２－エチルヘキサノエート０．１８質量部をメチルエチルケトン１質量部に溶解した溶液を１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３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マレイミド系共重合体Ｂ－１０を得た。得られたマレイミド系共重合体の分析結果を表２に示す。 <Production example of maleimide-based copolymer (B-10)>
In an autoclave with a volume of about 120 liters equipped with a stirrer, 84 parts by mass of styrene, 12 parts by mass of acrylonitrile, 1 part by mass of maleic acid anhydride, 0.57 parts by mass of α-methylstyrene dimer, and 26 parts by mass of methylethylketone were charged. After replacing the phase part with nitrogen gas, the temperature was raised to 92 ° C. over 40 minutes with stirring. After raising the temperature, while maintaining 92 ° C., a solution of 3 parts by mass of maleic anhydride and 0.82 parts by mass of t-butylperoxy-2-ethylhexanoate in 24 parts by mass of methyl ethyl ketone was added over 4.5 hours. Was added continuously. Further, after the addition of maleic anhydride was completed, a solution prepared by dissolving 0.18 parts by mass of t-butylperoxy-2-ethylhexanoate in 1 part by mass of methyl ethyl ketone was continuously added over 1 hour. 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. Then, 3 parts by mass of aniline and 0.1 part by mass of triethylamine were added to the polymerization solution, and the mixture was reacted at 140 ° C. for 7 hours. After the reaction was completed, the imidization reaction solution was put into a vent type screw extruder to remove volatile components to obtain a pellet-shaped maleimide-based copolymer B-10. The analysis results of the obtained maleimide-based copolymer are shown in Table 2.
＜塩素含有ポリマー系樹脂組成物＞
（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）
・製品名：ＴＨ－１０００（大洋塩ビ社製）を使用した。
（２）マレイミド系共重合体
・上述の製造例に従い得た（Ａ－１～Ａ－６、Ｂ－１～Ｂ－１０）を使用した。

実施例１～６、比較例１～１２（マレイミド系共重合体と塩素含有ポリマーとの混練混合）
　マレイミド系共重合体Ａ－１～Ａ－６、Ｂ－１～Ｂ－１２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一般に市販されている塩素含有ポリマー（製品名：ＴＨ－１０００、大洋塩ビ社製）とを表１～２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。結果を表１～２に示す。 <Chlorine-containing polymer resin composition>
(Raw materials used) The raw materials used in each example and each comparative example are shown below.
(1) Chlorine-containing polymer (PVC)
-Product name: TH-1000 (manufactured by Taiyo PVC Co., Ltd.) was used.
(2) Maleimide-based copolymer-(A-1 to A-6, B-1 to B-10) obtained according to the above-mentioned production example were used.

Examples 1 to 6 and Comparative Examples 1 to 12 (kneading and mixing of a maleimide-based copolymer and a chlorine-containing polymer)
A generally commercially available chlorine-containing polymer (product name: TH-1000) in which maleimide-based copolymers A-1 to A-6 and B-1 to B-12 are mixed with a stabilizer and a lubricant in advance with a Henshell mixer. , Taiyo PVC) is blended in the blending ratios shown in Tables 1 and 2, and then roll sheets are prepared using test rolls (φ6 x L15 test rolls, manufactured by Kansai Roll Co., Ltd.), and the roll sheets are stacked. A test piece was prepared by press molding and cutting or punching, and each physical property value was measured. The results are shown in Tables 1 and 2.
（組成分析）
各単量体単位の組成分析は、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 composition analysis of each monomer unit was measured by the C-13 NMR method under the measurement conditions described below.
Device name: FT-NMR AVANCE300 (BRUKER solvent: deuterated chloroform concentration: 14% by mass)
Temperature: 27 ° C
Accumulation number: 8000 times
（重量平均分子量）
　重量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）にて測定されるポリスチレン換算の値であり、以下の条件で測定した。
　測定名：ＳＹＳＴＥＭ－２１　Ｓｈｏｄｅｘ（昭和電工株式会社製）
　カラム：ＰＬ　ｇｅｌ　ＭＩＸＥＤ－Ｂ（ポリマーラボラトリーズ社製）を３本直列
　温度：４０℃
　検出：示差屈折率
　溶媒：テトラヒドロフラン
　濃度：２質量％
　検量線：標準ポリスチレン（ＰＳ）（ポリマーラボラトリーズ社製）を用いて作成 (Weight average molecular weight)
The weight average molecular weight is a polystyrene-equivalent value measured by gel permeation chromatography (GPC), and was measured under the following conditions.
Measurement name: SYSTEM-21 Shodex (manufactured by Showa Denko KK)
Column: 3 PL gel MIXED-B (manufactured by Polymer Laboratories) in series Temperature: 40 ° C
Detection: Differential Refractometer Solvent: Tetrahydrofuran Concentration: 2% by mass
Calibration curve: Created using standard polystyrene (PS) (manufactured by Polymer Laboratories)
（溶融粘度）
　　溶融粘度は、１９０℃、せん断速度１００／ｓｅｃの条件で、Ｌ＝４０ｍｍ、Ｄ＝１ｍｍのキャピラリーダイを用いて測定した。測定機は株式会社東洋精機製作所製キャピラリーレオメータ１Ｄを使用した。 (Melting viscosity)
The melt viscosity was measured using a capillary die with L = 40 mm and D = 1 mm under the conditions of 190 ° C. and a shear rate of 100 / sec. The measuring machine used was a capillary rheometer 1D manufactured by Toyo Seiki Seisakusho Co., Ltd.
（ビカット軟化点）
　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 was measured by the 50 method (load 50 N, heating rate 50 ° C./hour) based on JIS K7206: 1999, using a test piece having a size of 20 mm × 20 mm and a thickness of 4 mm. As the measuring machine, an HDT & VSPT test device manufactured by Toyo Seiki Seisakusho Co., Ltd. was used.
（黄色度（ＹＩ））
　ＪＩＳ　Ｋ－７３７３に準拠して測定した。具体的な手順は以下のとおりである。
マレイミド系共重合体１ｇを２５ｍＬのテトラヒドロフランに溶解させた。溶解後、測定用の角セルに移した。温度２３℃、湿度５０％の条件で、ＣＩＥ標準のＤ６５光源を使用した透過法により、テトラヒドロフラン溶液の角セルをブランクとして色差を求め、その値を黄色度とした。
装置名：ＳＥ７７００　分光色彩計（日本電色工業株式会社製）
角セル：Ａ０２２７７Ａ　１０×３６×５５Ｈ　角セル　２面透過 (Yellowness (YI))
Measured according to JIS K-7373. The specific procedure is as follows.
1 g of the maleimide-based copolymer was dissolved in 25 mL of tetrahydrofuran. After lysis, it was transferred to a square cell for measurement. The color difference was obtained by using a transmission method using a CIE standard D65 light source under the conditions of a temperature of 23 ° C. and a humidity of 50%, using a square cell of a tetrahydrofuran solution as a blank, and the value was defined as yellowness.
Device name: SE7700 Spectral colorimeter (manufactured by Nippon Denshoku Industries Co., Ltd.)
Square cell: A02277A 10 x 36 x 55H Square cell two-sided transmission
（最大トルク）
　各実施例及び比較例の最大トルクは、以下のようにして測定した。
　あらかじめ安定剤、滑剤等の添加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（ＴＨ－１０００、大洋塩ビ社製）８０質量部に対し、実施例及び比較例のマレイミド系共重合体を２０質量部加えた。マレイミド系共重合体と塩素含有ポリマーとの溶融混練において、ラボプラストミル（４Ｃ１５０型、ミキサー型式Ｒ６０、株式会社東洋精機製作所製）を用い、充填量６０．０ｇ、温度１９０℃、回転数６０ｒｐｍの条件で混練中の最大トルク（混練トルク、単位：Ｎ・ｍ）を測定した。
　最大トルクの値が低い場合には、溶融混練に有利であるため、好適に押出成形を行うことが可能になる。 (Maximum torque)
The maximum torque of each Example and Comparative Example was measured as follows.
20 parts by mass of the maleimide-based polymer of Examples and Comparative Examples was added to 80 parts by mass of a chlorine-containing polymer (TH-1000, manufactured by Taiyo PVC Co., Ltd.) in which additives such as stabilizers and lubricants were added in advance and mixed with a Henshell mixer. I added a part. In the melt-kneading of the maleimide-based copolymer and the chlorine-containing polymer, a lab-plast mill (4C150 type, mixer model R60, manufactured by Toyo Seiki Seisakusho Co., Ltd.) was used, and the filling amount was 60.0 g, the temperature was 190 ° C., and the rotation speed was 60 rpm. The maximum torque during kneading (kneading torque, unit: Nm) was measured under the conditions.
When the value of the maximum torque is low, it is advantageous for melt-kneading, so that extrusion molding can be suitably performed.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　本発明にかかるマレイミド系共重合体を採用した塩素含有ポリマー系樹脂組成物を用いた実施例１～６では、塩素含有ポリマーの耐熱性が十分に向上された。また、使用されるマレイミド系共重合体の黄色度を低く制御しており、樹脂組成物及びその成形体における着色を抑えることができる。さらに、マレイミド系共重合体と塩素含有ポリマーとの溶融混練時の最大トルクが低く抑えられた。成形品の押出成形が問題なく実施できると予想される。
　これに対し、本発明の規定を満たさないマレイミド系共重合体を採用した塩素含有ポリマー系樹脂組成物を用いた比較例１～１０では、塩素含有ポリマーの耐熱性が十分に向上されないものがあった。また、使用されるマレイミド系共重合体の黄色度が高い場合には、樹脂組成物及びその成形体の着色が問題となる可能性がある。さらに、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することが不可能となったり、溶融混練時の最大トルクが高くなる場合があった。 In Examples 1 to 6 using the chlorine-containing polymer-based resin composition using the maleimide-based copolymer according to the present invention, the heat resistance of the chlorine-containing polymer was sufficiently improved. In addition, the yellowness of the maleimide-based copolymer used is controlled to be low, and coloring in the resin composition and its molded product can be suppressed. Further, the maximum torque at the time of melt-kneading the maleimide-based copolymer and the chlorine-containing polymer was suppressed to a low level. It is expected that extrusion molding of molded products can be carried out without problems.
On the other hand, in Comparative Examples 1 to 10 using the chlorine-containing polymer-based resin composition using the maleimide-based copolymer that does not satisfy the provisions of the present invention, the heat resistance of the chlorine-containing polymer may not be sufficiently improved. rice field. Further, when the yellowness of the maleimide-based copolymer used is high, coloring of the resin composition and its molded product may become a problem. Further, the maleimide-based copolymer may not melt with the chlorine-containing polymer and cannot be kneaded, or the maximum torque during melt-kneading may increase.
　本発明により、塩素含有ポリマーの耐熱性を向上しつつ、着色が抑えられた塩素含有ポリマー系樹脂組成物を得ることができるマレイミド系共重合体、マレイミド系共重合体と塩素含有ポリマーを含む塩素含有ポリマー系樹脂組成物及びその成形体が提供され、耐熱性及び外観性能が要求される成形品、例えば雨どいやエアコンの配管カバー等に好適に利用される。また、本発明にかかる塩素含有ポリマー系樹脂組成物は、押出成形に好適に利用される。 INDUSTRIAL APPLICABILITY According to the present invention, it is possible to obtain a chlorine-containing polymer-based resin composition in which coloring is suppressed while improving the heat resistance of the chlorine-containing polymer, and chlorine containing a maleimide-based copolymer and a chlorine-containing polymer. A polymer-based resin composition and a molded product thereof are provided, and are suitably used for molded products that require heat resistance and appearance performance, such as raindrops and pipe covers for air conditioners. Further, the chlorine-containing polymer resin composition according to the present invention is suitably used for extrusion molding.

Claims (10)

  1. 　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、不飽和酸無水物単量体単位及びマレイミド系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５０～９０質量％と、前記シアン化ビニル系単量体単位０．５～２５質量％と、前記不飽和酸無水物単量体単位０～１０質量％と、前記マレイミド系単量体単位５～２５質量％とを有し、
    １９０℃、せん断速度１００／ｓｅｃの条件で測定した溶融粘度が２００～１０００００Ｐａ・ｓｅｃであり、
    重量平均分子量が２．５～１２万である、
    　塩素含有ポリマー用マレイミド系共重合体。     When the total of the aromatic vinyl-based monomer unit, the cyanide vinyl-based monomer unit, the unsaturated acid anhydride monomer unit, and the maleimide-based monomer unit is 100% by mass, the aromatic vinyl-based monomer unit is said. The monomer unit of 50 to 90% by mass, the vinyl cyanide-based monomer unit of 0.5 to 25% by mass, the unsaturated acid anhydride monomer unit of 0 to 10% by mass, and the maleimide-based single unit. It has a weight unit of 5 to 25% by mass,
    The melt viscosity measured under the conditions of 190 ° C. and a shear rate of 100 / sec is 200 to 100,000 Pa · sec.
    Weight average molecular weight is 250,000 to 120,000,
    Maleimide-based copolymer for chlorine-containing polymers.
  2. 　請求項１に記載のマレイミド系共重合体５～５０質量％と、塩素含有ポリマー５０～９５質量％と、を含有する、塩素含有ポリマー系樹脂組成物。 A chlorine-containing polymer-based resin composition containing 5 to 50% by mass of the maleimide-based copolymer according to claim 1 and 50 to 95% by mass of the chlorine-containing polymer.
  3. 　前記溶融粘度が２００～７００００Ｐａ・ｓｅｃである、請求項２に記載の塩素含有ポリマー系樹脂組成物。 The chlorine-containing polymer-based resin composition according to claim 2, wherein the melt viscosity is 200 to 70,000 Pa · sec.
  4. 　前記マレイミド系共重合体の重量平均分子量が５～１０万である、請求項２又は３に記載の塩素含有ポリマー系樹脂組成物。 The chlorine-containing polymer-based resin composition according to claim 2 or 3, wherein the maleimide-based copolymer has a weight average molecular weight of 50,000 to 100,000.
  5. 　前記マレイミド系共重合体が、芳香族ビニル系単量体単位を５０～８０質量％有する、請求項２～４のいずれか１項に記載の塩素含有ポリマー系樹脂組成物。 The chlorine-containing polymer-based resin composition according to any one of claims 2 to 4, wherein the maleimide-based copolymer has 50 to 80% by mass of an aromatic vinyl-based monomer unit.
  6. 　前記マレイミド系共重合体が、シアン化ビニル系単量体単位を５～２０質量％有する、請求項２～５のいずれか１項に記載の塩素含有ポリマー系樹脂組成物。 The chlorine-containing polymer-based resin composition according to any one of claims 2 to 5, wherein the maleimide-based copolymer has 5 to 20% by mass of vinyl cyanide-based monomer units.
  7. 　前記マレイミド系共重合体が、不飽和酸無水物単量体単位を０．３～５質量％有する、請求項２～６のいずれか１項に記載の塩素含有ポリマー系樹脂組成物。 The chlorine-containing polymer-based resin composition according to any one of claims 2 to 6, wherein the maleimide-based copolymer has 0.3 to 5% by mass of an unsaturated acid anhydride monomer unit.
  8. 　前記マレイミド系共重合体が、マレイミド系単量体単位を５～２４質量％有する、請求項２～７のいずれか１項に記載の塩素含有ポリマー系樹脂組成物。 The chlorine-containing polymer-based resin composition according to any one of claims 2 to 7, wherein the maleimide-based copolymer has 5 to 24% by mass of a maleimide-based monomer unit.
  9. 　前記マレイミド系単量体単位がＮ－アリールマレイミドである、請求項２～８のいずれか１項に記載の塩素含有ポリマー系樹脂組成物。 The chlorine-containing polymer-based resin composition according to any one of claims 2 to 8, wherein the maleimide-based monomer unit is N-arylmaleimide.
  10. 　請求項２～９のいずれか１項に記載の塩素含有ポリマー系樹脂組成物から成形されてなることを特徴とする成形体。 A molded product characterized by being molded from the chlorine-containing polymer-based resin composition according to any one of claims 2 to 9.
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