WO2023191064A1 - Heat-resistance imparter for chlorinated polymers, resin composition, and molded object formed from said resin composition - Google Patents

Heat-resistance imparter for chlorinated polymers, resin composition, and molded object formed from said resin composition Download PDF

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Publication number
WO2023191064A1
WO2023191064A1 PCT/JP2023/013575 JP2023013575W WO2023191064A1 WO 2023191064 A1 WO2023191064 A1 WO 2023191064A1 JP 2023013575 W JP2023013575 W JP 2023013575W WO 2023191064 A1 WO2023191064 A1 WO 2023191064A1
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mass
parts
chlorine
maleimide copolymer
monomer unit
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PCT/JP2023/013575
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French (fr)
Japanese (ja)
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達宏 松原
泰政 後藤
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デンカ株式会社
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Publication of WO2023191064A1 publication Critical patent/WO2023191064A1/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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C08L101/04—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride

Definitions

  • the present invention relates to a heat resistance imparting agent for chlorine-containing polymers, a resin composition, and a molded article formed from the resin composition.
  • Chlorine-containing polymers such as polyvinyl chloride and chlorinated polyvinyl chloride
  • polyvinyl chloride has the disadvantage of lacking heat resistance (thermal softening temperature).
  • thermal softening temperature For example, based on JIS K7206:1999, the Vicat The softening temperature is around 82°C, and the softening temperature is further lowered by stabilizers and plasticizers that are usually added during molding.
  • Patent Documents 1 to 4 a method is known in which a resin that imparts heat resistance is mixed with polyvinyl chloride.
  • Patent No. 06475501 JP 2006-265373 International publication WO2022/039098
  • the present invention provides a resin composition containing a heat resistance imparting agent for chlorine-containing polymers and a chlorine-containing polymer, while improving the balance between heat resistance and impact strength of the chlorine-containing polymer, even when an Sn-based stabilizer is blended.
  • the present invention aims to provide a heat resistance imparting agent for chlorine-containing polymers that can reduce the sticking of a resin composition to rolls in a roll kneading process.
  • a heat resistance imparting agent for chlorine-containing polymers containing a maleimide copolymer having a specific monomer unit composition and a specific range of melt viscosity and acid value was found to be suitable for chlorine-containing polymers. It has been found that an excellent balance between heat resistance and impact strength can be achieved when a resin composition is obtained by incorporating In addition, even when an Sn-based stabilizer is blended with the heat resistance imparting agent for chlorine-containing polymers, the heat resistance imparting agent for chlorine-containing polymers can be used in the roll kneading process of the resin composition containing the heat resistance imparting agent for chlorine-containing polymers and the chlorine-containing polymer.
  • a heat resistance imparting agent for chlorine-containing polymers comprising a maleimide copolymer having at least an aromatic vinyl monomer unit, a vinyl cyanide monomer unit, and a maleimide monomer unit
  • the maleimide copolymer has 100% by mass of the total monomer units contained in the maleimide copolymer, 40 to 90% by mass of the aromatic vinyl monomer unit, 0.5 to 30% by mass of the vinyl cyanide monomer unit, 5 to 30% by mass of the maleimide monomer unit
  • the maleimide copolymer has a melt viscosity of 200 to 100,000 Pa ⁇ sec measured at 190° C.
  • the maleimide copolymer further includes a monomer unit having an acid group, and the monomer unit having an acid group is an unsaturated acid anhydride monomer unit, a (meth)acrylic acid unit,
  • the heat resistance imparting agent for chlorine-containing polymers according to [1] which is at least one type selected from the group consisting of mer units.
  • the molded article according to [6] which is used as a rain gutter, a rain gutter component, a shape for fittings, a pipe, and a joint. Regarding.
  • the balance between heat resistance and impact strength of chlorine-containing polymers can be improved. Furthermore, even when a Sn-based stabilizer is blended, sticking of the resin composition to the rolls can be reduced in the roll kneading process of the resin composition containing the heat resistance imparting agent for chlorine-containing polymers and the chlorine-containing polymer.
  • the maleimide copolymer contained in the heat resistance imparting agent for chlorine-containing polymers according to the present embodiment contains at least an aromatic vinyl monomer unit, a vinyl cyanide monomer unit, and a maleimide monomer unit. do. Moreover, it may further contain a monomer unit having an acid group.
  • the monomer units contained in the maleimide copolymer will be explained below.
  • aromatic vinyl monomers that can be used in the maleimide copolymer contained in the heat resistance imparting agent for chlorine-containing polymers according to the present embodiment include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, and p-methylstyrene. -methylstyrene, 2,4-dimethylstyrene, ethylstyrene, p-tert-butylstyrene, ⁇ -methylstyrene, ⁇ -methyl-p-methylstyrene, and the like. Among these, styrene is preferred. In addition, styrene can further improve the balance of heat resistance, affinity with chlorine-containing polymers, and fluidity.
  • the aromatic vinyl monomer unit may be used alone, or two or more types may be used in combination.
  • the maleimide copolymer contained in the heat resistance imparting agent for chlorine-containing polymers according to the present embodiment is an aromatic vinyl monomer when the total monomer units contained in the maleimide copolymer is 100% by mass. It contains 40 to 90% by mass of mer units, preferably 50 to 85% by mass, and more preferably 60 to 80% by mass. Specifically, for example, it is 40, 50, 60, 65, 68, 70, 72, 75, 80, 85, or 90% by mass, and is within the range between any two of the numerical values exemplified here. Good too.
  • the amount of aromatic vinyl monomer units is less than 40% by mass, the amount of other monomer components contained in the maleimide copolymer will increase relatively, resulting in the maleimide copolymer becoming a chlorine-containing polymer. If the amount exceeds 90% by mass, it may not be possible to sufficiently improve the heat resistance of the resin composition. Moreover, within this range, the balance of heat resistance, affinity with chlorine-containing polymers, and fluidity can be further improved.
  • the content of the aromatic vinyl monomer units means the total amount of the aromatic vinyl monomer units used together.
  • vinyl cyanide monomer unit examples include acrylonitrile, methacrylonitrile, ethacrylonitrile, fumaronitrile, etc. can be mentioned. Among these, acrylonitrile is preferred from the viewpoint of imparting heat resistance to the resin composition. Furthermore, acrylonitrile can further improve the balance of heat resistance, affinity with chlorine-containing polymers, and fluidity.
  • the vinyl cyanide monomer unit may be used alone, or two or more types may be used in combination.
  • the maleimide copolymer contained in the heat resistance imparting agent for chlorine-containing polymers according to the present embodiment is a vinyl cyanide copolymer when the total monomer units contained in the maleimide copolymer is 100% by mass. It contains 0.5 to 30% by mass of mer units, preferably 0.5 to 20% by mass, and more preferably 0.5 to 15% by mass. Specifically, for example, it is 0.5, 1, 5, 6, 7, 8, 9, 10, 15, 20, 25, or 30% by mass, and a range between any two of the numerical values exemplified here. It may be within.
  • the heat resistance of the resin composition can be sufficiently improved, and by setting the amount to 30% by mass or less, the impact resistance of the resin composition can be improved.
  • the balance between heat resistance and heat resistance can be improved.
  • the balance of heat resistance, affinity with chlorine-containing polymers, and fluidity can be further improved.
  • the content of vinyl cyanide monomer units means the total amount of vinyl cyanide monomer units used together.
  • maleimide monomer units that can be used in the maleimide copolymer contained in the heat resistance imparting agent for chlorine-containing polymers according to the present embodiment include N-methylmaleimide, N-butylmaleimide, and N-cyclohexylmaleimide. and N-arylmaleimides such as N-phenylmaleimide, N-chlorophenylmaleimide, N-methylphenylmaleimide, N-methoxyphenylmaleimide, and N-tribromophenylmaleimide. Among these, N-arylmaleimide is preferred from the viewpoint of imparting heat resistance to the resin composition, and N-phenylmaleimide is more preferred.
  • the maleimide monomer unit may be used alone or in combination of two or more types.
  • a copolymer obtained by copolymerizing a raw material consisting of an unsaturated dicarboxylic acid monomer unit with other monomers is mixed with ammonia or It may be imidized with a class amine.
  • a raw material consisting of a maleimide monomer may be copolymerized with other monomers.
  • the maleimide copolymer contained in the heat resistance imparting agent for chlorine-containing polymers according to the present embodiment is a maleimide monomer when the total of monomer units contained in the maleimide copolymer is 100% by mass. It contains 5 to 30% by mass of units, preferably 10 to 30% by mass, and more preferably 15 to 30% by mass. Specifically, for example, it is 5, 10, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, or 30% by mass, and between any two of the numerical values exemplified here.
  • the heat resistance of the resin composition can be sufficiently improved, and by setting the amount to 30% by mass or less, the heat resistance imparting agent for chlorine-containing polymers can be It is possible to suppress the inability to melt and knead with the contained polymer. Moreover, within this range, the balance of heat resistance, affinity with chlorine-containing polymers, and fluidity can be further improved.
  • the content of the maleimide monomer unit means the total amount of the maleimide monomer unit used in combination.
  • the maleimide copolymer contained in the heat resistance imparting agent for chlorine-containing polymers according to the present embodiment further includes other copolymerizable monomer units having an acid group (hereinafter referred to as "monomer having an acid group”). (also referred to as “unit”).
  • the acid group here include a carboxyl group and a group having an acid anhydride structure.
  • Monomer units having an acid group that can be used in the maleimide copolymer contained in the heat resistance imparting agent for chlorine-containing polymers according to the present embodiment include unsaturated acid anhydride monomer units, (meth)acrylic Examples include acid monomer units.
  • the monomer unit having an acid group may be used alone, or two or more types may be used in combination.
  • the maleimide copolymer contained in the heat resistance imparting agent for chlorine-containing polymers according to the present embodiment is a monomer having an acid group, when the total of monomer units contained in the maleimide copolymer is 100% by mass.
  • the content of the mer unit is preferably 0 to 2.0% by mass, more preferably 0 to 1.5% by mass. Specifically, for example, 0, 0.2, 0.4, 0.6, 0.8, 1.0, 1.2, 1.4, 1.5, 1.6, 1.7, 1. 8, 1.9, or 2.0% by mass, and may be within a range between any two of the numerical values exemplified here.
  • the content of unsaturated acid anhydride monomer units By controlling the content of unsaturated acid anhydride monomer units to 2.0% by mass or less, the balance between heat resistance, impact strength, and processability during roll kneading (sticking to rolls) of the resin composition is improved. do. Moreover, within this range, the balance of heat resistance, affinity with chlorine-containing polymers, and fluidity can be further improved.
  • the content of the monomer unit having an acid group means the total amount of the monomer units having an acid group used together.
  • Examples of unsaturated acid anhydride monomer units that can be used in the maleimide copolymer included in the heat resistance imparting agent for chlorine-containing polymers according to the present embodiment include maleic anhydride, itaconic anhydride, and citracone. There are acid anhydrides, aconitic acid anhydrides, etc. Among these, maleic anhydride is preferred from the viewpoint of imparting heat resistance to the resin composition. In addition, maleic anhydride can further improve the balance of heat resistance, affinity with chlorine-containing polymers, and fluidity.
  • the unsaturated acid anhydride monomer unit may be used alone, or two or more types may be used in combination.
  • the maleimide copolymer contained in the heat resistance imparting agent for chlorine-containing polymers according to the present embodiment is an unsaturated acid anhydride when the total monomer units contained in the maleimide copolymer is 100% by mass. It preferably contains 0 to 1.5% by mass of monomer units, more preferably 0 to 1.0% by mass. Specifically, for example, it is 0, 0.2, 0.4, 0.6, 0.8, 1.0, 1.2, 1.4, or 1.5% by mass, and the numerical values exemplified here It may be within the range between any two.
  • the content of unsaturated acid anhydride monomer units By controlling the content of unsaturated acid anhydride monomer units to 1.5% by mass or less, the balance between heat resistance, impact strength, and processability during roll kneading (sticking to rolls) of the resin composition is improved. do. Moreover, within this range, the balance of heat resistance, affinity with chlorine-containing polymers, and fluidity can be further improved.
  • the content of the unsaturated acid anhydride monomer unit means the total amount of the unsaturated acid anhydride monomer unit used together.
  • (meth)acrylic acid monomer unit examples include acrylic acid, methacrylic acid, and the like. Among these, methacrylic acid is preferred from the viewpoint of affinity with chlorine-containing polymers.
  • the maleimide copolymer contained in the heat resistance imparting agent for chlorine-containing polymers according to the present embodiment has (meth)acrylic acid It preferably contains 0 to 1.5% by mass of monomer units, more preferably 0 to 1.0% by mass. Specifically, for example, it is 0, 0.2, 0.4, 0.6, 0.8, 1.0, 1.2, 1.4, or 1.5% by mass, and the numerical values exemplified here It may be within the range between any two.
  • the content of (meth)acrylic acid monomer units to 1.5% by mass or less, the balance between heat resistance and impact strength of the resin composition is improved. Moreover, within this range, the balance of heat resistance, affinity with chlorine-containing polymers, and fluidity can be further improved.
  • the content of (meth)acrylic acid monomer units means the total amount of (meth)acrylic acid monomer units used together.
  • the maleimide copolymer contained in the heat resistance imparting agent for chlorine-containing polymers according to the present embodiment includes aromatic vinyl monomers, vinyl cyanide monomers, monomers other than maleimide monomers, and monomers having acid groups. Copolymerizable monomers other than mer units may be copolymerized within a range that does not impede the effects of the present invention. Monomers that can be copolymerized with maleimide copolymers include acrylic ester monomers such as methyl acrylate, ethyl acrylate, and butyl acrylate, methyl methacrylate, and ethyl methacrylate.
  • Examples include methacrylic acid ester monomers, acrylamide, and methacrylic acid amide.
  • the monomers copolymerizable into the maleimide copolymer may be used alone, or two or more types may be used in combination. Such monomers can be copolymerized within a range that does not impede the effects of the present invention, but from the viewpoint of imparting heat resistance to the resin composition, the total number of monomer units contained in the maleimide copolymer may be When the content is 100% by mass, it is preferably 20% by mass or less, and more preferably 10% by mass or less.
  • the heat resistance imparting agent for chlorine-containing polymers according to the present embodiment may contain additives as described below within a range that does not impede the effects of the present invention.
  • heat stabilizers such as hindered phenol compounds, lactone compounds, phosphorus compounds, and sulfur compounds, hindered amine compounds, and benzotriazole compounds are added to the polymerization solution as necessary.
  • Additives such as light stabilizers, lubricants, plasticizers, colorants, antistatic agents, mineral oil, etc. may be added. The amount added is preferably less than 0.3 parts by mass per 100 parts by mass of the maleimide copolymer.
  • the heat resistance imparting agent for chlorine-containing polymers may consist essentially of a maleimide copolymer.
  • the heat resistance imparting agent for chlorine-containing polymers may be composed of a maleimide copolymer.
  • the melt viscosity of the maleimide copolymer contained in the heat resistance imparting agent for chlorine-containing polymers according to the present embodiment is 200 to 100,000 Pa ⁇ sec, preferably 200 to 70,000 Pa ⁇ sec, and more preferably 500 to 70,000 Pa ⁇ sec. be. Specifically, for example, it is 200, 500, 1000, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, 10000, 20000, 30000, 40000, 50000, or 100000 Pa ⁇ sec, and the numerical values illustrated here It may be within the range between any two.
  • the heat resistance of the resin composition can be sufficiently improved, and by setting the pressure to 100,000 Pa/sec or less, the heat resistance imparting agent for chlorine-containing polymers can be kneaded without melting with the chlorine-containing polymer. You can prevent things from becoming impossible. Moreover, within this range, the dispersibility of the heat resistance imparting agent for chlorine-containing polymers into chlorine-containing polymers can also be improved.
  • the melt viscosity of the maleimide copolymer contained in the heat resistance imparting agent for chlorine-containing polymers according to the present embodiment can be controlled by adjusting the blending ratio of monomer units constituting the maleimide copolymer. .
  • the melt viscosity can be increased by increasing the content of vinyl cyanide monomer units in a maleimide copolymer or by increasing the content of maleimide monomer units in a maleimide copolymer. It is possible to make it higher.
  • the melt viscosity can also be increased by increasing the weight average molecular weight of the maleimide copolymer.
  • the acid value of the maleimide copolymer contained in the heat resistance imparting agent for chlorine-containing polymers according to the present embodiment is 0 to 11 mg/g, preferably 0 to 10 mg/g, and more preferably 0 to 8 mg/g. It is g. Specifically, for example, it is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11 mg/g, and within the range between any two of the numerical values exemplified here. It may be.
  • the acid value of the maleimide copolymer is within the above range, the resin composition has an excellent balance of heat resistance, impact strength, and processability during roll kneading (sticking to rolls).
  • the acid value of the maleimide copolymer can be controlled by adjusting the blending ratio of monomer units constituting the maleimide copolymer. For example, the acid value can be lowered by reducing the content of unsaturated acid anhydride monomer units and (meth)acrylic acid monomer units in the maleimide copolymer. Furthermore, in the post-imidization method, it is possible to lower the acid value by increasing the amount of primary amine added.
  • the acid value is 0.1 mol/L in accordance with JIS K0070, in which 1 g of maleimide copolymer is dissolved in 50 mL of methyl ethyl ketone, and 1 mL of 1.0 w/v% phenolphthalein ethanol solution is added.
  • Acid value (mg/g) (titration amount (mL) - blank amount (mL)) x potassium hydroxide concentration (mol/L) x 56.11 (potassium hydroxide molar mass g/mol)/maleimide copolymer Combined amount (g)
  • the weight average molecular weight (Mw) of the maleimide copolymer contained in the heat resistance imparting agent for chlorine-containing polymers according to the present embodiment is preferably 30,000 to 120,000, more preferably 50,000 to 110,000. Specifically, for example, it is 3, 4, 5, 6, 7, 8, 9, 10, 11, or 120,000, and may be within a range between any two of the numerical values exemplified here. If the weight average molecular weight (Mw) of the maleimide copolymer is within the above range, the resin composition will have excellent impact strength.
  • the weight average molecular weight of the maleimide copolymer is a polystyrene equivalent value measured by gel permeation chromatography (GPC), and can be measured, for example, under the following conditions.
  • the polymerization mode of the maleimide copolymer contained in the heat resistance imparting agent for chlorine-containing polymers according to the present embodiment includes, for example, solution polymerization, bulk polymerization, and the like.
  • Solution polymerization is preferred from the viewpoint that a maleimide copolymer having a more uniform copolymerization composition can be obtained by polymerizing while performing partial addition or the like.
  • the solvent for solution polymerization is non-polymerizable from the viewpoint that by-products are less likely to be produced and there are fewer adverse effects.
  • ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and acetophenone
  • ethers such as tetrahydrofuran and 1,4-dioxane
  • aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene, N,N-dimethylformamide, and dimethyl
  • sulfoxide N-methyl-2-pyrrolidone, etc.
  • methyl ethyl ketone and methyl isobutyl ketone are preferred from the viewpoint of ease of solvent removal during devolatilization and recovery of the maleimide copolymer.
  • the polymerization process may be a continuous polymerization type, a batch type (batch type), or a semi-batch type.
  • the method for producing the maleimide copolymer included in the heat resistance imparting agent for chlorine-containing polymers according to the present embodiment is not particularly limited, but it can preferably be obtained by radical polymerization, and the polymerization temperature is 80 to 80°C. Preferably, the temperature is in the range of 150°C.
  • the polymerization initiator is not particularly limited, but includes known azo compounds such as azobisisobutyronitrile, azobiscyclohexanecarbonitrile, azobismethylpropionitrile, and azobismethylbutyronitrile, and benzoyl.
  • Peroxide t-butylperoxybenzoate, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethyl
  • organic peroxides such as hexanoate, di-t-butyl peroxide, dicumyl peroxide, and ethyl-3,3-di-(t-butylperoxy)butyrate can be used; You may use a species or a combination of two or more species.
  • the amount of the polymerization initiator used is not particularly limited, but it is preferably used in an amount of 0.1 to 1.5% by mass, more preferably 0.1 to 1.5% by mass based on 100% by mass of all monomer units. It is 1.0% by mass. It is preferable that the amount of the polymerization initiator used is 0.1% by mass or more because a sufficient polymerization rate can be obtained. When the amount of the polymerization initiator used is 1.5% by mass or less, the polymerization rate can be suppressed, so reaction control becomes easy and it becomes easy to obtain the target molecular weight.
  • a chain transfer agent can be used in the production of the maleimide copolymer contained in the heat resistance imparting agent for chlorine-containing polymers according to this embodiment.
  • the chain transfer agent used is not particularly limited, but includes, for example, n-octylmercaptan, n-dodecylmercaptan, t-dodecylmercaptan, ⁇ -methylstyrene dimer, ethyl thioglycolate, limonene, terpinolene, etc. be.
  • the amount of chain transfer used is not particularly limited as long as the target molecular weight can be obtained, but it should be 0.01 to 0.8% by mass based on 100% by mass of all monomer units. is preferable, and more preferably 0.1 to 0.5% by mass. If the amount of chain transfer agent used is 0.01% by mass to 0.8% by mass, the target molecular weight can be easily obtained.
  • the method for introducing the maleimide monomer unit of the maleimide copolymer contained in the heat resistance imparting agent for chlorine-containing polymers according to the present embodiment includes maleimide monomers, aromatic vinyl monomers, cyanide vinyl monomers, etc.
  • the post-imidization method is preferable because it reduces the amount of maleimide monomer remaining in the copolymer.
  • the primary amines used in the post-imidization method include, for example, methylamine, ethylamine, n-propylamine, iso-propylamine, n-butylamine, n-pentylamine, n-hexylamine, n-octylamine, and cyclohexyl.
  • Examples include amines, alkylamines such as decylamine, chloro- or bromine-substituted alkylamines, aromatic amines such as aniline, toluidine, and naphthylamine, and among these, aniline and cyclohexylamine are preferred.
  • These primary amines may be used alone or in combination of two or more.
  • the amount of primary amine added is not particularly limited, but is preferably 0.7 to 1.1 molar equivalent, more preferably 0.85 to 1.05 molar equivalent relative to the unsaturated acid anhydride group. It is. It is preferable that the amount is 0.7 molar equivalent or more based on the unsaturated acid anhydride monomer unit in the maleimide copolymer because thermal stability will be good. Moreover, if it is 1.1 molar equivalent or less, it is preferable because the amount of primary amine remaining in the maleimide copolymer is reduced. Further, by extending the time of the post-imidization step, the content of unsaturated acid anhydride monomer units in the maleimide copolymer can be reduced.
  • a catalyst may be used when introducing the maleimide monomer unit by the post-imidization method.
  • the catalyst can improve the dehydration ring closure reaction in the reaction between ammonia or a primary amine and an unsaturated acid anhydride group, particularly in the reaction of converting an unsaturated acid anhydride group into a maleimide group.
  • the type of catalyst is not particularly limited, for example, a tertiary amine can be used.
  • Tertiary amines are not particularly limited, but include, for example, trimethylamine, triethylamine, tripropylamine, tributylamine, N,N-dimethylaniline, N,N-diethylaniline, and the like.
  • the amount of the tertiary amine added is not particularly limited, it is preferably 0.01 molar equivalent or more based on the unsaturated 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. If the temperature of the imidization reaction is 100° C. or higher, the reaction rate is sufficiently high and it is preferable from the viewpoint of productivity. It is preferable that the temperature of the imidization reaction is 250° C. or lower, since it is possible to suppress deterioration of physical properties due to thermal deterioration of the maleimide copolymer.
  • devolatilization method There is a known method for removing volatile components such as the solvent used in solution polymerization and unreacted monomers from a solution after solution polymerization of a maleimide copolymer or a solution after post-imidization (devolatilization method).
  • This method can be adopted.
  • a vacuum devolatilization tank equipped with a heater or a devolatilization extruder equipped with a vent can be used.
  • the devolatilized maleimide copolymer in a molten state is transferred to a granulation process, extruded into strands from a multi-hole die, and processed into pellets using a cold cut method, an air hot cut method, or an underwater hot cut method. I can do it.
  • the maleimide copolymer contained in the resin composition according to this embodiment is also ground into powder form before use.
  • pulverization method There are no particular limitations on the pulverization method, and any known pulverization technique can be used. Suitable crushing equipment includes 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, etc.
  • the chlorine-containing polymer contained in the resin composition according to the present embodiment is obtained by polymerizing vinyl chloride monomer alone or a mixture of vinyl chloride monomer and one or more monomers copolymerizable with vinyl chloride monomer. and a chlorine-added polymer obtained by further adding chlorine to the polymer thus obtained.
  • the chlorine-containing polymer may also include a compound of the polymer thus obtained and a chlorine addition polymer.
  • Copolymerizable monomers include vinyl esters such as vinyl acetate and vinyl propionate, acrylic esters such as methyl acrylate and butyl acrylate, methacrylic esters such as methyl methacrylate and ethyl methacrylate, butyl maleate and diethyl ester.
  • fumaric acid esters such as esters, vinyl ethers such as vinyl methyl ether, vinyl butyl ether and vinyl octyl ether, vinyl cyanides such as acrylonitrile and methacrylonitrile, ⁇ -olefins such as ethylene and propylene, styrene, ⁇ -methyl Styrenes and their substituted products such as styrene, vinyltoluene, t-butylstyrene, and chlorostyrene, vinylidene halides other than vinyl chloride such as vinylidene chloride and vinyl bromide, vinyl halides, and phthalate esters such as diallylphthalate.
  • the chlorine-containing polymer is preferably polyvinyl chloride obtained by polymerizing vinyl chloride monomers.
  • the average degree of polymerization of the above chlorine-containing polymer is from 680 to 1,900, preferably from 700 to 1,700.
  • the maleimide copolymer can be uniformly dispersed, and by setting the average degree to 1900 or less, the kneadability with the maleimide copolymer is excellent.
  • the chlorine content of the chlorine-containing polymer contained in the resin composition according to the present embodiment is preferably 50.0 to 60.0%, more preferably 55.0 to 58.0%. When the chlorine content of the chlorine-containing polymer is within this range, excellent moldability and impact resistance can be obtained.
  • the chlorine-containing polymer contained in the resin composition according to the present embodiment may include a chlorine-containing polymer having a high chlorine content within a range that does not impede the effects of the present invention.
  • 100% by mass of the resin composition may contain a chlorine-containing polymer having a chlorine content of more than 60.0%, preferably less than 70%, more preferably less than 60%, and even more preferably less than 50%.
  • the method of polymerizing the chlorine-containing polymer is not particularly limited, and conventionally known bulk polymerization, solution polymerization, emulsion polymerization, etc. can be used.
  • the heat resistance imparting agent for chlorine-containing polymers in this embodiment can be blended with a chlorine-containing polymer to form a resin composition.
  • the blending ratio of the heat resistance imparting agent for chlorine-containing polymers and the chlorine-containing polymer is 5 to 100 parts by mass, preferably 5 to 80 parts by mass, of the maleimide copolymer per 100 parts by mass of the chlorine-containing polymer. The amount is more preferably 5 to 60 parts by mass.
  • the maleimide copolymer is 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 60, 70, 80, 90, or 100 parts by mass, and may be within a range between any two of the numerical values exemplified here.
  • the maleimide copolymer is added to 100 parts by weight of the chlorine-containing polymer at least 5 parts by weight, a sufficient effect of imparting heat resistance can be obtained, and by setting the amount to 100 parts by weight or less, mold release properties during kneading can be reduced. can be suppressed.
  • the balance between heat resistance, affinity with chlorine-containing polymers, and fluidity can be further improved.
  • the resin composition according to this embodiment may further contain a filler, if necessary. By blending the filler, the effect of improving the flexural modulus of the molded article obtained from the resin composition can be expected.
  • fillers that can be used in this embodiment include silica, diatomaceous earth, alumina, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, ferrites, calcium hydroxide, water Magnesium oxide, aluminum hydroxide, basic magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dawnite, hydrotalcite, calcium sulfate, barium sulfate, gypsum fiber, calcium silicate, talc, clay, mica , montmorillonite, bentonite, activated clay, sepiolite, imogolite, sericite, glass fiber, glass beads, silica balloons, aluminum nitride, boron nitride, silicon nit
  • filler is 1 to 100 parts by mass, preferably 1 to 75 parts by mass, and more preferably 1 to 50 parts by mass, per 100 parts by mass of the chlorine-containing polymer. be.
  • the blending amount of the filler is 1, 3, 5, 10, 20, 40, 60, 80, or 100 parts by mass with respect to 100 parts by mass of the chlorine-containing polymer, and the numerical values exemplified here. It may be within the range between any two.
  • the amount of the filler used means the total amount of the filler used in combination.
  • the resin composition according to this embodiment may further contain an impact modifier, if necessary.
  • an impact modifier By blending an impact modifier, the effect of improving the impact resistance of molded products obtained from the resin composition can be expected.
  • impact modifiers that can be used in this embodiment include ABS (acrylonitrile-butadiene-styrene) resin, MBS (methyl methacrylate-butadiene-styrene) resin, acrylic rubber, chlorinated polyethylene, and NBR (acrylonitrile-butadiene rubber). ).
  • ABS acrylonitrile-butadiene-styrene
  • MBS methyl methacrylate-butadiene-styrene
  • acrylic rubber chlorinated polyethylene
  • NBR acrylonitrile-butadiene rubber
  • the amount of the impact modifier according to the present embodiment is 1 to 50 parts by weight, preferably 1 to 40 parts by weight, and more preferably 1 to 40 parts by weight, per 100 parts by weight of the chlorine-containing polymer. It is 30 parts by mass.
  • the blending amount of the impact modifier is 1, 3, 5, 8, 10, 15, 20, 25, 30, 35, 40, 45, or 50 parts by mass with respect to 100 parts by mass of the chlorine-containing polymer. and may be within the range between any two of the numerical values exemplified here.
  • the amount of the impact modifier used means the total amount of the impact modifier used together.
  • the impact modifier By adding 1 part by mass or more of the impact modifier to 100 parts by mass of the chlorine-containing polymer, the effect of improving impact resistance can be obtained, and by setting it to 50 parts by mass or less, the flexural modulus can be reduced. It can be suppressed.
  • the resin composition according to this embodiment may further contain a processing aid, if necessary.
  • a processing aid it can be expected that the effect of promoting gelation during processing and improving the moldability of molded articles obtained from the resin composition can be expected.
  • processing aids that can be used in this embodiment include acrylic copolymers. These processing aids may be used alone or in combination of two or more.
  • the amount of the processing aid according to this embodiment is 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, per 100 parts by mass of the chlorine-containing polymer.
  • the amount of the processing aid added to 100 parts by mass of the chlorine-containing polymer is 0.01, 0.02, 0.05, 0.1, 0.2, 0.5, 1, 2, 5 or 10 parts by mass, and may be within a range between any two of the numerical values exemplified here.
  • the amount of the processing aid used means the total amount of the processing aid used together.
  • the resin composition according to the present embodiment may contain additives as described below to the extent that the effects of the present invention are not impaired, but the resin composition essentially consists of a heat resistance imparting agent for chlorine-containing polymers and a chlorine-containing polymer. Anything is fine. Moreover, in one embodiment, the resin composition may consist of a heat resistance imparting agent for chlorine-containing polymers and a chlorine-containing polymer. If necessary, a reinforcing agent, a stabilizer, a lubricant, a plasticizer, etc. may be added to the resin composition of the present invention, either singly or in combination of two or more. As other additives, light stabilizers, heat stabilizers, ultraviolet absorbers, antioxidants, pigments, dyes, flame retardants, etc. can be optionally added.
  • melt-kneading devices include a single screw extruder, an intermeshing type co-rotating or intermeshing type counter-rotating twin screw extruder, a screw extruder such as a non-intermeshing type twin screw extruder, a Banbury mixer, There are co-kneaders, mixing rolls, etc. Moreover, a plurality of these extruders can be used in combination.
  • a known method can be used for molding the resin composition. Examples include injection molding, sheet extrusion molding, vacuum molding, blow molding, foam molding, profile extrusion molding, and the like.
  • the resin composition is usually heated to 170 to 200°C and then processed, preferably at 180 to 200°C.
  • the molded product obtained as described above can be used for rain gutters, rain gutter parts, fittings, pipes, and joints.
  • maleimide copolymer (A-11) > 77 parts by mass of styrene, 9 parts by mass of acrylonitrile, 4 parts by mass of maleic anhydride, and 38 parts by mass of methyl ethyl ketone were placed in an autoclave with a volume of approximately 120 liters equipped with a stirrer, and after replacing the gas phase with nitrogen gas, the mixture was stirred. The temperature was raised to 92°C over 40 minutes.
  • ⁇ Resin composition> (Raw materials used) The raw materials used in each example and each comparative example are shown below.
  • Additive/Sn stabilizer TVS #8832 (manufactured by Nitto Kasei Co., Ltd.) was used.
  • - Lubricant (stearic acid): Sakura Stearate (manufactured by Nihon Yushi Corporation) was used.
  • MVS Metablane C-223A (Mitsubishi Chemical) was used.
  • -Impact modifier chlorinated PE
  • Elasthren 301A manufactured by Showa Denko
  • - Impact modifier acrylic rubber
  • Kane Ace FM-50 manufactured by Kaneka Corporation
  • Examples 1 to 16 Comparative Examples 1 to 9> (Kneading and mixing of maleimide copolymer and chlorine-containing polymer) Maleimide copolymers A-1 to A-14, B-1 to B-9, impact modifiers, and stabilizers and lubricants were added in advance and mixed in a Henschel mixer to commercially available chlorine-containing polymers (products). name: TH-1000, manufactured by Taiyo PVC Co., Ltd.) at the blending ratio shown in Tables 1 to 3, and then using a test roll ( ⁇ 6 x L15 test roll, manufactured by Kansai Roll Co., Ltd.) to form a roll sheet of the resin composition. was prepared, rolled sheets were piled up and press-formed, and test pieces were prepared by cutting or punching, and each physical property value was measured. The results are shown in Tables 1 and 2.
  • composition analysis The compositional analysis of each monomer unit in the maleimide copolymer was measured by C-13 NMR method under the measurement conditions described below.
  • the weight average molecular weight (Mw) of the maleimide copolymer is a polystyrene equivalent value measured by gel permeation chromatography (GPC), and was measured under the following conditions.
  • Equipment name SYSTEM-21 Shodex (manufactured by Showa Denko K.K.) Column: 3 PL gel MIXED-B in series Temperature: 40°C Detection: Differential refractive index Solvent: Tetrahydrofuran Concentration: 2% by mass Calibration curve: Prepared using standard polystyrene (PS) (manufactured by PL).
  • the measuring device used was a capillary rheometer 1D manufactured by Toyo Seiki Seisakusho Co., Ltd.
  • the Charpy impact strength of the heat resistance imparting agent was measured in accordance with JIS K-7111 using a notched test piece and using an edgewise impact direction at a relative humidity of 50% and an ambient temperature of 23°C.
  • the measuring device used was a digital impact tester manufactured by Toyo Seiki Seisakusho.
  • the Vicat softening temperature of the heat resistance imparting agent was measured based on JIS K7206:1999 using the B50 method (load 50 N, temperature increase rate 50° C./hour) using a test piece of 20 mm x 20 mm and 4 mm thickness.
  • the measuring device used was an HDT & VSPT testing device manufactured by Toyo Seiki Seisakusho.
  • the balance between heat resistance and impact strength of the chlorine-containing polymer is improved, and even when an Sn-based stabilizer is blended, the resin composition is A heat resistance imparting agent for chlorine-containing polymers that can reduce the sticking of objects to rolls is provided, and is suitably used for rain gutters, rain gutter parts, fitting shapes, pipes, and joints.

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Abstract

Provided are: a heat-resistance imparter for chlorinated polymers which, in a roll kneading step for kneading the heat-resistance imparter for chlorinated polymers together with a chlorinated polymer, can diminish the sticking of the resin composition to the rolls even when an Sn-based stabilizer was incorporated, while enabling the chlorinated polymer to have an improved balance between heat resistance and impact strength; a resin composition; and a molded object formed from the resin composition.　This heat-resistance imparter for chlorinated polymers comprises a maleimide-based copolymer at least including an aromatic vinyl monomer unit, a vinyl cyanide monomer unit, and a maleimide monomer unit, wherein, when the sum of the monomer units contained in the maleimide-based copolymer is taken as 100 mass%, then the maleimide-based copolymer includes 40-90 mass% the aromatic vinyl monomer unit, 0.5-30 mass% the vinyl cyanide monomer unit, and 5-30 mass% the maleimide monomer unit, and the maleimide-based copolymer has a melt viscosity, as measured under the conditions of 190°C and a shear rate of 100 /sec, of 200-100,000 Pa·sec and an acid value of 0-11 mg/g.

Description

塩素含有ポリマー用耐熱付与剤、樹脂組成物、ならびに当該樹脂組成物から成形される成形体Heat resistance imparting agent for chlorine-containing polymers, resin compositions, and molded objects formed from the resin compositions
　本発明は、塩素含有ポリマー用耐熱付与剤、樹脂組成物、ならびに当該樹脂組成物から成形される成形体に関するものである。 The present invention relates to a heat resistance imparting agent for chlorine-containing polymers, a resin composition, and a molded article formed from the resin composition.
　ポリ塩化ビニルや塩素化ポリ塩化ビニルに代表される塩素含有ポリマーは安価であり、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、ポリ塩化ビニルは耐熱性（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、Ｂ５０法（荷重５０Ｎ、昇温速度５０℃／時間）により測定されるビカット軟化温度は８２℃前後であり、通常成形加工時に配合される安定剤、可塑剤により、更に軟化温度は低下する。
　ポリ塩化ビニルの耐熱性を向上する方法としては、耐熱性を付与する樹脂をポリ塩化ビニルと混合する方法（特許文献１～４）が知られている。 Chlorine-containing polymers, such as polyvinyl chloride and chlorinated polyvinyl chloride, are inexpensive and have excellent chemical, physical, and mechanical properties, so they are produced in large quantities and used for a variety of purposes. ing.
However, polyvinyl chloride has the disadvantage of lacking heat resistance (thermal softening temperature). For example, based on JIS K7206:1999, the Vicat The softening temperature is around 82°C, and the softening temperature is further lowered by stabilizers and plasticizers that are usually added during molding.
As a method for improving the heat resistance of polyvinyl chloride, a method is known in which a resin that imparts heat resistance is mixed with polyvinyl chloride (Patent Documents 1 to 4).
特許０６４７５５０１号Patent No. 06475501 特開２００６－２６５３７３号JP 2006-265373 国際公開ＷＯ２０２２／０３９０９８号International publication WO2022/039098 国際公開ＷＯ２０２２／０３９０９９号International publication WO2022/039099
　本発明は、塩素含有ポリマーの耐熱性及び衝撃強度のバランスを向上しつつ、Ｓｎ系安定剤を配合した場合においても、塩素含有ポリマー用耐熱付与剤と塩素含有ポリマーとを含有する樹脂組成物のロール混練工程において樹脂組成物のロールへの張り付きを低減できる塩素含有ポリマー用耐熱付与剤を提供しようとするものである。 The present invention provides a resin composition containing a heat resistance imparting agent for chlorine-containing polymers and a chlorine-containing polymer, while improving the balance between heat resistance and impact strength of the chlorine-containing polymer, even when an Sn-based stabilizer is blended. The present invention aims to provide a heat resistance imparting agent for chlorine-containing polymers that can reduce the sticking of a resin composition to rolls in a roll kneading process.
　本発明者らの検討の結果、特定の単量体単位組成及び、特定の範囲の溶融粘度と酸価とを有するマレイミド系共重合体を含有する塩素含有ポリマー用耐熱付与剤を、塩素含有ポリマーに含有させて樹脂組成物を得た場合に、優れた耐熱性及び衝撃強度のバランスを達成できることを見出した。また、当該塩素含有ポリマー用耐熱付与剤は、Ｓｎ系安定剤を配合した場合においても、塩素含有ポリマー用耐熱付与剤と塩素含有ポリマーとを含有する樹脂組成物のロール混練工程において樹脂組成物のロールへの張り付きを低減できることを見出し、本発明の完成に至った。
　即ち、本発明は、
［１］　少なくとも芳香族ビニル系単量体単位、シアン化ビニル系単量体単位及びマレイミド系単量体単位を有するマレイミド系共重合体を含む塩素含有ポリマー用耐熱付与剤であり、
　前記マレイミド系共重合体は、前記マレイミド系共重合体に含有される単量体単位の合計を１００質量％とした場合に、
　　前記芳香族ビニル系単量体単位４０～９０質量％と、
　　前記シアン化ビニル系単量体単位０．５～３０質量％と、
　　前記マレイミド系単量体単位５～３０質量％と
を含み、
　前記マレイミド系共重合体の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、酸価が０～１１ｍｇ／ｇである、
塩素含有ポリマー用耐熱付与剤。
［２］　前記マレイミド系共重合体が、酸基を有する単量体単位をさらに含み、前記酸基を有する単量体単位が、不飽和酸無水物単量体単位、（メタ）アクリル酸単量体単位からなる群から選ばれる少なくとも一種である、［１］に記載の塩素含有ポリマー用耐熱付与剤。
［３］　前記酸基を有する単量体単位が、マレイン酸無水物単量体単位である、［２］に記載の塩素含有ポリマー用耐熱付与剤。
［４］　前記マレイミド系共重合体の重量平均分子量が、３～１２万である、［１］～［３］のいずれか一つに記載の塩素含有ポリマー用耐熱付与剤。
［５］　［１］～［４］のいずれか一つに記載の塩素含有ポリマー用耐熱付与剤と、塩素含有ポリマーを含有する樹脂組成物。
［６］　［５］に記載の樹脂組成物を用いた成形体。
［７］　雨どい、雨どい部品、建具用形材、パイプ及び継手として使用される［６］に記載の成形体。
に関する。 As a result of studies by the present inventors, a heat resistance imparting agent for chlorine-containing polymers containing a maleimide copolymer having a specific monomer unit composition and a specific range of melt viscosity and acid value was found to be suitable for chlorine-containing polymers. It has been found that an excellent balance between heat resistance and impact strength can be achieved when a resin composition is obtained by incorporating In addition, even when an Sn-based stabilizer is blended with the heat resistance imparting agent for chlorine-containing polymers, the heat resistance imparting agent for chlorine-containing polymers can be used in the roll kneading process of the resin composition containing the heat resistance imparting agent for chlorine-containing polymers and the chlorine-containing polymer. It was discovered that sticking to the roll can be reduced, leading to the completion of the present invention.
That is, the present invention
[1] A heat resistance imparting agent for chlorine-containing polymers comprising a maleimide copolymer having at least an aromatic vinyl monomer unit, a vinyl cyanide monomer unit, and a maleimide monomer unit,
The maleimide copolymer has 100% by mass of the total monomer units contained in the maleimide copolymer,
40 to 90% by mass of the aromatic vinyl monomer unit,
0.5 to 30% by mass of the vinyl cyanide monomer unit,
5 to 30% by mass of the maleimide monomer unit,
The maleimide copolymer has a melt viscosity of 200 to 100,000 Pa·sec measured at 190° C. and a shear rate of 100/sec, and an acid value of 0 to 11 mg/g.
Heat resistance imparting agent for chlorine-containing polymers.
[2] The maleimide copolymer further includes a monomer unit having an acid group, and the monomer unit having an acid group is an unsaturated acid anhydride monomer unit, a (meth)acrylic acid unit, The heat resistance imparting agent for chlorine-containing polymers according to [1], which is at least one type selected from the group consisting of mer units.
[3] The heat resistance imparting agent for chlorine-containing polymers according to [2], wherein the monomer unit having an acid group is a maleic anhydride monomer unit.
[4] The heat resistance imparting agent for chlorine-containing polymers according to any one of [1] to [3], wherein the maleimide copolymer has a weight average molecular weight of 30,000 to 120,000.
[5] A resin composition containing the heat resistance imparting agent for chlorine-containing polymers according to any one of [1] to [4] and a chlorine-containing polymer.
[6] A molded article using the resin composition according to [5].
[7] The molded article according to [6], which is used as a rain gutter, a rain gutter component, a shape for fittings, a pipe, and a joint.
Regarding.
　本発明の塩素含有ポリマー用耐熱付与剤を採用すれば、塩素含有ポリマーの耐熱性及び衝撃強度のバランスを向上することができる。さらに、Ｓｎ系安定剤を配合した場合においても、塩素含有ポリマー用耐熱付与剤と塩素含有ポリマーとを含有する樹脂組成物のロール混練工程において樹脂組成物のロールへの張り付きを低減できる。 By employing the heat resistance imparting agent for chlorine-containing polymers of the present invention, the balance between heat resistance and impact strength of chlorine-containing polymers can be improved. Furthermore, even when a Sn-based stabilizer is blended, sticking of the resin composition to the rolls can be reduced in the roll kneading process of the resin composition containing the heat resistance imparting agent for chlorine-containing polymers and the chlorine-containing polymer.
＜用語の説明＞
　本願明細書において、「Ａ～Ｂ」なる記載は、Ａ以上でありＢ以下であることを意味する。 <Explanation of terms>
In the present specification, the description "A to B" means greater than or equal to A and less than or equal to B.
　以下、本発明の実施形態について、詳細に説明する。本発明はこれに限定されるものではなく、その要旨を逸脱しない範囲で様々な変形が可能である。以下に示す実施形態中で示した各種特徴事項は互いに組み合わせ可能である。また、各特徴事項について独立して発明が成立する。 Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited to this, and various modifications can be made without departing from the gist thereof. Various features shown in the embodiments described below can be combined with each other. Further, the invention is established independently for each characteristic matter.
＜マレイミド系共重合体に含有される単量体単位＞
　本実施形態にかかる塩素含有ポリマー用耐熱付与剤に含まれるマレイミド系共重合体は、少なくとも芳香族ビニル系単量体単位、シアン化ビニル系単量体単位、及びマレイミド系単量体単位を含有する。また、酸基を有する単量体単位をさらに含有してもよい。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。 <Monomer unit contained in maleimide copolymer>
The maleimide copolymer contained in the heat resistance imparting agent for chlorine-containing polymers according to the present embodiment contains at least an aromatic vinyl monomer unit, a vinyl cyanide monomer unit, and a maleimide monomer unit. do. Moreover, it may further contain a monomer unit having an acid group. The monomer units contained in the maleimide copolymer will be explained below.
＜芳香族ビニル系単量体単位＞
　本実施形態にかかる塩素含有ポリマー用耐熱付与剤に含まれ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系単量体としては、例えば、スチレン、ｏ－メチルスチレン、ｍ－メチルスチレン、ｐ－メチルスチレン、２，４－ジメチルスチレン、エチルスチレン、ｐ－ｔｅｒｔ－ブチルスチレン、α－メチルスチレン、α－メチル－ｐ－メチルスチレン等が挙げられる。これらの中でもスチレンが好ましい。また、スチレンであれば耐熱性、塩素含有ポリマーとの親和性、流動性のバランスをより一層向上させることもできる。芳香族ビニル系単量体単位は、単独でも良いが２種類以上を併用しても良い。 <Aromatic vinyl monomer unit>
Examples of aromatic vinyl monomers that can be used in the maleimide copolymer contained in the heat resistance imparting agent for chlorine-containing polymers according to the present embodiment include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, and p-methylstyrene. -methylstyrene, 2,4-dimethylstyrene, ethylstyrene, p-tert-butylstyrene, α-methylstyrene, α-methyl-p-methylstyrene, and the like. Among these, styrene is preferred. In addition, styrene can further improve the balance of heat resistance, affinity with chlorine-containing polymers, and fluidity. The aromatic vinyl monomer unit may be used alone, or two or more types may be used in combination.
　本実施形態にかかる塩素含有ポリマー用耐熱付与剤に含まれるマレイミド系共重合体は、マレイミド系共重合体に含有される単量体単位の合計を１００質量％とした場合に芳香族ビニル系単量体単位を４０～９０質量％含有し、好ましくは５０～８５質量％含有し、さらに好ましくは６０～８０質量％含有する。具体的には例えば、４０、５０、６０、６５、６８、７０、７２、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４０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があり、９０質量％を超えると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。また、この範囲内であれば、耐熱性、塩素含有ポリマーとの親和性、流動性のバランスをより一層向上させることもできる。
　なお、芳香族ビニル系単量体単位を併用する場合には、芳香族ビニル系単量体単位の含有量は、併用する芳香族ビニル系単量体単位の合計量を意味する。 The maleimide copolymer contained in the heat resistance imparting agent for chlorine-containing polymers according to the present embodiment is an aromatic vinyl monomer when the total monomer units contained in the maleimide copolymer is 100% by mass. It contains 40 to 90% by mass of mer units, preferably 50 to 85% by mass, and more preferably 60 to 80% by mass. Specifically, for example, it is 40, 50, 60, 65, 68, 70, 72, 75, 80, 85, or 90% by mass, and is within the range between any two of the numerical values exemplified here. Good too. If the amount of aromatic vinyl monomer units is less than 40% by mass, the amount of other monomer components contained in the maleimide copolymer will increase relatively, resulting in the maleimide copolymer becoming a chlorine-containing polymer. If the amount exceeds 90% by mass, it may not be possible to sufficiently improve the heat resistance of the resin composition. Moreover, within this range, the balance of heat resistance, affinity with chlorine-containing polymers, and fluidity can be further improved.
In addition, when aromatic vinyl monomer units are used together, the content of the aromatic vinyl monomer units means the total amount of the aromatic vinyl monomer units used together.
＜シアン化ビニル系単量体単位＞
　本実施形態にかかる塩素含有ポリマー用耐熱付与剤に含まれ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。また、アクリロニトリルであれば、耐熱性、塩素含有ポリマーとの親和性、流動性のバランスをより一層向上させることもできる。シアン化ビニル系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。 <Vinyl cyanide monomer unit>
Examples of vinyl cyanide monomer units that can be used in the maleimide copolymer contained in the heat resistance imparting agent for chlorine-containing polymers according to the present embodiment include acrylonitrile, methacrylonitrile, ethacrylonitrile, fumaronitrile, etc. can be mentioned. Among these, acrylonitrile is preferred from the viewpoint of imparting heat resistance to the resin composition. Furthermore, acrylonitrile can further improve the balance of heat resistance, affinity with chlorine-containing polymers, and fluidity. The vinyl cyanide monomer unit may be used alone, or two or more types may be used in combination.
　本実施形態にかかる塩素含有ポリマー用耐熱付与剤に含まれるマレイミド系共重合体は、マレイミド系共重合体に含有される単量体単位の合計を１００質量％とした場合にシアン化ビニル系単量体単位を０．５～３０質量％含有し、好ましくは０．５～２０質量％含有し、さらに好ましくは０．５～１５質量％含有する。具体的には例えば、０．５、１、５、６、７、８、９、１０、１５、２０、２５、又は３０質量％であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。シアン化ビニル系単量体単位の量を０．５質量以上とすることにより樹脂組成物の耐熱性を十分に向上させることができ、３０質量％以下とすることで樹脂組成物の耐衝撃性と耐熱性のバランスを向上させることができる。また、この範囲内であれば、耐熱性、塩素含有ポリマーとの親和性、流動性のバランスをより一層向上させることもできる。
　なお、シアン化ビニル系単量体単位を併用する場合には、シアン化ビニル系単量体単位の含有量は、併用するシアン化ビニル系単量体単位の合計量を意味する。 The maleimide copolymer contained in the heat resistance imparting agent for chlorine-containing polymers according to the present embodiment is a vinyl cyanide copolymer when the total monomer units contained in the maleimide copolymer is 100% by mass. It contains 0.5 to 30% by mass of mer units, preferably 0.5 to 20% by mass, and more preferably 0.5 to 15% by mass. Specifically, for example, it is 0.5, 1, 5, 6, 7, 8, 9, 10, 15, 20, 25, or 30% by mass, and a range between any two of the numerical values exemplified here. It may be within. By setting the amount of vinyl cyanide monomer units to 0.5% by mass or more, the heat resistance of the resin composition can be sufficiently improved, and by setting the amount to 30% by mass or less, the impact resistance of the resin composition can be improved. The balance between heat resistance and heat resistance can be improved. Moreover, within this range, the balance of heat resistance, affinity with chlorine-containing polymers, and fluidity can be further improved.
In addition, when vinyl cyanide monomer units are used together, the content of vinyl cyanide monomer units means the total amount of vinyl cyanide monomer units used together.
＜マレイミド系単量体単位＞
　本実施形態にかかる塩素含有ポリマー用耐熱付与剤に含まれ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、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。また、Ｎ－フェニルマレイミドであれば、剛性を向上させることもできる。マレイミド系単量体単位は、単独でも良いが２種類以上を併用しても良い。
　マレイミド系共重合体にマレイミド系単量体単位を含有させるには、例えば、不飽和ジカルボン酸単量体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。 <Maleimide monomer unit>
Examples of maleimide monomer units that can be used in the maleimide copolymer contained in the heat resistance imparting agent for chlorine-containing polymers according to the present embodiment include N-methylmaleimide, N-butylmaleimide, and N-cyclohexylmaleimide. and N-arylmaleimides such as N-phenylmaleimide, N-chlorophenylmaleimide, N-methylphenylmaleimide, N-methoxyphenylmaleimide, and N-tribromophenylmaleimide. Among these, N-arylmaleimide is preferred from the viewpoint of imparting heat resistance to the resin composition, and N-phenylmaleimide is more preferred. Furthermore, if N-phenylmaleimide is used, rigidity can also be improved. The maleimide monomer unit may be used alone or in combination of two or more types.
In order to contain maleimide monomer units in a maleimide copolymer, for example, a copolymer obtained by copolymerizing a raw material consisting of an unsaturated dicarboxylic acid monomer unit with other monomers is mixed with ammonia or It may be imidized with a class amine. Alternatively, a raw material consisting of a maleimide monomer may be copolymerized with other monomers.
　本実施形態にかかる塩素含有ポリマー用耐熱付与剤に含まれるマレイミド系共重合体は、マレイミド系共重合体に含有される単量体単位の合計を１００質量％とした場合にマレイミド系単量体単位を５～３０質量％含有し、好ましくは１０～３０質量％含有し、より好ましくは１５～３０質量％含有する。具体的には例えば、５、１０、１５、１６、１７、１８、１９、２０、２１、２２、２３、２４、２５、又は３０質量％であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。マレイミド系単量体単位の量を５質量％以上とすることで、樹脂組成物の耐熱性を十分に向上させることができ、３０質量％以下とすることで塩素含有ポリマー用耐熱付与剤が塩素含有ポリマーと溶融せず混練することができなくなることを抑制することができる。また、この範囲内であれば、耐熱性、塩素含有ポリマーとの親和性、流動性のバランスをより一層向上させることもできる。
　なお、マレイミド系単量体単位を併用する場合には、マレイミド系単量体単位の含有量は、併用するマレイミド系単量体単位の合計量を意味する。 The maleimide copolymer contained in the heat resistance imparting agent for chlorine-containing polymers according to the present embodiment is a maleimide monomer when the total of monomer units contained in the maleimide copolymer is 100% by mass. It contains 5 to 30% by mass of units, preferably 10 to 30% by mass, and more preferably 15 to 30% by mass. Specifically, for example, it is 5, 10, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, or 30% by mass, and between any two of the numerical values exemplified here. may be within the range of By setting the amount of maleimide monomer units to 5% by mass or more, the heat resistance of the resin composition can be sufficiently improved, and by setting the amount to 30% by mass or less, the heat resistance imparting agent for chlorine-containing polymers can be It is possible to suppress the inability to melt and knead with the contained polymer. Moreover, within this range, the balance of heat resistance, affinity with chlorine-containing polymers, and fluidity can be further improved.
In addition, when a maleimide monomer unit is used in combination, the content of the maleimide monomer unit means the total amount of the maleimide monomer unit used in combination.
＜酸基を有する単量体単位＞
　本実施形態にかかる塩素含有ポリマー用耐熱付与剤に含まれるマレイミド系共重合体は、さらに酸基を有するその他共重合可能な単量体単位（本明細書中、「酸基を有する単量体単位」とも称する）を含有してもよい。ここでいう酸基とは、例えば、カルボキシル基、酸無水物構造を有する基が挙げられる。
　本実施形態にかかる塩素含有ポリマー用耐熱付与剤に含まれるマレイミド系共重合体に用いることのできる酸基を有する単量体単位としては、不飽和酸無水物単量体単位、（メタ）アクリル酸単量体単位が挙げられる。酸基を有する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。 <Monomeric unit having acid group>
The maleimide copolymer contained in the heat resistance imparting agent for chlorine-containing polymers according to the present embodiment further includes other copolymerizable monomer units having an acid group (hereinafter referred to as "monomer having an acid group"). (also referred to as "unit"). Examples of the acid group here include a carboxyl group and a group having an acid anhydride structure.
Monomer units having an acid group that can be used in the maleimide copolymer contained in the heat resistance imparting agent for chlorine-containing polymers according to the present embodiment include unsaturated acid anhydride monomer units, (meth)acrylic Examples include acid monomer units. The monomer unit having an acid group may be used alone, or two or more types may be used in combination.
　本実施形態にかかる塩素含有ポリマー用耐熱付与剤に含まれるマレイミド系共重合体は、マレイミド系共重合体に含有される単量体単位の合計を１００質量％とした場合に酸基を有する単量体単位を０～２．０質量％含有することが好ましく、より好ましくは０～１．５質量％含有する。具体的には例えば、０、０．２、０．４、０．６、０．８、１．０、１．２、１．４、１．５、１．６、１．７、１．８、１．９、又は２．０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含有量を２．０質量％以下とすることにより、樹脂組成物の耐熱性と衝撃強度、ロール混練時の加工性（ロールへの張り付き）のバランスが向上する。また、この範囲内であれば、耐熱性、塩素含有ポリマーとの親和性、流動性のバランスをより一層向上させることもできる。
　なお、酸基を有する単量体単位を併用する場合には、酸基を有する単量体単位の含有量は、併用する酸基を有する単量体単位の合計量を意味する。 The maleimide copolymer contained in the heat resistance imparting agent for chlorine-containing polymers according to the present embodiment is a monomer having an acid group, when the total of monomer units contained in the maleimide copolymer is 100% by mass. The content of the mer unit is preferably 0 to 2.0% by mass, more preferably 0 to 1.5% by mass. Specifically, for example, 0, 0.2, 0.4, 0.6, 0.8, 1.0, 1.2, 1.4, 1.5, 1.6, 1.7, 1. 8, 1.9, or 2.0% by mass, and may be within a range between any two of the numerical values exemplified here. By controlling the content of unsaturated acid anhydride monomer units to 2.0% by mass or less, the balance between heat resistance, impact strength, and processability during roll kneading (sticking to rolls) of the resin composition is improved. do. Moreover, within this range, the balance of heat resistance, affinity with chlorine-containing polymers, and fluidity can be further improved.
In addition, when a monomer unit having an acid group is used together, the content of the monomer unit having an acid group means the total amount of the monomer units having an acid group used together.
＜不飽和酸無水物単量体単位＞
　本実施形態にかかる塩素含有ポリマー用耐熱付与剤に含まれ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。また、マレイン酸無水物であれば、耐熱性、塩素含有ポリマーとの親和性、流動性のバランスをより一層向上させることもできる。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。 <Unsaturated acid anhydride monomer unit>
Examples of unsaturated acid anhydride monomer units that can be used in the maleimide copolymer included in the heat resistance imparting agent for chlorine-containing polymers according to the present embodiment include maleic anhydride, itaconic anhydride, and citracone. There are acid anhydrides, aconitic acid anhydrides, etc. Among these, maleic anhydride is preferred from the viewpoint of imparting heat resistance to the resin composition. In addition, maleic anhydride can further improve the balance of heat resistance, affinity with chlorine-containing polymers, and fluidity. The unsaturated acid anhydride monomer unit may be used alone, or two or more types may be used in combination.
　本実施形態にかかる塩素含有ポリマー用耐熱付与剤に含まれるマレイミド系共重合体は、マレイミド系共重合体に含有される単量体単位の合計を１００質量％とした場合に不飽和酸無水物単量体単位を０～１．５質量％含有することが好ましく、より好ましくは０～１．０質量％含有する。具体的には例えば、０、０．２、０．４、０．６、０．８、１．０、１．２、１．４、又は１．５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含有量を１．５質量％以下とすることにより、樹脂組成物の耐熱性と衝撃強度、ロール混練時の加工性（ロールへの張り付き）のバランスが向上する。また、この範囲内であれば、耐熱性、塩素含有ポリマーとの親和性、流動性のバランスをより一層向上させることもできる。
　なお、不飽和酸無水物単量体単位を併用する場合には、不飽和酸無水物単量体単位の含有量は、併用する不飽和酸無水物単量体単位の合計量を意味する。 The maleimide copolymer contained in the heat resistance imparting agent for chlorine-containing polymers according to the present embodiment is an unsaturated acid anhydride when the total monomer units contained in the maleimide copolymer is 100% by mass. It preferably contains 0 to 1.5% by mass of monomer units, more preferably 0 to 1.0% by mass. Specifically, for example, it is 0, 0.2, 0.4, 0.6, 0.8, 1.0, 1.2, 1.4, or 1.5% by mass, and the numerical values exemplified here It may be within the range between any two. By controlling the content of unsaturated acid anhydride monomer units to 1.5% by mass or less, the balance between heat resistance, impact strength, and processability during roll kneading (sticking to rolls) of the resin composition is improved. do. Moreover, within this range, the balance of heat resistance, affinity with chlorine-containing polymers, and fluidity can be further improved.
In addition, when an unsaturated acid anhydride monomer unit is used together, the content of the unsaturated acid anhydride monomer unit means the total amount of the unsaturated acid anhydride monomer unit used together.
＜（メタ）アクリル酸単量体単位＞
　本実施形態にかかる塩素含有ポリマー用耐熱付与剤に含まれるマレイミド系共重合体に用いることのできる（メタ）アクリル酸単量体単位としては、例えば、アクリル酸、メタクリル酸等がある。これらの中でも塩素含有ポリマーとの親和性の観点からメタクリル酸が好ましい。 <(meth)acrylic acid monomer unit>
Examples of (meth)acrylic acid monomer units that can be used in the maleimide copolymer included in the heat resistance imparting agent for chlorine-containing polymers according to the present embodiment include acrylic acid, methacrylic acid, and the like. Among these, methacrylic acid is preferred from the viewpoint of affinity with chlorine-containing polymers.
　本実施形態にかかる塩素含有ポリマー用耐熱付与剤に含まれるマレイミド系共重合体は、マレイミド系共重合体に含有される単量体単位の合計を１００質量％とした場合に（メタ）アクリル酸単量体単位を０～１．５質量％含有することが好ましく、より好ましくは０～１．０質量％含有する。具体的には例えば、０、０．２、０．４、０．６、０．８、１．０、１．２、１．４、又は１．５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。（メタ）アクリル酸単量体単位の含有量を１．５質量％以下とすることにより、樹脂組成物の耐熱性と衝撃強度のバランスが向上する。また、この範囲内であれば、耐熱性、塩素含有ポリマーとの親和性、流動性のバランスをより一層向上させることもできる。
　なお、（メタ）アクリル酸単量体単位を併用する場合には、（メタ）アクリル酸単量体単位の含有量は、併用する（メタ）アクリル酸単量体単位の合計量を意味する。 The maleimide copolymer contained in the heat resistance imparting agent for chlorine-containing polymers according to the present embodiment has (meth)acrylic acid It preferably contains 0 to 1.5% by mass of monomer units, more preferably 0 to 1.0% by mass. Specifically, for example, it is 0, 0.2, 0.4, 0.6, 0.8, 1.0, 1.2, 1.4, or 1.5% by mass, and the numerical values exemplified here It may be within the range between any two. By controlling the content of (meth)acrylic acid monomer units to 1.5% by mass or less, the balance between heat resistance and impact strength of the resin composition is improved. Moreover, within this range, the balance of heat resistance, affinity with chlorine-containing polymers, and fluidity can be further improved.
In addition, when (meth)acrylic acid monomer units are used together, the content of (meth)acrylic acid monomer units means the total amount of (meth)acrylic acid monomer units used together.
＜共重合可能な単量体＞
　本実施形態にかかる塩素含有ポリマー用耐熱付与剤に含まれるマレイミド系共重合体は、芳香族ビニル系単量体、シアン化ビニル単量体、マレイミド系単量体以外、及び酸基を有する単量体単位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、樹脂組成物への耐熱性付与の観点からマレイミド系共重合体に含有される単量体単位の合計を１００質量％とした場合に２０質量％以下とすることが好ましく、１０質量％以下とすることがさらに好ましい。 <Copolymerizable monomer>
The maleimide copolymer contained in the heat resistance imparting agent for chlorine-containing polymers according to the present embodiment includes aromatic vinyl monomers, vinyl cyanide monomers, monomers other than maleimide monomers, and monomers having acid groups. Copolymerizable monomers other than mer units may be copolymerized within a range that does not impede the effects of the present invention. Monomers that can be copolymerized with maleimide copolymers include acrylic ester monomers such as methyl acrylate, ethyl acrylate, and butyl acrylate, methyl methacrylate, and ethyl methacrylate. Examples include methacrylic acid ester monomers, acrylamide, and methacrylic acid amide. The monomers copolymerizable into the maleimide copolymer may be used alone, or two or more types may be used in combination.
Such monomers can be copolymerized within a range that does not impede the effects of the present invention, but from the viewpoint of imparting heat resistance to the resin composition, the total number of monomer units contained in the maleimide copolymer may be When the content is 100% by mass, it is preferably 20% by mass or less, and more preferably 10% by mass or less.
＜添加剤＞
　本実施形態にかかる塩素含有ポリマー用耐熱付与剤は、本発明の効果を阻害しない範囲において以下に説明されるような添加剤を含有し得る。
　マレイミド系共重合体の重合終了後、重合液には必要に応じて、ヒンダードフェノール系化合物、ラクトン系化合物、リン系化合物、イオウ系化合物などの耐熱安定剤、ヒンダードアミン系化合物、ベンゾトリアゾール系化合物等の耐光安定剤、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。その添加量はマレイミド系共重合体１００質量部に対して０．３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。
　一実施形態においては、塩素含有ポリマー用耐熱付与剤は、実質的にマレイミド系共重合体からなるものでも良い。
　また、別の実施形態おいては、塩素含有ポリマー用耐熱付与剤は、マレイミド系共重合体からなるものでも良い。 <Additives>
The heat resistance imparting agent for chlorine-containing polymers according to the present embodiment may contain additives as described below within a range that does not impede the effects of the present invention.
After the completion of polymerization of the maleimide copolymer, heat stabilizers such as hindered phenol compounds, lactone compounds, phosphorus compounds, and sulfur compounds, hindered amine compounds, and benzotriazole compounds are added to the polymerization solution as necessary. Additives such as light stabilizers, lubricants, plasticizers, colorants, antistatic agents, mineral oil, etc. may be added. The amount added is preferably less than 0.3 parts by mass per 100 parts by mass of the maleimide copolymer. These additives may be used alone or in combination of two or more.
In one embodiment, the heat resistance imparting agent for chlorine-containing polymers may consist essentially of a maleimide copolymer.
In another embodiment, the heat resistance imparting agent for chlorine-containing polymers may be composed of a maleimide copolymer.
＜マレイミド系共重合体の物性＞
＜マレイミド系共重合体の溶融粘度＞
　本実施形態にかかる塩素含有ポリマー用耐熱付与剤に含まれ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以上とすることで樹脂組成物の耐熱性を十分に向上させることができ、１０００００Ｐａ・ｓｅｃ以下とすることで塩素含有ポリマー用耐熱付与剤が塩素含有ポリマーと溶融せず混練することができなくなることを抑制することができる。また、この範囲内であれば、塩素含有ポリマー用耐熱付与剤の塩素含有ポリマーへの分散性を向上させることもできる。
　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値である。 <Physical properties of maleimide copolymer>
<Melt viscosity of maleimide copolymer>
The melt viscosity of the maleimide copolymer contained in the heat resistance imparting agent for chlorine-containing polymers according to the present embodiment is 200 to 100,000 Pa·sec, preferably 200 to 70,000 Pa·sec, and more preferably 500 to 70,000 Pa·sec. be. Specifically, for example, it is 200, 500, 1000, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, 10000, 20000, 30000, 40000, 50000, or 100000 Pa・sec, and the numerical values illustrated here It may be within the range between any two. By setting the pressure to 200 Pa/sec or more, the heat resistance of the resin composition can be sufficiently improved, and by setting the pressure to 100,000 Pa/sec or less, the heat resistance imparting agent for chlorine-containing polymers can be kneaded without melting with the chlorine-containing polymer. You can prevent things from becoming impossible. Moreover, within this range, the dispersibility of the heat resistance imparting agent for chlorine-containing polymers into chlorine-containing polymers can also be improved.
The melt viscosity is a value measured using a capillary rheometer 1D manufactured by Toyo Seiki Seisakusho Co., Ltd. with a capillary die of L=40 mm and D=1 mm.
　本実施形態にかかる塩素含有ポリマー用耐熱付与剤に含まれる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制御することが可能である。例えば、マレイミド系共重合体の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したりする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 copolymer contained in the heat resistance imparting agent for chlorine-containing polymers according to the present embodiment can be controlled by adjusting the blending ratio of monomer units constituting the maleimide copolymer. . For example, the melt viscosity can be increased by increasing the content of vinyl cyanide monomer units in a maleimide copolymer or by increasing the content of maleimide monomer units in a maleimide copolymer. It is possible to make it higher. The melt viscosity can also be increased by increasing the weight average molecular weight of the maleimide copolymer. These adjustment methods can be used in combination.
＜マレイミド系共重合体の酸価＞
　本実施形態にかかる塩素含有ポリマー用耐熱付与剤に含まれるマレイミド系共重合体の酸価は、０～１１ｍｇ／ｇであり、好ましくは０～１０ｍｇ／ｇであり、さらに好ましくは０～８ｍｇ／ｇである。具体的には、例えば、０、１、２、３、４、５、６、７、８、９、１０、又は１１ｍｇ／ｇ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。マレイミド系共重合体の酸価が上記範囲内であれば、樹脂組成物の耐熱性と衝撃強度、ロール混練時の加工性（ロールへの張り付き）のバランスが優れる。マレイミド系共重合体の酸価を制御するには、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制御することが可能である。例えば、マレイミド系共重合体の中の不飽和酸無水物単量体単位や（メタ）アクリル酸単量体単位の含有量を少なくすることにより酸価を低くすることが可能である。また、後イミド化法においては、第１級アミンの添加量を増やすことにより酸価を低くすることが可能である。
　酸価は、例えば、ＪＩＳ　Ｋ００７０に準拠して、マレイミド系共重合体１ｇをメチルエチルケトン５０ｍＬに溶解し、１．０ｗ／ｖ％フェノールフタレインエタノール溶液を１ｍＬを加えた溶液を、０．１ｍｏｌ／Ｌエタノール性水酸化カリウム溶液で中和滴定し、下記の式で計算することにより測定することができる。
　酸価（ｍｇ／ｇ）＝（滴定量（ｍＬ）－ブランク量（ｍＬ））×水酸化カリウム濃度（ｍｏｌ／Ｌ）×５６．１１（水酸化カリウムモル質量ｇ／ｍｏｌ）／マレイミド系共重合体量（ｇ） <Acid value of maleimide copolymer>
The acid value of the maleimide copolymer contained in the heat resistance imparting agent for chlorine-containing polymers according to the present embodiment is 0 to 11 mg/g, preferably 0 to 10 mg/g, and more preferably 0 to 8 mg/g. It is g. Specifically, for example, it is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11 mg/g, and within the range between any two of the numerical values exemplified here. It may be. When the acid value of the maleimide copolymer is within the above range, the resin composition has an excellent balance of heat resistance, impact strength, and processability during roll kneading (sticking to rolls). The acid value of the maleimide copolymer can be controlled by adjusting the blending ratio of monomer units constituting the maleimide copolymer. For example, the acid value can be lowered by reducing the content of unsaturated acid anhydride monomer units and (meth)acrylic acid monomer units in the maleimide copolymer. Furthermore, in the post-imidization method, it is possible to lower the acid value by increasing the amount of primary amine added.
For example, the acid value is 0.1 mol/L in accordance with JIS K0070, in which 1 g of maleimide copolymer is dissolved in 50 mL of methyl ethyl ketone, and 1 mL of 1.0 w/v% phenolphthalein ethanol solution is added. It can be measured by performing neutralization titration with an ethanolic potassium hydroxide solution and calculating using the following formula.
Acid value (mg/g) = (titration amount (mL) - blank amount (mL)) x potassium hydroxide concentration (mol/L) x 56.11 (potassium hydroxide molar mass g/mol)/maleimide copolymer Combined amount (g)
＜マレイミド系共重合体の重量平均分子量（Ｍｗ）＞
　本実施形態にかかる塩素含有ポリマー用耐熱付与剤に含まれるマレイミド系共重合体の重量平均分子量（Ｍｗ）は３万～１２万であることが好ましく、より好ましくは５万～１１万である。具体的には例えば、３、４、５、６、７、８、９、１０、１１、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。マレイミド系共重合体の重量平均分子量（Ｍｗ）が上記範囲内であれば、樹脂組成物の衝撃強度が優れる。マレイミド系共重合体の重量平均分子量（Ｍｗ）を制御するには、重合温度、重合時間、および重合開始剤添加量の調整に加えて、溶媒濃度および連鎖移動剤添加量を調整する等の方法がある。マレイミド系共重合体の重量平均分子量は、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、例えば、次の条件で測定することができる。
　　装置名：ＳＹＳＴＥＭ－２１　Ｓｈｏｄｅｘ（昭和電工株式会社製）
　　カラム：ＰＬ　ｇｅｌ　ＭＩＸＥＤ－Ｂ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）（ＰＬ社製）を用いて作製する。 <Weight average molecular weight (Mw) of maleimide copolymer>
The weight average molecular weight (Mw) of the maleimide copolymer contained in the heat resistance imparting agent for chlorine-containing polymers according to the present embodiment is preferably 30,000 to 120,000, more preferably 50,000 to 110,000. Specifically, for example, it is 3, 4, 5, 6, 7, 8, 9, 10, 11, or 120,000, and may be within a range between any two of the numerical values exemplified here. If the weight average molecular weight (Mw) of the maleimide copolymer is within the above range, the resin composition will have excellent impact strength. To control the weight average molecular weight (Mw) of the maleimide copolymer, in addition to adjusting the polymerization temperature, polymerization time, and amount of polymerization initiator added, there are methods such as adjusting the solvent concentration and the amount of chain transfer agent added. There is. The weight average molecular weight of the maleimide copolymer is a polystyrene equivalent value measured by gel permeation chromatography (GPC), and can be measured, for example, under the following conditions.
Equipment name: SYSTEM-21 Shodex (manufactured by Showa Denko K.K.)
Column: 3 PL gel MIXED-B in series Temperature: 40℃
Detection: Differential refractive index Solvent: Tetrahydrofuran Concentration: 2% by mass
Calibration curve: Prepared using standard polystyrene (PS) (manufactured by PL).
＜マレイミド系共重合体の製造＞
　本実施形態にかかる塩素含有ポリマー用耐熱付与剤に含まれる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。 <Production of maleimide copolymer>
The polymerization mode of the maleimide copolymer contained in the heat resistance imparting agent for chlorine-containing polymers according to the present embodiment includes, for example, solution polymerization, bulk polymerization, and the like. Solution polymerization is preferred from the viewpoint that a maleimide copolymer having a more uniform copolymerization composition can be obtained by polymerizing while performing partial addition or the like. It is preferable that the solvent for solution polymerization is non-polymerizable from the viewpoint that by-products are less likely to be produced and there are fewer adverse effects. For example, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and acetophenone, ethers such as tetrahydrofuran and 1,4-dioxane, aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene, N,N-dimethylformamide, and dimethyl These include sulfoxide, N-methyl-2-pyrrolidone, etc., and methyl ethyl ketone and methyl isobutyl ketone are preferred from the viewpoint of ease of solvent removal during devolatilization and recovery of the maleimide copolymer. The polymerization process may be a continuous polymerization type, a batch type (batch type), or a semi-batch type.
　本実施形態にかかる塩素含有ポリマー用耐熱付与剤に含まれるマレイミド系共重合体の製造方法としては、特に限定されるものではないが、好ましくはラジカル重合により得ることができ、重合温度は８０～１５０℃の範囲であることが好ましい。重合開始剤としては特に限定されるものではないが、例えばアゾビスイソブチロニトリル、アゾビスシクロヘキサンカルボニトリル、アゾビスメチルプロピオニトリル、アゾビスメチルブチロニトリル等の公知のアゾ化合物や、ベンゾイルパーオキサイド、ｔ－ブチルパーオキシベンゾエート、１，１－ビス（ｔ－ブチルパーオキシ）－３，３，５－トリメチルシクロヘキサン、ｔ－ブチルパーオキシイソプロピルモノカーボネート、ｔ－ブチルパーオキシ－２－エチルヘキサノエート、ジ－ｔ－ブチルパーオキサイド、ジクミルパーオキサイド、エチル－３，３－ジ－（ｔ－ブチルパーオキシ）ブチレート等の公知の有機過酸化物を用いることができ、これらの１種あるいは２種類以上を組み合わせて使用しても良い。重合の反応速度や重合率制御の観点から、１０時間半減期が７０～１２０℃であるアゾ化合物や有機過酸化物を用いるのが好ましい。重合開始剤の使用量は、特に限定されるものではないが、全単量体単位１００質量％に対して０．１～１．５質量％使用することが好ましく、さらに好ましくは０．１～１．０質量％である。重合開始剤の使用量が０．１質量％以上であれば、十分な重合速度が得られるため好ましい。重合開始剤の使用量が１．５質量％以下であれば、重合速度が抑制できるため反応制御が容易になり、目標分子量を得ることが容易になる。 The method for producing the maleimide copolymer included in the heat resistance imparting agent for chlorine-containing polymers according to the present embodiment is not particularly limited, but it can preferably be obtained by radical polymerization, and the polymerization temperature is 80 to 80°C. Preferably, the temperature is in the range of 150°C. The polymerization initiator is not particularly limited, but includes known azo compounds such as azobisisobutyronitrile, azobiscyclohexanecarbonitrile, azobismethylpropionitrile, and azobismethylbutyronitrile, and benzoyl. Peroxide, t-butylperoxybenzoate, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethyl Known organic peroxides such as hexanoate, di-t-butyl peroxide, dicumyl peroxide, and ethyl-3,3-di-(t-butylperoxy)butyrate can be used; You may use a species or a combination of two or more species. From the viewpoint of polymerization reaction rate and polymerization rate control, it is preferable to use an azo compound or an organic peroxide having a 10-hour half-life of 70 to 120°C. The amount of the polymerization initiator used is not particularly limited, but it is preferably used in an amount of 0.1 to 1.5% by mass, more preferably 0.1 to 1.5% by mass based on 100% by mass of all monomer units. It is 1.0% by mass. It is preferable that the amount of the polymerization initiator used is 0.1% by mass or more because a sufficient polymerization rate can be obtained. When the amount of the polymerization initiator used is 1.5% by mass or less, the polymerization rate can be suppressed, so reaction control becomes easy and it becomes easy to obtain the target molecular weight.
　本実施形態にかかる塩素含有ポリマー用耐熱付与剤に含まれる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 copolymer contained in the heat resistance imparting agent for chlorine-containing polymers according to this embodiment. The chain transfer agent used is not particularly limited, but includes, for example, n-octylmercaptan, n-dodecylmercaptan, t-dodecylmercaptan, α-methylstyrene dimer, ethyl thioglycolate, limonene, terpinolene, etc. be. The amount of chain transfer used is not particularly limited as long as the target molecular weight can be obtained, but it should be 0.01 to 0.8% by mass based on 100% by mass of all monomer units. is preferable, and more preferably 0.1 to 0.5% by mass. If the amount of chain transfer agent used is 0.01% by mass to 0.8% by mass, the target molecular weight can be easily obtained.
　本実施形態にかかる塩素含有ポリマー用耐熱付与剤に含まれるマレイミド系共重合体のマレイミド系単量体単位の導入方法としては、マレイミド系単量体、芳香族ビニル系単量体、シアン化ビニル単量体とを共重合する方法（直接法）、或いは不飽和酸無水物単量体、芳香族ビニル系単量体、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級アミンで不飽和酸無水物基を反応させることにより不飽和酸無水物基をマレイミド系単量体単位に変換する方法（後イミド化法）がある。後イミド化法の方が、共重合体中の残存マレイミド系単量体量が少なくなるので好ましい。 The method for introducing the maleimide monomer unit of the maleimide copolymer contained in the heat resistance imparting agent for chlorine-containing polymers according to the present embodiment includes maleimide monomers, aromatic vinyl monomers, cyanide vinyl monomers, etc. A method of copolymerizing with a monomer (direct method), or a method of copolymerizing in advance with an unsaturated acid anhydride monomer, an aromatic vinyl monomer, or a vinyl cyanide monomer, and then adding ammonia or There is a method (post-imidization method) of converting an unsaturated acid anhydride group into a maleimide monomer unit by reacting the unsaturated acid anhydride group with a primary amine. The post-imidization method is preferable because it reduces the amount of maleimide monomer remaining in the copolymer.
　後イミド化法で用いる第１級アミンとは、例えば、メチルアミン、エチルアミン、ｎ－プロピルアミン、ｉｓｏ－プロピルアミン、ｎ－ブチルアミン、ｎ－ペンチルアミン、ｎ－ヘキシルアミン、ｎ－オクチルアミン、シクロヘキシルアミン、デシルアミン等のアルキルアミン類及びクロル又はブロム置換アルキルアミン、アニリン、トルイジン、ナフチルアミン等の芳香族アミンがあり、この中でもアニリン、シクロヘキシルアミンが好ましい。これらの第１級アミンは、単独で使用しても２種類以上を組み合わせて使用しても良い。第１級アミンの添加量は特に限定されるものではないが、不飽和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。また、後イミド化工程の時間を延長すれば、マレイミド系共重合体中の不飽和酸無水物単量体単位の含有量を低減させることができる。 The primary amines used in the post-imidization method include, for example, methylamine, ethylamine, n-propylamine, iso-propylamine, n-butylamine, n-pentylamine, n-hexylamine, n-octylamine, and cyclohexyl. Examples include amines, alkylamines such as decylamine, chloro- or bromine-substituted alkylamines, aromatic amines such as aniline, toluidine, and naphthylamine, and among these, aniline and cyclohexylamine are preferred. These primary amines may be used alone or in combination of two or more. The amount of primary amine added is not particularly limited, but is preferably 0.7 to 1.1 molar equivalent, more preferably 0.85 to 1.05 molar equivalent relative to the unsaturated acid anhydride group. It is. It is preferable that the amount is 0.7 molar equivalent or more based on the unsaturated acid anhydride monomer unit in the maleimide copolymer because thermal stability will be good. Moreover, if it is 1.1 molar equivalent or less, it is preferable because the amount of primary amine remaining in the maleimide copolymer is reduced. Further, by extending the time of the post-imidization step, the content of unsaturated acid anhydride monomer units in the maleimide copolymer can be reduced.
　マレイミド系単量体単位を後イミド化法で導入する際に触媒を用いてもよい。触媒は、アンモニア又は第１級アミンと不飽和酸無水物基との反応、特に不飽和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ことができる。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ことができる。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 post-imidization method. The catalyst can improve the dehydration ring closure reaction in the reaction between ammonia or a primary amine and an unsaturated acid anhydride group, particularly in the reaction of converting an unsaturated acid anhydride group into a maleimide group. Although the type of catalyst is not particularly limited, for example, a tertiary amine can be used. Tertiary amines are not particularly limited, but include, for example, trimethylamine, triethylamine, tripropylamine, tributylamine, N,N-dimethylaniline, N,N-diethylaniline, and the like. Although the amount of the tertiary amine added is not particularly limited, it is preferably 0.01 molar equivalent or more based on the unsaturated 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. If the temperature of the imidization reaction is 100° C. or higher, the reaction rate is sufficiently high and it is preferable from the viewpoint of productivity. It is preferable that the temperature of the imidization reaction is 250° C. or lower, since it is possible to suppress deterioration of physical properties due to thermal deterioration of the maleimide copolymer.
　マレイミド系共重合体の溶液重合終了後の溶液或いは後イミド化終了後の溶液から、溶液重合に用いた溶媒や未反応の単量体などの揮発分を取り除く方法（脱揮方法）は、公知の手法が採用できる。例えば、加熱器付きの真空脱揮槽やベント付き脱揮押出機を用いることができる。脱揮された溶融状態のマレイミド系共重合体は、造粒工程に移送され、多孔ダイよりストランド状に押出し、コールドカット方式や空中ホットカット方式、水中ホットカット方式にてペレット状に加工することができる。
　塩素含有ポリマーがパウダー形状である場合は、本実施形態にかかる樹脂組成物に含まれる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。 There is a known method for removing volatile components such as the solvent used in solution polymerization and unreacted monomers from a solution after solution polymerization of a maleimide copolymer or a solution after post-imidization (devolatilization method). This method can be adopted. For example, a vacuum devolatilization tank equipped with a heater or a devolatilization extruder equipped with a vent can be used. The devolatilized maleimide copolymer in a molten state is transferred to a granulation process, extruded into strands from a multi-hole die, and processed into pellets using a cold cut method, an air hot cut method, or an underwater hot cut method. I can do it.
When the chlorine-containing polymer is in powder form, it is preferable that the maleimide copolymer contained in the resin composition according to this embodiment is also ground into powder form before use. There are no particular limitations on the pulverization method, and any known pulverization technique can be used. Suitable crushing equipment includes 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, etc. .
＜塩素含有ポリマー＞
　本実施形態にかかる樹脂組成物に含まれる塩素含有ポリマーは、塩化ビニル単量体単独または塩化ビニル単量体とこれと共重合可能な１種類以上の単量体との混合物を重合して得られた重合体、及びこのようにして得られた重合体を更に塩素付加した塩素付加重合体である。また、塩素含有ポリマーには、このようにして得られた重合体と塩素付加重合体とのコンパウンドも含み得る。共重合可能な単量体としては、酢酸ビニルやプロピオン酸ビニル等のビニルエステル類、メチルアクリレートやブチルアクリレート等のアクリル酸エステル類、メチルメタクリレートやエチルメタクリレート等のメタクリル酸エステル類、ブチルマレートやジエチルマレート等のフマル酸エステル類、ビニルメチルエーテル、ビニルブチルエーテル及びビニルオクチルエーテル等のビニルエーテル類、アクリロニトリルやメタクリロニトリル等のシアン化ビニル類、エチレン、プロピレン等のα－オレフィン類、スチレン、α－メチルスチレン、ビニルトルエン、ｔ－ブチルスチレン、クロロスチレン等のスチレン類及びその置換体、塩化ビニリデンや臭化ビニル等の塩化ビニル以外のハロゲン化ビニリデンやハロゲン化ビニル類、ジアリルフタレート等のフタル酸エステル類が挙げられる。
　塩素含有ポリマーは、耐熱付与効果の観点から、塩化ビニル単量体を重合して得られるポリ塩化ビニルが好ましい。 <Chlorine-containing polymer>
The chlorine-containing polymer contained in the resin composition according to the present embodiment is obtained by polymerizing vinyl chloride monomer alone or a mixture of vinyl chloride monomer and one or more monomers copolymerizable with vinyl chloride monomer. and a chlorine-added polymer obtained by further adding chlorine to the polymer thus obtained. The chlorine-containing polymer may also include a compound of the polymer thus obtained and a chlorine addition polymer. Copolymerizable monomers include vinyl esters such as vinyl acetate and vinyl propionate, acrylic esters such as methyl acrylate and butyl acrylate, methacrylic esters such as methyl methacrylate and ethyl methacrylate, butyl maleate and diethyl ester. fumaric acid esters such as esters, vinyl ethers such as vinyl methyl ether, vinyl butyl ether and vinyl octyl ether, vinyl cyanides such as acrylonitrile and methacrylonitrile, α-olefins such as ethylene and propylene, styrene, α-methyl Styrenes and their substituted products such as styrene, vinyltoluene, t-butylstyrene, and chlorostyrene, vinylidene halides other than vinyl chloride such as vinylidene chloride and vinyl bromide, vinyl halides, and phthalate esters such as diallylphthalate. can be mentioned.
From the viewpoint of imparting heat resistance, the chlorine-containing polymer is preferably polyvinyl chloride obtained by polymerizing vinyl chloride monomers.
　上記塩素含有ポリマーの平均重合度は６８０～１９００であり、好ましくは７００～１７００である。平均重合度を６８０以上とすることで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 above chlorine-containing polymer is from 680 to 1,900, preferably from 700 to 1,700. By setting the average degree of polymerization to 680 or more, the maleimide copolymer can be uniformly dispersed, and by setting the average degree to 1900 or less, the kneadability with the maleimide copolymer is excellent.
＜塩素含有ポリマーの塩素含有率＞
　本実施形態にかかる樹脂組成物に含まれる塩素含有ポリマーの塩素含有率は、５０．０～６０．０％であることが好ましく、さらに好ましくは５５．０～５８．０％である。塩素含有ポリマーの塩素含有率がこの範囲内であると優れた成形性と耐衝撃性が得られる。 <Chlorine content of chlorine-containing polymer>
The chlorine content of the chlorine-containing polymer contained in the resin composition according to the present embodiment is preferably 50.0 to 60.0%, more preferably 55.0 to 58.0%. When the chlorine content of the chlorine-containing polymer is within this range, excellent moldability and impact resistance can be obtained.
＜塩素含有率の高い塩素含有ポリマー＞
　本実施形態にかかる樹脂組成物に含まれる塩素含有ポリマーは、本発明の効果を阻害しない範囲内において塩素含有率の高い塩素含有ポリマーを含んでもよい。例えば、樹脂組成物１００質量％中に、塩素含有率が６０．０％を超える塩素含有ポリマーを、好ましくは７０％未満、さらに好ましくは６０％未満、より好ましくは５０％未満含んでもよい。塩素含有率が６０．０％を超える塩素含有ポリマーの含有量をこのような範囲に制御することにより、優れた成形性と耐衝撃性が得られる。 <Chlorine-containing polymer with high chlorine content>
The chlorine-containing polymer contained in the resin composition according to the present embodiment may include a chlorine-containing polymer having a high chlorine content within a range that does not impede the effects of the present invention. For example, 100% by mass of the resin composition may contain a chlorine-containing polymer having a chlorine content of more than 60.0%, preferably less than 70%, more preferably less than 60%, and even more preferably less than 50%. By controlling the content of the chlorine-containing polymer having a chlorine content of more than 60.0% within this range, excellent moldability and impact resistance can be obtained.
＜塩素含有ポリマーの製造＞
　塩素含有ポリマーの重合方法は特に限定されず、従来公知の塊状重合、溶液重合、乳化重合等が用いられる。 <Production of chlorine-containing polymer>
The method of polymerizing the chlorine-containing polymer is not particularly limited, and conventionally known bulk polymerization, solution polymerization, emulsion polymerization, etc. can be used.
＜塩素含有ポリマー用耐熱付与剤と塩素含有ポリマーとを含有する樹脂組成物＞
　本実施形態における塩素含有ポリマー用耐熱付与剤を塩素含有ポリマーに配合し、樹脂組成物とすることができる。本実施形態における塩素含有ポリマー用耐熱付与剤と塩素含有ポリマーの配合割合は、塩素含有ポリマー１００質量部に対してマレイミド系共重合体５～１００質量部であり、好ましくは５～８０質量部であり、さらに好ましくは５～６０質量部である。具体的には例えば、塩素含有ポリマー１００質量部に対してマレイミド系共重合体が５、１０、１５、２０、２５、３０、３５、４０、４５、５０、６０、７０、８０、９０、又は１００質量部であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。塩素含有ポリマー１００質量部に対するマレイミド系共重合体の配合量を５質量部以上とすることで十分な耐熱付与効果が得られ、また、１００質量部以下とすることで混練時の離型性悪化が抑えられる。また、この範囲内であれば、耐熱性、塩素含有ポリマーとの親和性、流動性のバランスをより一層を向上させることもできる。 <Resin composition containing heat resistance imparting agent for chlorine-containing polymer and chlorine-containing polymer>
The heat resistance imparting agent for chlorine-containing polymers in this embodiment can be blended with a chlorine-containing polymer to form a resin composition. In this embodiment, the blending ratio of the heat resistance imparting agent for chlorine-containing polymers and the chlorine-containing polymer is 5 to 100 parts by mass, preferably 5 to 80 parts by mass, of the maleimide copolymer per 100 parts by mass of the chlorine-containing polymer. The amount is more preferably 5 to 60 parts by mass. Specifically, for example, the maleimide copolymer is 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 60, 70, 80, 90, or 100 parts by mass, and may be within a range between any two of the numerical values exemplified here. By adding the maleimide copolymer to 100 parts by weight of the chlorine-containing polymer at least 5 parts by weight, a sufficient effect of imparting heat resistance can be obtained, and by setting the amount to 100 parts by weight or less, mold release properties during kneading can be reduced. can be suppressed. Moreover, within this range, the balance between heat resistance, affinity with chlorine-containing polymers, and fluidity can be further improved.
＜樹脂組成物の充填剤＞
　本実施形態にかかる樹脂組成物は、必要に応じて充填剤をさらに配合してもよい。充填剤を配合することによって、樹脂組成物から得られる成形品の曲げ弾性率を向上させる効果が期待できる。本実施形態において用いることができる充填剤としては、例えば、シリカ、珪藻土、アルミナ、酸化亜鉛、酸化チタン、酸化カルシウム、酸化マグネシウム、酸化鉄、酸化錫、酸化アンチモン、フェライト類、水酸化カルシウム、水酸化マグネシウム、水酸化アルミニウム、塩基性炭 酸マグネシウム、炭酸カルシウム、炭酸マグネシウム、炭酸亜鉛、炭酸バリウム、ドーンナイト、ハイドロタルサイト、硫酸カルシウム、硫酸バリウム、石膏繊維、ケイ酸カルシウム、タルク、クレー、マイカ、モンモリロナイト、ベントナイト、活性白土、セピオライト、イモゴライト、セリサイト、ガラス繊維、ガラスビーズ、シリカ系バルン、窒化アルミニウム、窒化ホウ素、窒化ケイ素、カーボンブラック、グラファイト、炭素繊維、炭 素バルン、木炭粉末、各種金属粉、チタン酸カリウム、硫酸マグネシウム、チタン酸ジルコン酸鉛、アルミニウムボレート、硫化モリブデン、炭化ケイ素、ステンレス繊維、ホウ酸亜鉛、各種磁性粉、スラグ繊維、フライアッシュ、脱水汚泥等またこれらを表面処理したものが挙げられる。これらの中でも機械物性・ビカット軟化温度向上性を向上させる効果の高い炭酸カルシウム、ケイ酸カルシウム、水酸化カルシウム、酸化カルシウム、炭酸マグネシウム、水酸化マグネシウム、酸化マグネシウム、炭酸バリウム、水酸化アルミニウム、酸化亜鉛、水酸化亜鉛、酸化鉄等の塩基性無機充填剤、タルクが好ましい。これらの充填剤は、１種を単独で用いてもよく、２種類以上を併用してもよい。
　本実施形態にかかる充填剤の配合量は、塩素含有ポリマー１００質量部に対して充填剤１～１００質量部であり、好ましくは１～７５質量部であり、さらに好ましくは１～５０質量部である。具体的には例えば、塩素含有ポリマー１００質量部に対して充填剤の配合量が１、３、５、１０、２０、４０、６０、８０、又は１００質量部であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。なお、充填剤を併用する場合には、充填剤の配合量は、併用する充填剤の合計量を意味する。塩素含有ポリマー１００質量部に対する充填剤の配合量を１質量部以上とすることで曲げ弾性率を向上させる効果が得られ、また、５０質量部以下とすることで分散性低下が抑えられる。 <Filler for resin composition>
The resin composition according to this embodiment may further contain a filler, if necessary. By blending the filler, the effect of improving the flexural modulus of the molded article obtained from the resin composition can be expected. Examples of fillers that can be used in this embodiment include silica, diatomaceous earth, alumina, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, ferrites, calcium hydroxide, water Magnesium oxide, aluminum hydroxide, basic magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dawnite, hydrotalcite, calcium sulfate, barium sulfate, gypsum fiber, calcium silicate, talc, clay, mica , montmorillonite, bentonite, activated clay, sepiolite, imogolite, sericite, glass fiber, glass beads, silica balloons, aluminum nitride, boron nitride, silicon nitride, carbon black, graphite, carbon fiber, carbon balloons, charcoal powder, various Metal powder, potassium titanate, magnesium sulfate, lead zirconate titanate, aluminum borate, molybdenum sulfide, silicon carbide, stainless fiber, zinc borate, various magnetic powders, slag fiber, fly ash, dehydrated sludge, etc. Also, surface treatment of these The following can be mentioned. Among these, calcium carbonate, calcium silicate, calcium hydroxide, calcium oxide, magnesium carbonate, magnesium hydroxide, magnesium oxide, barium carbonate, aluminum hydroxide, and zinc oxide are highly effective in improving mechanical properties and Vicat softening temperature. , basic inorganic fillers such as zinc hydroxide, iron oxide, and talc are preferred. These fillers may be used alone or in combination of two or more.
The blending amount of the filler according to this embodiment is 1 to 100 parts by mass, preferably 1 to 75 parts by mass, and more preferably 1 to 50 parts by mass, per 100 parts by mass of the chlorine-containing polymer. be. Specifically, for example, the blending amount of the filler is 1, 3, 5, 10, 20, 40, 60, 80, or 100 parts by mass with respect to 100 parts by mass of the chlorine-containing polymer, and the numerical values exemplified here. It may be within the range between any two. In addition, when a filler is used in combination, the amount of the filler used means the total amount of the filler used in combination. By setting the amount of the filler to be 1 part by mass or more to 100 parts by mass of the chlorine-containing polymer, the effect of improving the flexural modulus can be obtained, and by setting it to 50 parts by mass or less, a decrease in dispersibility can be suppressed.
＜樹脂組成物の衝撃改質剤＞
　本実施形態にかかる樹脂組成物は、必要に応じて衝撃改質剤をさらに配合してもよい。衝撃改質剤を配合することによって、樹脂組成物から得られる成形品の耐衝撃性を向上させる効果が期待できる。本実施形態において用いることができる衝撃改質剤としては、例えば、ＡＢＳ（アクリロニトリル－ブタジエン－スチレン）樹脂、ＭＢＳ（メチルメタクリレート－ブタジエン－スチレン）樹脂、アクリルゴム、塩素化ポリエチレン、ＮＢＲ（アクリロニトリルブタジエンゴム）が挙げられる。これらの中でも耐衝撃性を向上させる効果の高いＭＢＳ樹脂、アクリルゴム、塩素化ポリエチレンが好ましい。これらの衝撃改質剤は、１種を単独で用いてもよく、２種類以上を併用してもよい。
　本実施形態にかかる衝撃改質剤の配合量は、塩素含有ポリマー１００質量部に対して衝撃改質剤１～５０質量部であり、好ましくは１～４０質量部であり、さらに好ましくは１～３０質量部である。具体的には例えば、塩素含有ポリマー１００質量部に対して衝撃改質剤の配合量が１、３、５、８、１０、１５、２０、２５、３０、３５、４０、４５又は５０質量部であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。なお、衝撃改質剤を併用する場合には、衝撃改質剤の配合量は、併用する衝撃改質剤の合計量を意味する。塩素含有ポリマー１００質量部に対する衝撃改質剤の配合量を１質量部以上とすることで耐衝撃性を向上させる効果が得られ、また、５０質量部以下とすることで曲げ弾性率の低下が抑えられる。 <Impact modifier for resin composition>
The resin composition according to this embodiment may further contain an impact modifier, if necessary. By blending an impact modifier, the effect of improving the impact resistance of molded products obtained from the resin composition can be expected. Examples of impact modifiers that can be used in this embodiment include ABS (acrylonitrile-butadiene-styrene) resin, MBS (methyl methacrylate-butadiene-styrene) resin, acrylic rubber, chlorinated polyethylene, and NBR (acrylonitrile-butadiene rubber). ). Among these, MBS resin, acrylic rubber, and chlorinated polyethylene are preferable because they are highly effective in improving impact resistance. These impact modifiers may be used alone or in combination of two or more.
The amount of the impact modifier according to the present embodiment is 1 to 50 parts by weight, preferably 1 to 40 parts by weight, and more preferably 1 to 40 parts by weight, per 100 parts by weight of the chlorine-containing polymer. It is 30 parts by mass. Specifically, for example, the blending amount of the impact modifier is 1, 3, 5, 8, 10, 15, 20, 25, 30, 35, 40, 45, or 50 parts by mass with respect to 100 parts by mass of the chlorine-containing polymer. and may be within the range between any two of the numerical values exemplified here. In addition, when using an impact modifier together, the amount of the impact modifier used means the total amount of the impact modifier used together. By adding 1 part by mass or more of the impact modifier to 100 parts by mass of the chlorine-containing polymer, the effect of improving impact resistance can be obtained, and by setting it to 50 parts by mass or less, the flexural modulus can be reduced. It can be suppressed.
＜樹脂組成物の加工助剤＞
　本実施形態にかかる樹脂組成物は、必要に応じて加工助剤をさらに配合してもよい。加工助剤を配合することによって、加工時のゲル化の促進や樹脂組成物から得られる成形品の成形性を向上させる効果が期待できる。本実施形態において用いることができる加工助剤としては、例えば、アクリル系共重合体が挙げられる。これらの加工助剤は、１種を単独で用いてもよく、２種類以上を併用してもよい。
　本実施形態にかかる加工助剤の配合量は、塩素含有ポリマー１００質量部に対して加工助剤０．０１～１０質量部であり、好ましくは０．０５～５質量部である。具体的には例えば、塩素含有ポリマー１００質量部に対して加工助剤の配合量が０．０１、０．０２、０．０５、０．１、０．２、０．５、１、２、５又は１０質量部であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。なお、加工助剤を併用する場合には、加工助剤の配合量は、併用する加工助剤の合計量を意味する。塩素含有ポリマー１００質量部に対する加工助剤の配合量を０．０１質量部以上とすることで加工性を向上させる効果が得られ、また、１０質量部以下とすることで機械物性低下が抑えられる。 <Processing aid for resin composition>
The resin composition according to this embodiment may further contain a processing aid, if necessary. By incorporating a processing aid, it can be expected that the effect of promoting gelation during processing and improving the moldability of molded articles obtained from the resin composition can be expected. Examples of processing aids that can be used in this embodiment include acrylic copolymers. These processing aids may be used alone or in combination of two or more.
The amount of the processing aid according to this embodiment is 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, per 100 parts by mass of the chlorine-containing polymer. Specifically, for example, the amount of the processing aid added to 100 parts by mass of the chlorine-containing polymer is 0.01, 0.02, 0.05, 0.1, 0.2, 0.5, 1, 2, 5 or 10 parts by mass, and may be within a range between any two of the numerical values exemplified here. In addition, when a processing aid is used together, the amount of the processing aid used means the total amount of the processing aid used together. By setting the amount of the processing aid to 100 parts by mass of the chlorine-containing polymer to be 0.01 parts by mass or more, the effect of improving processability can be obtained, and by setting it to 10 parts by mass or less, deterioration of mechanical properties can be suppressed. .
＜樹脂組成物の添加剤＞
　本実施形態にかかる樹脂組成物は、本発明の効果を阻害しない範囲において以下に説明されるような添加剤を含有し得るが、実質的に塩素含有ポリマー用耐熱付与剤と塩素含有ポリマーからなるものでも良い。また、一実施形態においては、樹脂組成物は、塩素含有ポリマー用耐熱付与剤と塩素含有ポリマーからなるものでも良い。
　本発明の樹脂組成物に、必要に応じ、更に強化剤、安定剤、滑剤、可塑剤等を単独または２種類以上組み合わせて添加することもできる。
　その他の添加剤としては、光安定剤、熱安定剤、紫外線吸収剤、酸化防止剤、顔料、染料、難燃剤等を任意に添加することができる。 <Additives for resin composition>
The resin composition according to the present embodiment may contain additives as described below to the extent that the effects of the present invention are not impaired, but the resin composition essentially consists of a heat resistance imparting agent for chlorine-containing polymers and a chlorine-containing polymer. Anything is fine. Moreover, in one embodiment, the resin composition may consist of a heat resistance imparting agent for chlorine-containing polymers and a chlorine-containing polymer.
If necessary, a reinforcing agent, a stabilizer, a lubricant, a plasticizer, etc. may be added to the resin composition of the present invention, either singly or in combination of two or more.
As other additives, light stabilizers, heat stabilizers, ultraviolet absorbers, antioxidants, pigments, dyes, flame retardants, etc. can be optionally added.
＜樹脂組成物の製造＞
　塩素含有ポリマー用耐熱付与剤と塩素含有ポリマーとを混練混合して本実施形態にかかる樹脂組成物を得る方法については、特に限定はなく、公知の溶融混練技術を用いることが出来る。好適に使用できる溶融混練装置としては、単軸押出機、噛合形同方向回転または噛合形異方向回転二軸押出機、非または不完全噛合形二軸押出機等のスクリュー押出機、バンバリーミキサー、コニーダー及び混合ロール等がある。また、これらの押出機を複数組み合わせて使用することもできる。 <Manufacture of resin composition>
There is no particular limitation on the method of kneading and mixing the heat resistance imparting agent for chlorine-containing polymers and the chlorine-containing polymer to obtain the resin composition according to the present embodiment, and any known melt-kneading technique can be used. Suitable melt-kneading devices include a single screw extruder, an intermeshing type co-rotating or intermeshing type counter-rotating twin screw extruder, a screw extruder such as a non-intermeshing type twin screw extruder, a Banbury mixer, There are co-kneaders, mixing rolls, etc. Moreover, a plurality of these extruders can be used in combination.
　樹脂組成物の成形方法は、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、樹脂組成物を１７０～２００℃に加熱した後、加工されるが、１８０～２００℃であることが好ましい。 A known method can be used for molding the resin composition. Examples include injection molding, sheet extrusion molding, vacuum molding, blow molding, foam molding, profile extrusion molding, and the like. During molding, the resin composition is usually heated to 170 to 200°C and then processed, preferably at 180 to 200°C.
　上述のようにして得られた成形体は、雨どい、雨どい部品、建具用形材、パイプ及び継手の用途に利用できる。 The molded product obtained as described above can be used for rain gutters, rain gutter parts, fittings, pipes, and joints.
　以下、詳細な内容について実施例を用いて説明するが、本発明は以下の実施例に限定されるものではない。 Hereinafter, detailed contents will be explained using examples, but the present invention is not limited to the following examples.
　＜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７７質量部、アクリロニトリル９質量部、マレイン酸無水物４質量部、α－メチルスチレンダイマーを０．４５質量部、メチルエチルケトン３８質量部を仕込み、気相部を窒素ガスで置換した後、撹拌しながら４０分かけて９２℃まで昇温した。昇温後９２℃を保持しながら、マレイン酸無水物９質量部とｔ－ブチルパーオキシ－２－エチルヘキサノエート０．８０質量部をメチルエチルケトン４７質量部に溶解した溶液を５時間かけて連続的に添加した。添加終了後、１２０℃に昇温し、１時間反応させて重合を終了させた。その後、重合液にアニリン１３質量部、トリエチルアミン０．２質量部を加え１４０℃で１５時間反応させた。反応終了後のイミド化反応液をベントタイプスクリュー式押出機に投入し、揮発分を除去してペレット状のマレイミド系共重合体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。 <Production example of maleimide copolymer (A-1)>
In an autoclave with a capacity of approximately 120 liters equipped with a stirrer, 77 parts by mass of styrene, 9 parts by mass of acrylonitrile, 4 parts by mass of maleic anhydride, 0.45 parts by mass of α-methylstyrene dimer, and 38 parts by mass of methyl ethyl ketone were charged. After replacing the phase with nitrogen gas, the temperature was raised to 92° C. over 40 minutes while stirring. After raising the temperature, a solution of 9 parts by mass of maleic anhydride and 0.80 parts by mass of t-butylperoxy-2-ethylhexanoate dissolved in 47 parts by mass of methyl ethyl ketone was continuously heated for 5 hours while maintaining the temperature at 92°C. added. After the addition was completed, the temperature was raised to 120°C, and the reaction was carried out for 1 hour to complete the polymerization. Thereafter, 13 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 15 hours. After the reaction was completed, the imidization reaction solution was charged into a vent type screw extruder to remove volatile components to obtain pellet-shaped maleimide copolymer A-1. Table 1 shows the analysis results of the obtained maleimide copolymer.
　＜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７７質量部、アクリロニトリル９質量部、マレイン酸無水物４質量部、α－メチルスチレンダイマーを０．４５質量部、メチルエチルケトン３８質量部を仕込み、気相部を窒素ガスで置換した後、撹拌しながら４０分かけて９２℃まで昇温した。昇温後９２℃を保持しながら、マレイン酸無水物９質量部とｔ－ブチルパーオキシ－２－エチルヘキサノエート０．８０質量部をメチルエチルケトン４７質量部に溶解した溶液を５時間かけて連続的に添加した。添加終了後、１２０℃に昇温し、１時間反応させて重合を終了させた。その後、重合液にアニリン１２質量部、トリエチルアミン０．２質量部を加え１４０℃で１５時間反応させた。反応終了後のイミド化反応液をベントタイプスクリュー式押出機に投入し、揮発分を除去してペレット状のマレイミド系共重合体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 copolymer (A-2)>
In an autoclave with a capacity of approximately 120 liters equipped with a stirrer, 77 parts by mass of styrene, 9 parts by mass of acrylonitrile, 4 parts by mass of maleic anhydride, 0.45 parts by mass of α-methylstyrene dimer, and 38 parts by mass of methyl ethyl ketone were charged. After replacing the phase with nitrogen gas, the temperature was raised to 92° C. over 40 minutes while stirring. After raising the temperature, a solution of 9 parts by mass of maleic anhydride and 0.80 parts by mass of t-butylperoxy-2-ethylhexanoate dissolved in 47 parts by mass of methyl ethyl ketone was continuously heated for 5 hours while maintaining the temperature at 92°C. added. After the addition was completed, the temperature was raised to 120°C, and the reaction was carried out for 1 hour to complete the polymerization. Thereafter, 12 parts by mass of aniline and 0.2 parts by mass of triethylamine were added to the polymerization solution, and the mixture was reacted at 140° C. for 15 hours. After the completion of the reaction, the imidization reaction solution was charged into a vent type screw extruder to remove volatile components to obtain pellet-shaped maleimide copolymer A-2. Table 1 shows the analysis results of the obtained maleimide copolymer.
　＜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７７質量部、アクリロニトリル９質量部、マレイン酸無水物４質量部、α－メチルスチレンダイマーを０．４５質量部、メチルエチルケトン３８質量部を仕込み、気相部を窒素ガスで置換した後、撹拌しながら４０分かけて９２℃まで昇温した。昇温後９２℃を保持しながら、マレイン酸無水物９質量部とｔ－ブチルパーオキシ－２－エチルヘキサノエート０．８０質量部をメチルエチルケトン４７質量部に溶解した溶液を５時間かけて連続的に添加した。添加終了後、１２０℃に昇温し、１時間反応させて重合を終了させた。その後、重合液にアニリン１２質量部、トリエチルアミン０．２質量部を加え１４０℃で１０時間反応させた。反応終了後のイミド化反応液をベントタイプスクリュー式押出機に投入し、揮発分を除去してペレット状のマレイミド系共重合体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 copolymer (A-3)>
In an autoclave with a capacity of approximately 120 liters equipped with a stirrer, 77 parts by mass of styrene, 9 parts by mass of acrylonitrile, 4 parts by mass of maleic anhydride, 0.45 parts by mass of α-methylstyrene dimer, and 38 parts by mass of methyl ethyl ketone were charged. After replacing the phase with nitrogen gas, the temperature was raised to 92° C. over 40 minutes while stirring. After raising the temperature, a solution of 9 parts by mass of maleic anhydride and 0.80 parts by mass of t-butylperoxy-2-ethylhexanoate dissolved in 47 parts by mass of methyl ethyl ketone was continuously heated for 5 hours while maintaining the temperature at 92°C. added. After the addition was completed, the temperature was raised to 120°C, and the reaction was carried out for 1 hour to complete the polymerization. Thereafter, 12 parts by mass of aniline and 0.2 parts by mass of triethylamine were added to the polymerization solution and reacted at 140° C. for 10 hours. After the reaction was completed, the imidization reaction solution was charged into a vent type screw extruder to remove volatile components to obtain pellet-shaped maleimide copolymer A-3. Table 1 shows the analysis results of the obtained maleimide copolymer.
　＜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７７質量部、アクリロニトリル９質量部、マレイン酸無水物４質量部、α－メチルスチレンダイマーを０．４５質量部、メチルエチルケトン３８質量部を仕込み、気相部を窒素ガスで置換した後、撹拌しながら４０分かけて９２℃まで昇温した。昇温後９２℃を保持しながら、マレイン酸無水物９質量部とｔ－ブチルパーオキシ－２－エチルヘキサノエート０．８０質量部をメチルエチルケトン４７質量部に溶解した溶液を５時間かけて連続的に添加した。添加終了後、１２０℃に昇温し、１時間反応させて重合を終了させた。その後、重合液にアニリン１１質量部、トリエチルアミン０．２質量部を加え１４０℃で１５時間反応させた。反応終了後のイミド化反応液をベントタイプスクリュー式押出機に投入し、揮発分を除去してペレット状のマレイミド系共重合体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 copolymer (A-4)>
In an autoclave with a capacity of approximately 120 liters equipped with a stirrer, 77 parts by mass of styrene, 9 parts by mass of acrylonitrile, 4 parts by mass of maleic anhydride, 0.45 parts by mass of α-methylstyrene dimer, and 38 parts by mass of methyl ethyl ketone were charged. After replacing the phase with nitrogen gas, the temperature was raised to 92° C. over 40 minutes while stirring. After raising the temperature, a solution of 9 parts by mass of maleic anhydride and 0.80 parts by mass of t-butylperoxy-2-ethylhexanoate dissolved in 47 parts by mass of methyl ethyl ketone was continuously heated for 5 hours while maintaining the temperature at 92°C. added. After the addition was completed, the temperature was raised to 120°C, and the reaction was carried out for 1 hour to complete the polymerization. Thereafter, 11 parts by mass of aniline and 0.2 parts by mass of triethylamine were added to the polymerization solution, and the mixture was reacted at 140° C. for 15 hours. After the completion of the reaction, the imidization reaction solution was charged into a vent type screw extruder to remove volatile components to obtain pellet-shaped maleimide copolymer A-4. Table 1 shows the analysis results of the obtained maleimide copolymer.
　＜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８３質量部、アクリロニトリル３質量部、マレイン酸無水物４質量部、α－メチルスチレンダイマーを０．４５質量部、メチルエチルケトン３８質量部を仕込み、気相部を窒素ガスで置換した後、撹拌しながら４０分かけて９２℃まで昇温した。昇温後９２℃を保持しながら、マレイン酸無水物９質量部とｔ－ブチルパーオキシ－２－エチルヘキサノエート０．８０質量部をメチルエチルケトン４７質量部に溶解した溶液を５時間かけて連続的に添加した。添加終了後、１２０℃に昇温し、１時間反応させて重合を終了させた。その後、重合液にアニリン１２質量部、トリエチルアミン０．２質量部を加え１４０℃で１３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 copolymer (A-5)>
In an autoclave with a capacity of about 120 liters equipped with a stirrer, 83 parts by mass of styrene, 3 parts by mass of acrylonitrile, 4 parts by mass of maleic anhydride, 0.45 parts by mass of α-methylstyrene dimer, and 38 parts by mass of methyl ethyl ketone were charged. After replacing the phase with nitrogen gas, the temperature was raised to 92° C. over 40 minutes while stirring. After raising the temperature, a solution of 9 parts by mass of maleic anhydride and 0.80 parts by mass of t-butylperoxy-2-ethylhexanoate dissolved in 47 parts by mass of methyl ethyl ketone was continuously heated for 5 hours while maintaining the temperature at 92°C. added. After the addition was completed, the temperature was raised to 120°C, and the reaction was carried out for 1 hour to complete the polymerization. Thereafter, 12 parts by mass of aniline and 0.2 parts by mass of triethylamine were added to the polymerization solution, and the mixture was reacted at 140° C. for 13 hours. After the reaction was completed, the imidization reaction solution was charged into a vent type screw extruder to remove volatile components to obtain pellet-shaped maleimide copolymer A-5. Table 1 shows the analysis results of the obtained maleimide copolymer.
　＜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７８質量部、アクリロニトリル１３質量部、マレイン酸無水物２質量部、α－メチルスチレンダイマーを０．１６質量部、メチルエチルケトン３０質量部を仕込み、気相部を窒素ガスで置換した後、撹拌しながら４０分かけて９２℃まで昇温した。昇温後９２℃を保持しながら、マレイン酸無水物６質量部とｔ－ブチルパーオキシ－２－エチルヘキサノエート０．７０質量部をメチルエチルケトン３２質量部に溶解した溶液を４．５時間かけて連続的に添加した。添加終了後、１２０℃に昇温し、１．５時間反応させて重合を終了させた。その後、重合液にアニリン８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－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 copolymer (A-6)>
In an autoclave with a capacity of approximately 120 liters equipped with a stirrer, 78 parts by mass of styrene, 13 parts by mass of acrylonitrile, 2 parts by mass of maleic anhydride, 0.16 parts by mass of α-methylstyrene dimer, and 30 parts by mass of methyl ethyl ketone were charged. After replacing the phase with nitrogen gas, the temperature was raised to 92° C. over 40 minutes while stirring. After raising the temperature, a solution of 6 parts by mass of maleic anhydride and 0.70 parts by mass of t-butylperoxy-2-ethylhexanoate dissolved in 32 parts by mass of methyl ethyl ketone was heated for 4.5 hours while maintaining the temperature at 92°C. was added continuously. After the addition was completed, the temperature was raised to 120° C., and the reaction was carried out for 1.5 hours to complete the polymerization. Thereafter, 8 parts by mass of aniline and 0.1 parts by mass of triethylamine were added to the polymerization solution and reacted at 140° C. for 7 hours. After the completion of the reaction, the imidization reaction solution was charged into a vent type screw extruder to remove volatile components to obtain pellet-shaped maleimide copolymer A-6. Table 1 shows the analysis results of the obtained maleimide copolymer.
　＜マレイミド系共重合体（Ａ－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７１質量部、アクリロニトリル１０質量部、マレイン酸無水物４質量部、α－メチルスチレンダイマーを０．８０質量部、メチルエチルケトン４１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１５質量部とｔ－ブチルパーオキシ－２－エチルヘキサノエート０．４０質量部をメチルエチルケトン７５質量部に溶解した溶液を４．５時間かけて連続的に添加した。添加終了後、１２０℃に昇温し、１．５時間反応させて重合を終了させた。その後、重合液にアニリン１７質量部、トリエチルアミン０．３質量部を加え１４０℃で１０時間反応させた。反応終了後のイミド化反応液をベントタイプスクリュー式押出機に投入し、揮発分を除去してペレット状のマレイミド系共重合体Ａ－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１に示す。 <Production example of maleimide copolymer (A-7)>
In an autoclave with a capacity of approximately 120 liters equipped with a stirrer, 71 parts by mass of styrene, 10 parts by mass of acrylonitrile, 4 parts by mass of maleic anhydride, 0.80 parts by mass of α-methylstyrene dimer, and 41 parts by mass of methyl ethyl ketone were charged. After replacing the phase with nitrogen gas, the temperature was raised to 92° C. over 40 minutes while stirring. After raising the temperature, a solution of 15 parts by mass of maleic anhydride and 0.40 parts by mass of t-butylperoxy-2-ethylhexanoate dissolved in 75 parts by mass of methyl ethyl ketone was heated for 4.5 hours while maintaining the temperature at 92°C. was added continuously. After the addition was completed, the temperature was raised to 120° C., and the reaction was carried out for 1.5 hours to complete the polymerization. Thereafter, 17 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 10 hours. After the completion of the reaction, the imidization reaction solution was charged into a vent type screw extruder to remove volatile components to obtain pellet-shaped maleimide copolymer A-7. Table 1 shows the analysis results of the obtained maleimide copolymer.
　＜マレイミド系共重合体（Ａ－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０．２５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１２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－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 copolymer (A-8)>
In an autoclave with a capacity of approximately 120 liters equipped with a stirrer, 27 parts by mass of styrene, 33 parts by mass of acrylonitrile, 2 parts by mass of maleic anhydride, 0.25 parts by mass of α-methylstyrene dimer, and 24 parts by mass of methyl ethyl ketone were charged. After replacing the phase with nitrogen gas, the temperature was raised to 92° C. over 40 minutes while stirring. After raising the temperature, a solution of 31 parts by mass of styrene, 7 parts by mass of maleic anhydride, and 0.38 parts by mass of t-butylperoxy-2-ethylhexanoate dissolved in 37 parts by mass of methyl ethyl ketone was prepared while maintaining the temperature at 92°C. Addition was made continuously over 3.5 hours. Furthermore, after the addition of maleic anhydride was completed, a solution of 0.22 parts by mass of t-butylperoxy-2-ethylhexanoate dissolved 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. Thereafter, 6 parts by mass of aniline and 0.1 parts by mass of triethylamine were added to the polymerization solution, and the mixture was reacted at 140° C. for 12 hours. After the completion of the reaction, the imidization reaction solution was charged into a vent type screw extruder to remove volatile components to obtain pellet-shaped maleimide copolymer A-8. Table 2 shows the analysis results of the obtained maleimide copolymer.
　＜マレイミド系共重合体（Ａ－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０．１４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６質量部、トリエチルアミン０．１質量部を加え１４０℃で１４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－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 copolymer (A-9)>
In an autoclave with a capacity of approximately 120 liters equipped with a stirrer, 85 parts by mass of styrene, 7 parts by mass of acrylonitrile, 1 part by mass of maleic anhydride, 0.14 parts by mass of α-methylstyrene dimer, and 30 parts by mass of methyl ethyl ketone were charged. After replacing the phase with nitrogen gas, the temperature was raised to 92° C. over 40 minutes while stirring. After raising the temperature, a solution of 7 parts by mass of maleic anhydride and 0.80 parts by mass of t-butylperoxy-2-ethylhexanoate dissolved in 33 parts by mass of methyl ethyl ketone was continuously heated over 6 hours while maintaining the temperature at 92°C. added. After the addition was completed, the temperature was raised to 120°C, and the reaction was carried out for 1 hour to complete the polymerization. Thereafter, 6 parts by mass of aniline and 0.1 parts by mass of triethylamine were added to the polymerization solution, and the mixture was reacted at 140° C. for 14 hours. After the completion of the reaction, the imidization reaction solution was put into a vent type screw extruder, and volatile components were removed to obtain pellet-shaped maleimide copolymer A-9. Table 2 shows the analysis results of the obtained maleimide copolymer.
　＜マレイミド系共重合体（Ａ－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１９質量部、アクリロニトリル２５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１．１０質量部、メチルエチルケトン３４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２０質量部とｔ－ブチルパーオキシ－２－エチルヘキサノエート０．２３質量部をメチルエチルケトン１００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０．１９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２．５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１９質量部、トリエチルアミン０．３質量部を加え１４０℃で１０時間反応させた。反応終了後のイミド化反応液をベントタイプスクリュー式押出機に投入し、揮発分を除去してペレット状のマレイミド系共重合体Ａ－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 copolymer (A-10)>
In an autoclave with a capacity of approximately 120 liters equipped with a stirrer, 19 parts by mass of styrene, 25 parts by mass of acrylonitrile, 3 parts by mass of maleic anhydride, 1.10 parts by mass of α-methylstyrene dimer, and 34 parts by mass of methyl ethyl ketone were charged. After replacing the phase with nitrogen gas, the temperature was raised to 92° C. over 40 minutes while stirring. After raising the temperature, a solution of 34 parts by mass of styrene, 20 parts by mass of maleic anhydride, and 0.23 parts by mass of t-butylperoxy-2-ethylhexanoate dissolved in 100 parts by mass of methyl ethyl ketone was prepared while maintaining the temperature at 92 °C. The addition was continued over a period of 3 hours. Furthermore, after the addition of maleic anhydride was completed, a solution of 0.19 parts by mass of t-butylperoxy-2-ethylhexanoate dissolved in 2 parts 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. Thereafter, 19 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 10 hours. After the completion of the reaction, the imidization reaction solution was put into a vent type screw extruder, and volatile components were removed to obtain maleimide copolymer A-10 in the form of pellets. Table 2 shows the analysis results of the obtained maleimide copolymer.
　＜マレイミド系共重合体（Ａ－１１）の製造例＞
攪拌機を備えた容積約１２０リットルのオートクレーブ中にスチレン７７質量部、アクリロニトリル９質量部、マレイン酸無水物４質量部、メチルエチルケトン３８質量部を仕込み、気相部を窒素ガスで置換した後、撹拌しながら４０分かけて９２℃まで昇温した。昇温後９２℃を保持しながら、マレイン酸無水物９質量部とｔ－ブチルパーオキシ－２－エチルヘキサノエート０．８０質量部をメチルエチルケトン４７質量部に溶解した溶液を５時間かけて連続的に添加した。添加終了後、１２０℃に昇温し、１時間反応させて重合を終了させた。その後、重合液にアニリン１２質量部、トリエチルアミン０．２質量部を加え１４０℃で１３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－１１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 copolymer (A-11)>
77 parts by mass of styrene, 9 parts by mass of acrylonitrile, 4 parts by mass of maleic anhydride, and 38 parts by mass of methyl ethyl ketone were placed in an autoclave with a volume of approximately 120 liters equipped with a stirrer, and after replacing the gas phase with nitrogen gas, the mixture was stirred. The temperature was raised to 92°C over 40 minutes. After raising the temperature, a solution of 9 parts by mass of maleic anhydride and 0.80 parts by mass of t-butylperoxy-2-ethylhexanoate dissolved in 47 parts by mass of methyl ethyl ketone was continuously heated for 5 hours while maintaining the temperature at 92°C. added. After the addition was completed, the temperature was raised to 120°C, and the reaction was carried out for 1 hour to complete the polymerization. Thereafter, 12 parts by mass of aniline and 0.2 parts by mass of triethylamine were added to the polymerization solution, and the mixture was reacted at 140° C. for 13 hours. After the reaction was completed, the imidization reaction solution was charged into a vent type screw extruder to remove volatile components to obtain pellet-shaped maleimide copolymer A-11. Table 2 shows the analysis results of the obtained maleimide copolymer.
　＜マレイミド系共重合体（Ａ－１２）の製造例＞
攪拌機を備えた容積約１２０リットルのオートクレーブ中にスチレン７７質量部、アクリロニトリル９質量部、マレイン酸無水物４質量部、α－メチルスチレンダイマーを０．７２質量部、メチルエチルケトン３８質量部を仕込み、気相部を窒素ガスで置換した後、撹拌しながら４０分かけて９２℃まで昇温した。昇温後９２℃を保持しながら、マレイン酸無水物９質量部とｔ－ブチルパーオキシ－２－エチルヘキサノエート０．８０質量部をメチルエチルケトン４７質量部に溶解した溶液を５時間かけて連続的に添加した。添加終了後、１２０℃に昇温し、１時間反応させて重合を終了させた。その後、重合液にアニリン１１質量部、トリエチルアミン０．２質量部を加え１４０℃で１５時間反応させた。反応終了後のイミド化反応液をベントタイプスクリュー式押出機に投入し、揮発分を除去してペレット状のマレイミド系共重合体Ａ－１２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 copolymer (A-12)>
In an autoclave with a capacity of approximately 120 liters equipped with a stirrer, 77 parts by mass of styrene, 9 parts by mass of acrylonitrile, 4 parts by mass of maleic anhydride, 0.72 parts by mass of α-methylstyrene dimer, and 38 parts by mass of methyl ethyl ketone were charged. After replacing the phase with nitrogen gas, the temperature was raised to 92° C. over 40 minutes while stirring. After raising the temperature, a solution of 9 parts by mass of maleic anhydride and 0.80 parts by mass of t-butylperoxy-2-ethylhexanoate dissolved in 47 parts by mass of methyl ethyl ketone was continuously heated for 5 hours while maintaining the temperature at 92°C. added. After the addition was completed, the temperature was raised to 120°C, and the reaction was carried out for 1 hour to complete the polymerization. Thereafter, 11 parts by mass of aniline and 0.2 parts by mass of triethylamine were added to the polymerization solution, and the mixture was reacted at 140° C. for 15 hours. After the reaction was completed, the imidization reaction solution was charged into a vent type screw extruder to remove volatile components to obtain pellet-shaped maleimide copolymer A-12. Table 2 shows the analysis results of the obtained maleimide copolymer.
　＜マレイミド系共重合体（Ａ－１３）の製造例＞
攪拌機を備えた容積約１２０リットルのオートクレーブ中にスチレン７７質量部、アクリロニトリル９質量部、マレイン酸無水物４質量部、メタクリル酸０．８質量部、α－メチルスチレンダイマーを０．４４質量部、メチルエチルケトン３８質量部を仕込み、気相部を窒素ガスで置換した後、撹拌しながら４０分かけて９２℃まで昇温した。昇温後９２℃を保持しながら、マレイン酸無水物９質量部とｔ－ブチルパーオキシ－２－エチルヘキサノエート０．８０質量部をメチルエチルケトン４７質量部に溶解した溶液を５時間かけて連続的に添加した。添加終了後、１２０℃に昇温し、１時間反応させて重合を終了させた。その後、重合液にアニリン１２質量部、トリエチルアミン０．２質量部を加え１４０℃で１５時間反応させた。反応終了後のイミド化反応液をベントタイプスクリュー式押出機に投入し、揮発分を除去してペレット状のマレイミド系共重合体Ａ－１３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 copolymer (A-13)>
In an autoclave with a volume of about 120 liters equipped with a stirrer, 77 parts by mass of styrene, 9 parts by mass of acrylonitrile, 4 parts by mass of maleic anhydride, 0.8 parts by mass of methacrylic acid, 0.44 parts by mass of α-methylstyrene dimer, After charging 38 parts by mass of methyl ethyl ketone and replacing the gas phase with nitrogen gas, the temperature was raised to 92° C. over 40 minutes with stirring. After raising the temperature, a solution of 9 parts by mass of maleic anhydride and 0.80 parts by mass of t-butylperoxy-2-ethylhexanoate dissolved in 47 parts by mass of methyl ethyl ketone was continuously heated for 5 hours while maintaining the temperature at 92°C. added. After the addition was completed, the temperature was raised to 120°C, and the reaction was carried out for 1 hour to complete the polymerization. Thereafter, 12 parts by mass of aniline and 0.2 parts by mass of triethylamine were added to the polymerization solution, and the mixture was reacted at 140° C. for 15 hours. After the completion of the reaction, the imidization reaction solution was put into a vent type screw extruder, and volatile components were removed to obtain maleimide copolymer A-13 in the form of pellets. Table 2 shows the analysis results of the obtained maleimide copolymer.
　＜マレイミド系共重合体（Ａ－１４）の製造例＞
攪拌機を備えた容積約１２０リットルのオートクレーブ中にスチレン７７質量部、アクリロニトリル９質量部、マレイン酸無水物４質量部、メタクリル酸１．７質量部、α－メチルスチレンダイマーを０．４３質量部、メチルエチルケトン３８質量部を仕込み、気相部を窒素ガスで置換した後、撹拌しながら４０分かけて９２℃まで昇温した。昇温後９２℃を保持しながら、マレイン酸無水物９質量部とｔ－ブチルパーオキシ－２－エチルヘキサノエート０．８０質量部をメチルエチルケトン４７質量部に溶解した溶液を５時間かけて連続的に添加した。添加終了後、１２０℃に昇温し、１時間反応させて重合を終了させた。その後、重合液にアニリン１３質量部、トリエチルアミン０．２質量部を加え１４０℃で１５時間反応させた。反応終了後のイミド化反応液をベントタイプスクリュー式押出機に投入し、揮発分を除去してペレット状のマレイミド系共重合体Ａ－１４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 copolymer (A-14)>
In an autoclave with a volume of about 120 liters equipped with a stirrer, 77 parts by mass of styrene, 9 parts by mass of acrylonitrile, 4 parts by mass of maleic anhydride, 1.7 parts by mass of methacrylic acid, 0.43 parts by mass of α-methylstyrene dimer, After charging 38 parts by mass of methyl ethyl ketone and replacing the gas phase with nitrogen gas, the temperature was raised to 92° C. over 40 minutes with stirring. After raising the temperature, a solution of 9 parts by mass of maleic anhydride and 0.80 parts by mass of t-butylperoxy-2-ethylhexanoate dissolved in 47 parts by mass of methyl ethyl ketone was continuously heated for 5 hours while maintaining the temperature at 92°C. added. After the addition was completed, the temperature was raised to 120°C, and the reaction was carried out for 1 hour to complete the polymerization. Thereafter, 13 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 15 hours. After the reaction was completed, the imidization reaction solution was charged into a vent type screw extruder to remove volatile components to obtain pellet-shaped maleimide copolymer A-14. Table 2 shows the analysis results of the obtained maleimide copolymer.
　＜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７７質量部、アクリロニトリル９質量部、マレイン酸無水物４質量部、α－メチルスチレンダイマーを０．４３質量部、メチルエチルケトン３８質量部を仕込み、気相部を窒素ガスで置換した後、撹拌しながら４０分かけて９２℃まで昇温した。昇温後９２℃を保持しながら、マレイン酸無水物９質量部とｔ－ブチルパーオキシ－２－エチルヘキサノエート０．８０質量部をメチルエチルケトン４７質量部に溶解した溶液を５時間かけて連続的に添加した。添加終了後、１２０℃に昇温し、１時間反応させて重合を終了させた。その後、重合液にアニリン１１質量部、トリエチルアミン０．２質量部を加え１４０℃で１３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３に示す。 <Production example of maleimide copolymer (B-1)>
In an autoclave with a capacity of about 120 liters equipped with a stirrer, 77 parts by mass of styrene, 9 parts by mass of acrylonitrile, 4 parts by mass of maleic anhydride, 0.43 parts by mass of α-methylstyrene dimer, and 38 parts by mass of methyl ethyl ketone were charged. After replacing the phase with nitrogen gas, the temperature was raised to 92° C. over 40 minutes while stirring. After raising the temperature, a solution of 9 parts by mass of maleic anhydride and 0.80 parts by mass of t-butylperoxy-2-ethylhexanoate dissolved in 47 parts by mass of methyl ethyl ketone was continuously heated for 5 hours while maintaining the temperature at 92°C. added. After the addition was completed, the temperature was raised to 120°C, and the reaction was carried out for 1 hour to complete the polymerization. Thereafter, 11 parts by mass of aniline and 0.2 parts by mass of triethylamine were added to the polymerization solution, and the mixture was reacted at 140° C. for 13 hours. After the completion of the reaction, the imidization reaction solution was put into a vent type screw extruder, and volatile components were removed to obtain pellet-shaped maleimide copolymer B-1. Table 3 shows the analysis results of the obtained maleimide copolymer.
　＜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７７質量部、アクリロニトリル９質量部、マレイン酸無水物４質量部、メタクリル酸２．３質量部、α－メチルスチレンダイマーを０．４３質量部、メチルエチルケトン３８質量部を仕込み、気相部を窒素ガスで置換した後、撹拌しながら４０分かけて９２℃まで昇温した。昇温後９２℃を保持しながら、マレイン酸無水物９質量部とｔ－ブチルパーオキシ－２－エチルヘキサノエート０．８０質量部をメチルエチルケトン４７質量部に溶解した溶液を５時間かけて連続的に添加した。添加終了後、１２０℃に昇温し、１時間反応させて重合を終了させた。その後、重合液にアニリン１３質量部、トリエチルアミン０．２質量部を加え１４０℃で１５時間反応させた。反応終了後のイミド化反応液をベントタイプスクリュー式押出機に投入し、揮発分を除去してペレット状のマレイミド系共重合体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３に示す。 <Production example of maleimide copolymer (B-2)>
In an autoclave with a volume of about 120 liters equipped with a stirrer, 77 parts by mass of styrene, 9 parts by mass of acrylonitrile, 4 parts by mass of maleic anhydride, 2.3 parts by mass of methacrylic acid, 0.43 parts by mass of α-methylstyrene dimer, After charging 38 parts by mass of methyl ethyl ketone and replacing the gas phase with nitrogen gas, the temperature was raised to 92° C. over 40 minutes with stirring. After raising the temperature, a solution of 9 parts by mass of maleic anhydride and 0.80 parts by mass of t-butylperoxy-2-ethylhexanoate dissolved in 47 parts by mass of methyl ethyl ketone was continuously heated for 5 hours while maintaining the temperature at 92°C. added. After the addition was completed, the temperature was raised to 120°C, and the reaction was carried out for 1 hour to complete the polymerization. Thereafter, 13 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 15 hours. After the completion of the reaction, the imidization reaction solution was charged into a vent type screw extruder to remove volatile components to obtain pellet-shaped maleimide copolymer B-2. Table 3 shows the analysis results of the obtained maleimide copolymer.
　＜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０．１０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０．４１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８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１０時間反応させた。反応終了後のイミド化反応液をベントタイプスクリュー式押出機に投入し、揮発分を除去してペレット状のマレイミド系共重合体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３に示す。 <Production example of maleimide copolymer (B-3)>
In an autoclave with a volume of approximately 120 liters equipped with a stirrer, 94 parts by mass of styrene, 2 parts by mass of acrylonitrile, 0.4 parts by mass of maleic anhydride, 0.10 parts by mass of α-methylstyrene dimer, and 28 parts by mass of methyl ethyl ketone were charged. After replacing the gas phase with nitrogen gas, the temperature was raised to 92° C. over 40 minutes with stirring. After raising the temperature, a solution of 4 parts by mass of maleic anhydride and 0.41 parts by mass of t-butylperoxy-2-ethylhexanoate dissolved in 18 parts by mass of methyl ethyl ketone was continuously heated for 8 hours while maintaining the temperature at 92°C. added. After the addition was completed, the temperature was raised to 120°C, and the reaction was carried out for 1 hour to complete the polymerization. Thereafter, 3 parts by mass of aniline and 0.1 parts by mass of triethylamine were added to the polymerization solution, and the mixture was reacted at 140° C. for 10 hours. After the reaction was completed, the imidization reaction solution was charged into a vent type screw extruder to remove volatile components to obtain pellet-shaped maleimide copolymer B-3. Table 3 shows the analysis results of the obtained maleimide copolymer.
　＜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７質量部、アクリロニトリル３３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０．６５質量部、メチルエチルケトン３７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３６質量部及びマレイン酸無水物２１質量部とｔ－ブチルパーオキシ－２－エチルヘキサノエート０．１８質量部をメチルエチルケトン１０５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。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１５質量部、トリエチルアミン０．４質量部を加え１４０℃で１０時間反応させた。反応終了後のイミド化反応液をベントタイプスクリュー式押出機に投入し、揮発分を除去してペレット状のマレイミド系共重合体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３に示す。 <Production example of maleimide copolymer (B-4)>
In an autoclave with a capacity of approximately 120 liters equipped with a stirrer, 7 parts by mass of styrene, 33 parts by mass of acrylonitrile, 3 parts by mass of maleic anhydride, 0.65 parts by mass of α-methylstyrene dimer, and 37 parts by mass of methyl ethyl ketone were charged. After replacing the phase with nitrogen gas, the temperature was raised to 92° C. over 40 minutes while stirring. After raising the temperature, a solution of 36 parts by mass of styrene, 21 parts by mass of maleic anhydride, and 0.18 parts by mass of t-butylperoxy-2-ethylhexanoate dissolved in 105 parts by mass of methyl ethyl ketone was prepared while maintaining the temperature at 92°C. Additions were made continuously over 2.5 hours. Furthermore, after the addition of maleic anhydride was completed, a solution of 0.18 parts by mass of t-butylperoxy-2-ethylhexanoate dissolved 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. Thereafter, 15 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 10 hours. After the reaction was completed, the imidization reaction solution was put into a vent type screw extruder to remove volatile components to obtain pellet-shaped maleimide copolymer B-4. Table 3 shows the analysis results of the obtained maleimide copolymer.
　＜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０．０９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０．８２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１０時間反応させた。反応終了後のイミド化反応液をベントタイプスクリュー式押出機に投入し、揮発分を除去してペレット状のマレイミド系共重合体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３に示す。 <Production example of maleimide copolymer (B-5)>
88 parts by mass of styrene, 1 part by mass of maleic anhydride, 0.09 parts by mass of α-methylstyrene dimer, and 29 parts by mass of methyl ethyl ketone were placed in an autoclave with a capacity of approximately 120 liters equipped with a stirrer, and the gas phase was filled with nitrogen gas. After replacing the mixture with , the temperature was raised to 92° C. over 40 minutes while stirring. After raising the temperature, a solution of 11 parts by mass of maleic anhydride and 0.82 parts by mass of t-butylperoxy-2-ethylhexanoate dissolved in 56 parts by mass of methyl ethyl ketone was heated for 8.5 hours while maintaining the temperature at 92°C. was added continuously. After the addition was completed, the temperature was raised to 120°C, and the reaction was carried out for 1 hour to complete the polymerization. Thereafter, 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 10 hours. After the reaction was completed, the imidization reaction solution was charged into a vent type screw extruder to remove volatile components to obtain maleimide copolymer B-5 in the form of pellets. Table 3 shows the analysis results of the obtained maleimide copolymer.
　＜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７質量部、アクリロニトリル４０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０．５７質量部、メチルエチルケトン３４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４０質量部及びマレイン酸無水物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０．２１質量部をメチルエチルケトン５５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０．１４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１０質量部、トリエチルアミン０．２質量部を加え１４０℃で１０時間反応させた。反応終了後のイミド化反応液をベントタイプスクリュー式押出機に投入し、揮発分を除去してペレット状のマレイミド系共重合体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３に示す。 <Production example of maleimide copolymer (B-6)>
In an autoclave with a capacity of about 120 liters equipped with a stirrer, 7 parts by mass of styrene, 40 parts by mass of acrylonitrile, 2 parts by mass of maleic anhydride, 0.57 parts by mass of α-methylstyrene dimer, and 34 parts by mass of methyl ethyl ketone were charged. After replacing the phase with nitrogen gas, the temperature was raised to 92° C. over 40 minutes while stirring. After raising the temperature, a solution of 40 parts by mass of styrene, 11 parts by mass of maleic anhydride, and 0.21 parts by mass of t-butylperoxy-2-ethylhexanoate dissolved in 55 parts by mass of methyl ethyl ketone was prepared while maintaining the temperature at 92°C. The addition was continued over a period of 3 hours. Furthermore, after the addition of maleic anhydride was completed, a solution of 0.14 parts by mass of t-butylperoxy-2-ethylhexanoate dissolved in 1 part 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. Thereafter, 10 parts by mass of aniline and 0.2 parts by mass of triethylamine were added to the polymerization solution, and the mixture was reacted at 140° C. for 10 hours. After the completion of the reaction, the imidization reaction solution was charged into a vent type screw extruder, and volatile components were removed to obtain maleimide copolymer B-6 in the form of pellets. Table 3 shows the analysis results of the obtained maleimide copolymer.
　＜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１０時間反応させた。反応終了後のイミド化反応液をベントタイプスクリュー式押出機に投入し、揮発分を除去してペレット状のマレイミド系共重合体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３に示す。 <Production example of maleimide copolymer (B-7)>
77 parts by mass of styrene, 19 parts by mass of acrylonitrile, 1 part by mass of maleic anhydride, and 25 parts by mass of methyl ethyl ketone were placed in an autoclave with a volume of approximately 120 liters equipped with a stirrer, and after replacing the gas phase with nitrogen gas, the mixture was stirred. The temperature was raised to 92°C over 40 minutes. After raising the temperature, a solution of 3 parts by mass of maleic anhydride and 0.82 parts by mass of t-butylperoxy-2-ethylhexanoate dissolved in 23 parts by mass of methyl ethyl ketone was heated over 4.5 hours while maintaining the temperature at 92°C. was added continuously. Furthermore, after the addition of maleic anhydride was completed, a solution of 0.18 parts by mass of t-butylperoxy-2-ethylhexanoate dissolved 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. Thereafter, 2 parts by mass of aniline and 0.1 parts by mass of triethylamine were added to the polymerization solution, and the mixture was reacted at 140° C. for 10 hours. After the reaction was completed, the imidization reaction solution was put into a vent type screw extruder to remove volatile components to obtain pellet-shaped maleimide copolymer B-7. Table 3 shows the analysis results of the obtained maleimide copolymer.
　＜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０．２３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１０時間反応させた。反応終了後のイミド化反応液をベントタイプスクリュー式押出機に投入し、揮発分を除去してペレット状のマレイミド系共重合体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３に示す。 <Production example of maleimide copolymer (B-8)>
In an autoclave with a capacity of approximately 120 liters equipped with a stirrer, 22 parts by mass of styrene, 10 parts by mass of acrylonitrile, 3 parts by mass of maleic anhydride, 0.23 parts by mass of α-methylstyrene dimer, and 39 parts by mass of methyl ethyl ketone were charged. After replacing the phase with nitrogen gas, the temperature was raised to 92° C. over 40 minutes while stirring. After raising the temperature, a solution of 41 parts by mass of styrene, 23 parts by mass of maleic anhydride, and 0.42 parts by mass of t-butylperoxy-2-ethylhexanoate dissolved in 116 parts by mass of methyl ethyl ketone was prepared while maintaining the temperature at 92°C. The addition was continued over a period of 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. Thereafter, 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 10 hours. After the completion of the reaction, the imidization reaction solution was charged into a vent type screw extruder to remove volatile components to obtain pellet-shaped maleimide copolymer B-8. Table 3 shows the analysis results of the obtained maleimide copolymer.
　＜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０．８０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１０時間反応させた。反応終了後のイミド化反応液をベントタイプスクリュー式押出機に投入し、揮発分を除去してペレット状のマレイミド系共重合体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３に示す。 <Production example of maleimide copolymer (B-9)>
In an autoclave with a capacity of approximately 120 liters equipped with a stirrer, 84 parts by mass of styrene, 12 parts by mass of acrylonitrile, 1 part by mass of maleic anhydride, 0.80 parts by mass of α-methylstyrene dimer, and 26 parts by mass of methyl ethyl ketone were charged. After replacing the phase with nitrogen gas, the temperature was raised to 92° C. over 40 minutes while stirring. After raising the temperature, a solution of 3 parts by mass of maleic anhydride and 0.82 parts by mass of t-butylperoxy-2-ethylhexanoate dissolved in 24 parts by mass of methyl ethyl ketone was heated for 4.5 hours while maintaining the temperature at 92°C. was added continuously. Furthermore, after the addition of maleic anhydride was completed, a solution of 0.18 parts by mass of t-butylperoxy-2-ethylhexanoate dissolved 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. Thereafter, 3 parts by mass of aniline and 0.1 parts by mass of triethylamine were added to the polymerization solution, and the mixture was reacted at 140° C. for 10 hours. After the completion of the reaction, the imidization reaction solution was charged into a vent type screw extruder to remove volatile components to obtain pellet-shaped maleimide copolymer B-9. Table 3 shows the analysis results of the obtained maleimide copolymer.
＜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
・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－１４、Ｂ－１～Ｂ－９）を使用した。
（３）添加剤
・Ｓｎ系安定剤：ＴＶＳ＃８８３２（日東化成社製）を使用した。
・滑剤（ステアリン酸）：ステアリン酸さくら（日本油脂社製）を使用した。
・衝撃改質剤（ＭＢＳ）：メタブレンＣ－２２３Ａ（三菱ケミカル）を使用した。
・衝撃改質剤（塩素化ＰＥ）：エラスレン３０１Ａ（昭和電工社製）を使用した。
・衝撃改質剤（アクリルゴム）：カネエースＦＭ－５０（カネカ社製）を使用した。 <Resin composition>
(Raw materials used) The raw materials used in each example and each comparative example are shown below.
(1) Chlorine-containing polymer, product name: TH-1000 (manufactured by Taiyo PVC Co., Ltd.) was used.
(2) Maleimide copolymers (A-1 to A-14, B-1 to B-9) obtained according to the above production examples were used.
(3) Additive/Sn stabilizer: TVS #8832 (manufactured by Nitto Kasei Co., Ltd.) was used.
- Lubricant (stearic acid): Sakura Stearate (manufactured by Nihon Yushi Corporation) was used.
- Impact modifier (MBS): Metablane C-223A (Mitsubishi Chemical) was used.
-Impact modifier (chlorinated PE): Elasthren 301A (manufactured by Showa Denko) was used.
- Impact modifier (acrylic rubber): Kane Ace FM-50 (manufactured by Kaneka Corporation) was used.
　＜実施例１～１６、比較例１～９＞（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－１４、Ｂ－１～Ｂ－９、衝撃改質剤と、あらかじめ安定剤、滑剤を加えてヘンシェルミキサーで混合した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１～３に示した配合割合でブレンドした後、テストロール（φ６×Ｌ１５テストロール、関西ロール社製）を用いて樹脂組成物の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。 <Examples 1 to 16, Comparative Examples 1 to 9> (Kneading and mixing of maleimide copolymer and chlorine-containing polymer)
Maleimide copolymers A-1 to A-14, B-1 to B-9, impact modifiers, and stabilizers and lubricants were added in advance and mixed in a Henschel mixer to commercially available chlorine-containing polymers (products). name: TH-1000, manufactured by Taiyo PVC Co., Ltd.) at the blending ratio shown in Tables 1 to 3, and then using a test roll (φ6 x L15 test roll, manufactured by Kansai Roll Co., Ltd.) to form a roll sheet of the resin composition. was prepared, rolled sheets were piled up and press-formed, and test pieces were prepared by cutting or punching, and each physical property value was measured. The results are shown in Tables 1 and 2.
（組成分析）
マレイミド系共重合体における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 compositional analysis of each monomer unit in the maleimide copolymer was measured by C-13 NMR method under the measurement conditions described below.
Equipment name: FT-NMR AVANCE300 (manufactured by BRUKER)
Solvent: Deuterated chloroform Concentration: 14% by mass
Temperature: 27℃
Accumulated number of times: 8000 times
（重量平均分子量）
　マレイミド系共重合体の重量平均分子量（Ｍｗ）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、次の条件で測定した。
　　装置名：ＳＹＳＴＥＭ－２１　Ｓｈｏｄｅｘ（昭和電工株式会社製）
　　カラム：ＰＬ　ｇｅｌ　ＭＩＸＥＤ－Ｂ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）（ＰＬ社製）を用いて作製した。 (Weight average molecular weight)
The weight average molecular weight (Mw) of the maleimide copolymer is a polystyrene equivalent value measured by gel permeation chromatography (GPC), and was measured under the following conditions.
Equipment name: SYSTEM-21 Shodex (manufactured by Showa Denko K.K.)
Column: 3 PL gel MIXED-B in series Temperature: 40℃
Detection: Differential refractive index Solvent: Tetrahydrofuran Concentration: 2% by mass
Calibration curve: Prepared using standard polystyrene (PS) (manufactured by PL).
（溶融粘度）
　マレイミド系共重合体の溶融粘度は、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。 (melt viscosity)
The melt viscosity of the maleimide copolymer 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 device used was a capillary rheometer 1D manufactured by Toyo Seiki Seisakusho Co., Ltd.
（酸価）
　マレイミド系共重合体の酸価は、ＪＩＳ　Ｋ００７０に準拠して、マレイミド系共重合体１ｇをメチルエチルケトン５０ｍＬに溶解し、１．０ｗ／ｖ％フェノールフタレインエタノール溶液を１ｍＬを加えた溶液を、０．１ｍｏｌ／Ｌエタノール性水酸化カリウム溶液で中和滴定し、下記の式で計算することにより測定した。
　酸価（ｍｇ／ｇ）＝（滴定量（ｍＬ）－ブランク量（ｍＬ））×水酸化カリウム濃度（ｍｏｌ／Ｌ）×５６．１１（水酸化カリウムモル質量ｇ／ｍｏｌ）／マレイミド系共重合体量（ｇ） (Acid value)
The acid value of the maleimide copolymer is determined according to JIS K0070 by dissolving 1 g of the maleimide copolymer in 50 mL of methyl ethyl ketone and adding 1 mL of a 1.0 w/v% phenolphthalein ethanol solution. It was measured by neutralization titration with .1 mol/L ethanolic potassium hydroxide solution and calculation using the following formula.
Acid value (mg/g) = (titration amount (mL) - blank amount (mL)) x potassium hydroxide concentration (mol/L) x 56.11 (potassium hydroxide molar mass g/mol)/maleimide copolymer Combined amount (g)
（ロール混練時の張り付き）
　耐熱付与剤のロール混練時の張り付きは、塩素含有ポリマー用耐熱付与剤、Ｓｎ系安定剤としてのＴＶＳ＃８８３２、その他添加剤、及び塩素含有ポリマーをロール混練する際の樹脂組成物のテストロールへの張り付きを目視で観察し、以下の判断基準に基づき評価した。
　◎（優れる）：　ロールへの樹脂組成物の張り付きは、塩素含有ポリマー用耐熱付与剤を添加しない場合と同等
　○（良好）：　ロールへの樹脂組成物の張り付きは、塩素含有ポリマー用耐熱付与剤を添加しない場合と比較して強くなるが、ロールシートを回収できる程度
　×（劣る）：　ロールへの樹脂組成物の張り付きが強くなり、ロールシートがはがれない (Sticking during roll kneading)
Sticking of the heat resistance imparting agent during roll kneading is determined by using the heat resistance imparting agent for chlorine-containing polymers, TVS #8832 as a Sn-based stabilizer, other additives, and the test roll of the resin composition when roll-kneading chlorine-containing polymers. The adhesion was visually observed and evaluated based on the following criteria.
◎ (Excellent): The adhesion of the resin composition to the roll is the same as when the heat resistance imparting agent for chlorine-containing polymers is not added. ○ (Good): The adhesion of the resin composition to the roll is the same as when the heat resistance imparting agent for chlorine-containing polymers is not added. It is stronger than when not adding, but to the extent that the rolled sheet can be recovered × (inferior): The resin composition sticks to the roll so strongly that the rolled sheet cannot be peeled off.
（シャルピー衝撃強度）
　耐熱付与剤のシャルピー衝撃強度は、ＪＩＳ　Ｋ－７１１１に準拠して、ノッチあり試験片を用い、打撃方向はエッジワイズを採用して相対湿度５０％、雰囲気温度２３℃の条件で測定した。なお、測定機は東洋精機製作所社製デジタル衝撃試験機を使用した。 (Charpy impact strength)
The Charpy impact strength of the heat resistance imparting agent was measured in accordance with JIS K-7111 using a notched test piece and using an edgewise impact direction at a relative humidity of 50% and an ambient temperature of 23°C. The measuring device used was a digital impact tester manufactured by Toyo Seiki Seisakusho.
（ビカット軟化温度）
　耐熱付与剤のビカット軟化温度は、ＪＩＳ　Ｋ７２０６：１９９９に基づき、Ｂ５０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 temperature)
The Vicat softening temperature of the heat resistance imparting agent was measured based on JIS K7206:1999 using the B50 method (load 50 N, temperature increase rate 50° C./hour) using a test piece of 20 mm x 20 mm and 4 mm thickness. The measuring device used was an HDT & VSPT testing device manufactured by Toyo Seiki Seisakusho.
　本発明にかかる塩素含有ポリマー用耐熱付与剤を用いた実施例１～１６では、樹脂組成物の耐熱性及び衝撃強度のバランスが十分に向上されていた。さらに、Ｓｎ系安定剤を配合した場合においても、塩素含有ポリマー用耐熱付与剤と塩素含有ポリマーとのロール混練工程において樹脂組成物のロールへの張り付きがあまりなかった。
　これに対し、本発明の規定を満たさない塩素含有ポリマー用耐熱付与剤を用いた比較例１～９では、樹脂組成物の耐熱性又は衝撃強度が十分に向上されないものがあった。また、Ｓｎ系安定剤を配合した場合において、塩素含有ポリマー用耐熱付与剤と塩素含有ポリマーとのロール混練工程において樹脂組成物のロールへの張り付きが強くなるものや、溶融混練できないものもあった。 In Examples 1 to 16 using the heat resistance imparting agent for chlorine-containing polymers according to the present invention, the balance between heat resistance and impact strength of the resin compositions was sufficiently improved. Furthermore, even when the Sn-based stabilizer was blended, the resin composition did not stick much to the roll during the roll kneading process of the heat resistance imparting agent for chlorine-containing polymer and the chlorine-containing polymer.
On the other hand, in Comparative Examples 1 to 9 using heat resistance imparting agents for chlorine-containing polymers that do not meet the specifications of the present invention, the heat resistance or impact strength of the resin compositions was not sufficiently improved in some cases. In addition, when Sn-based stabilizers were blended, in some cases the resin composition stuck to the rolls strongly during the roll kneading process of the heat resistance imparting agent for chlorine-containing polymers and the chlorine-containing polymer, and in some cases it was impossible to melt-knead the resin composition. .
　本発明により、塩素含有ポリマーの耐熱性及び衝撃強度のバランスを向上しつつ、Ｓｎ系安定剤を配合した場合においても、塩素含有ポリマー用耐熱付与剤と塩素含有ポリマーとのロール混練工程において樹脂組成物のロールへの張り付きを低減できる塩素含有ポリマー用耐熱付与剤が提供され、雨どい、雨どい部品、建具用形材、パイプ及び継手の用途に好適に利用される。 According to the present invention, the balance between heat resistance and impact strength of the chlorine-containing polymer is improved, and even when an Sn-based stabilizer is blended, the resin composition is A heat resistance imparting agent for chlorine-containing polymers that can reduce the sticking of objects to rolls is provided, and is suitably used for rain gutters, rain gutter parts, fitting shapes, pipes, and joints.

Claims (7)

  1. 　少なくとも芳香族ビニル系単量体単位、シアン化ビニル系単量体単位及びマレイミド系単量体単位を有するマレイミド系共重合体を含む塩素含有ポリマー用耐熱付与剤であり、
    　前記マレイミド系共重合体は、前記マレイミド系共重合体に含有される単量体単位の合計を１００質量％とした場合に、
    　　前記芳香族ビニル系単量体単位４０～９０質量％と、
    　　前記シアン化ビニル系単量体単位０．５～３０質量％と、
    　　前記マレイミド系単量体単位５～３０質量％と
    を含み、
    　前記マレイミド系共重合体の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、酸価が０～１１ｍｇ／ｇである、
    塩素含有ポリマー用耐熱付与剤。     A heat resistance imparting agent for chlorine-containing polymers comprising a maleimide copolymer having at least an aromatic vinyl monomer unit, a vinyl cyanide monomer unit, and a maleimide monomer unit,
    The maleimide copolymer has 100% by mass of the total monomer units contained in the maleimide copolymer,
    40 to 90% by mass of the aromatic vinyl monomer unit,
    0.5 to 30% by mass of the vinyl cyanide monomer unit,
    5 to 30% by mass of the maleimide monomer unit,
    The maleimide copolymer has a melt viscosity of 200 to 100,000 Pa·sec measured at 190° C. and a shear rate of 100/sec, and an acid value of 0 to 11 mg/g.
    Heat resistance imparting agent for chlorine-containing polymers.
  2. 　前記マレイミド系共重合体が、酸基を有する単量体単位をさらに含み、前記酸基を有する単量体単位が、不飽和酸無水物単量体単位、（メタ）アクリル酸単量体単位からなる群から選ばれる少なくとも一種である、請求項１に記載の塩素含有ポリマー用耐熱付与剤。 The maleimide copolymer further includes a monomer unit having an acid group, and the monomer unit having an acid group is an unsaturated acid anhydride monomer unit or a (meth)acrylic acid monomer unit. The heat resistance imparting agent for chlorine-containing polymers according to claim 1, which is at least one selected from the group consisting of:
  3. 　前記酸基を有する単量体単位が、マレイン酸無水物単量体単位である、請求項２に記載の塩素含有ポリマー用耐熱付与剤。 The heat resistance imparting agent for chlorine-containing polymers according to claim 2, wherein the monomer unit having an acid group is a maleic anhydride monomer unit.
  4. 　前記マレイミド系共重合体の重量平均分子量が、３～１２万である、請求項１に記載の塩素含有ポリマー用耐熱付与剤。 The heat resistance imparting agent for chlorine-containing polymers according to claim 1, wherein the maleimide copolymer has a weight average molecular weight of 30,000 to 120,000.
  5. 　請求項１～請求項４のいずれか一項に記載の塩素含有ポリマー用耐熱付与剤と、塩素含有ポリマーを含有する樹脂組成物。 A resin composition containing the heat resistance imparting agent for chlorine-containing polymers according to any one of claims 1 to 4 and a chlorine-containing polymer.
  6. 　請求項５に記載の樹脂組成物を用いた成形体。 A molded article using the resin composition according to claim 5.
  7. 　雨どい、雨どい部品、建具用形材、パイプ及び継手として使用される請求項６に記載の成形体。 The molded article according to claim 6, which is used as a rain gutter, a rain gutter component, a shape for fittings, a pipe, and a joint.
PCT/JP2023/013575 2022-03-31 2023-03-31 Heat-resistance imparter for chlorinated polymers, resin composition, and molded object formed from said resin composition WO2023191064A1 (en)

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Citations (7)

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

Patent Citations (7)

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

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