TW202402837A - Heat-resistance imparter for chlorinated polymers, resin composition, and molded object formed from said resin composition - Google Patents

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 DEG C and a shear rate of 100 /sec, of 200-100,000 Pa.sec and an acid value of 0-11 mg/g.

Description

Heat resistance imparting agent for chlorine-containing polymers, resin composition, and molded article molded from the resin composition

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 represented by polyvinyl chloride or chlorinated polyvinyl chloride are mass-produced and used for various purposes due to their low price and excellent chemical, physical and mechanical properties. However, polyvinyl chloride has the disadvantage of insufficient heat resistance (thermal softening temperature). For example, based on JIS K7206: 1999, the Vickers softening temperature measured by the B50 method (load 50 N, heating rate 50°C/hour) is 82°C. Around 10%, and the softening temperature will be further reduced due to the stabilizers and plasticizers usually prepared during forming processing. As a method of improving the heat resistance of polyvinyl chloride, a method of mixing a heat-resistant resin and polyvinyl chloride is known (Patent Documents 1 to 4). [Prior technical literature] [Patent Document]

[Patent Document 1] Japanese Patent No. 06475501 [Patent Document 2] Japanese Patent Application Publication No. 2006-265373 [Patent Document 3] International Publication No. WO2022/039098 [Patent Document 4] International Publication No. WO2022/039099

[Problem to be solved by the invention]

The present invention aims to provide a heat-resistant imparting agent for chlorine-containing polymers, which can improve the balance between heat resistance and impact strength of chlorine-containing polymers, and can also improve the performance of chlorine-containing polymers even when a Sn-based stabilizer is blended. In the roller kneading step of the resin composition of the heat-resistant imparting agent and the chlorine-containing polymer, the adhesion of the resin composition to the roller is reduced. [Technical means to solve problems]

The inventors of the present invention conducted research and found that when a resin composition is obtained by containing a heat resistance-imparting agent for chlorine-containing polymers in a chlorine-containing polymer, an excellent balance between heat resistance and impact strength can be achieved. The heat-resistant imparting agent for polymers contains a maleimide copolymer with a specific monomer unit composition, a melt viscosity and an acid value within a specific range. Furthermore, the present inventors have found that even when a Sn-based stabilizer is blended with the heat-resistant imparting agent for chlorine-containing polymers, the heat-resistant imparting agent for chlorine-containing polymers and the chlorine-containing polymer can be combined with a resin. The present invention was completed by reducing the adhesion of the resin composition to the roller during the roller kneading step of the product. That is, the present invention relates to the following contents. [1] A heat resistance imparting agent for chlorine-containing polymers, which contains male butene having at least an aromatic vinyl monomer unit, a vinyl cyanide monomer unit, and a maleic imine monomer unit. Diamine copolymers, When the total number of monomer units contained in the above-mentioned maleimine copolymer is 100% by mass, the above-mentioned maleimine copolymer contains: 40 to 90% by mass of the above aromatic vinyl monomer units, 0.5 to 30% by mass of the above vinyl cyanide monomer unit, and The above-mentioned maleic imine monomer unit is 5 to 30% by mass, and The melt viscosity of the above-mentioned maleimide copolymer measured at 190°C and a shear rate of 100/sec is 200 to 100000 Pa·sec, and the acid value is 0 to 11 mg/g. [2] The heat resistance-imparting agent for chlorine-containing polymers according to [1], wherein the maleimide copolymer further contains a monomer unit having an acid group, and the monomer unit having an acid group is At least one selected from the group consisting of unsaturated acid anhydride monomer units and (meth)acrylic acid monomer 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 weight average molecular weight of the maleic imine copolymer is 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 described in [5]. [7] The molded article described in [6] is used as rain gutters, rain gutter parts, profiles for doors and windows, pipes and joints. [Effects of the invention]

If the heat resistance imparting agent for chlorine-containing polymers of the present invention is used, the balance between heat resistance and impact strength of the chlorine-containing polymer can be improved. Furthermore, even when a Sn-based stabilizer is blended, adhesion of the resin composition to the roll can be reduced in the roll kneading step of the resin composition containing the heat resistance imparting agent for chlorine-containing polymer and the chlorine-containing polymer.

＜Explanation of terminology＞ In the description of this case, the description "A～B" means above A and below B.

Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited to this, and various changes can be made without departing from the gist of the invention. Various features disclosed in the embodiments shown below can be combined with each other. In addition, each characteristic matter independently constitutes the invention.

＜Monomer units contained in maleimide copolymer＞ The maleic imine copolymer contained in the heat resistance-imparting agent for chlorine-containing polymers according to the present embodiment contains at least aromatic vinyl monomer units, vinyl cyanide monomer units, and maleic imine copolymers. Imide monomer unit. Moreover, you may further contain the monomer unit which has an acid group. The monomer units contained in the maleimide copolymer will be described below.

＜Aromatic vinyl monomer unit＞ Examples of the aromatic vinyl monomer 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-methyl Styrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, ethylstyrene, p-tert-butylstyrene, α-methylstyrene, α-methylp-methylstyrene Methyl styrene etc. Among these, styrene is preferred. In addition, if it is styrene, the balance between heat resistance, affinity with chlorine-containing polymers, and fluidity can be further improved. The aromatic vinyl monomer unit may be used alone, or two or more types may be used in combination.

Regarding the maleic imine copolymer contained in the heat resistance imparting agent for chlorine-containing polymers of the present embodiment, the total design of the monomer units contained in the maleic imine copolymer is In the case of 100% by mass, the aromatic vinyl monomer units are contained in an amount of 40 to 90% by mass, preferably 50 to 85% by mass, and further preferably 60 to 80% by mass. Specifically, it is, for example, 40, 50, 60, 65, 68, 70, 72, 75, 80, 85, or 90% by mass, or it may be in a range between any two of the numerical values illustrated here. If the amount of aromatic vinyl monomer units is less than 40% by mass, the other monomer components contained in the maleimine copolymer will relatively increase, resulting in maleimine copolymerization. The content does not melt with the chlorine-containing polymer and cannot be kneaded. If it exceeds 90% by mass, the heat resistance of the resin composition may not be sufficiently improved. Moreover, if it is within this range, the balance of heat resistance, affinity with a chlorine-containing polymer, and fluidity can be further improved. In addition, when aromatic vinyl-based monomer units are used together, the content of aromatic vinyl-based monomer units means the total amount of aromatic vinyl-based monomer units used together.

＜Cyanide vinyl 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 and methacrylonitrile. , ethacrylonitrile, fumaronitrile, etc. Among these, acrylonitrile is preferred from the viewpoint of imparting heat resistance to the resin composition. In addition, if it is acrylonitrile, the balance between heat resistance, affinity with chlorine-containing polymers, and fluidity can be further improved. The vinyl cyanide-based monomer unit may be used alone, or two or more types may be used in combination.

Regarding the maleic imine copolymer contained in the heat resistance imparting agent for chlorine-containing polymers of the present embodiment, the total design of the monomer units contained in the maleic imine copolymer is When it is 100 mass %, it contains 0.5-30 mass % of vinyl cyanide monomer units, Preferably it contains 0.5-20 mass %, More preferably, it contains 0.5-15 mass %. Specifically, it is, for example, 0.5, 1, 5, 6, 7, 8, 9, 10, 15, 20, 25, or 30% by mass, or it may be in a range between any two of the numerical values illustrated here. . By setting the amount of vinyl cyanide-based monomer units to 0.5 mass % or more, the heat resistance of the resin composition can be fully improved, and by setting it to 30 mass % or less, the impact resistance and heat resistance of the resin composition can be improved. balance. Moreover, if it is within this range, the balance of heat resistance, affinity with a chlorine-containing polymer, and fluidity can be further improved. In addition, when vinyl cyanide-based monomer units are used together, the content of vinyl cyanide-based monomer units means the total amount of vinyl cyanide-based monomer units used together.

＜Maleimide monomer unit＞ Examples of maleimine monomer units that can be used in the maleimine copolymer contained in the heat resistance imparting agent for chlorine-containing polymers according to this embodiment include: N-methyl N-alkyl maleimides such as maleimide, N-butylmaleimide, N-cyclohexylmaleimide, and N-phenylmaleimine Diamine, N-chlorophenylmaleimide, N-methylphenylmaleimide, N-methoxyphenylmaleimide, N-triamine Bromophenylmaleimide and other N-arylmaleimide and so on. Among these, from the viewpoint of imparting heat resistance to the resin composition, N-arylmaleimide is preferred, and N-phenylmaleimide is further preferred. In addition, if it is N-phenylmaleimide, the rigidity may also be improved. The maleimide monomer unit may be used alone, or two or more types may be used in combination. In order to make the maleimine copolymer contain maleimine monomer units, for example, a raw material containing unsaturated dicarboxylic acid monomer units and other monomers may be copolymerized using ammonia or a primary amine. The resulting copolymer can be imidized. Alternatively, a raw material containing a maleimine monomer and other monomers may be copolymerized.

Regarding the maleic imine copolymer contained in the heat resistance imparting agent for chlorine-containing polymers of the present embodiment, the total design of the monomer units contained in the maleic imine copolymer is When it is 100 mass %, it contains 5-30 mass % of maleimide monomer units, Preferably it contains 10-30 mass %, More preferably, it contains 15-30 mass %. Specifically, it is, for example, 5, 10, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, or 30% by mass, or any two of the numerical values illustrated here. within the range. By setting the amount of maleimide-based monomer units to 5 mass % or more, the heat resistance of the resin composition can be sufficiently improved, and by setting it to 30 mass % or less, the heat resistance of the chlorine-containing polymer can be suppressed. The imparting agent does not melt with the chlorine-containing polymer and cannot be kneaded. Moreover, if it is within this range, the balance of heat resistance, affinity with a chlorine-containing polymer, and fluidity can be further improved. In addition, when maleimine monomer units are used together, the content of maleimine monomer units means the total number of maleimine monomer units used together. quantity.

＜Monomer unit having acid group＞ The maleic imine copolymer contained in the heat resistance-imparting agent for chlorine-containing polymers of the present embodiment may further contain other copolymerizable monomer units having an acid group (also referred to as " Monomeric units with acidic groups"). Examples of the acid group here include a carboxyl group and a group having an acid anhydride structure. Examples of monomer units having an acid group that can be used in the maleimide copolymer contained in the heat-resistant imparting agent for chlorine-containing polymers according to the present embodiment include unsaturated acid anhydride monomer units, ( Meth)acrylic acid monomer unit. The monomer unit having an acid group may be used alone, or two or more types may be used in combination.

Regarding the maleic imine copolymer contained in the heat resistance imparting agent for chlorine-containing polymers of the present embodiment, the total design of the monomer units contained in the maleic imine copolymer is When it is 100 mass %, it is preferable that it contains 0-2.0 mass % of the monomer unit which has an acid group, and it is more preferable that it contains 0-1.5 mass %. Specifically, it is, 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, or any two of the numerical values illustrated here. within the range. By setting the content of the unsaturated acid anhydride monomer unit to 2.0% by mass or less, the balance between the heat resistance and impact strength of the resin composition and the processability (adhesion to the roll) during roll kneading is improved. Moreover, if it is within this range, the balance of heat resistance, affinity with a chlorine-containing polymer, 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.

＜Unsaturated acid anhydride monomer unit＞ Examples of the unsaturated acid anhydride monomer unit that can be used in the maleic imine copolymer contained in the heat resistance-imparting agent for chlorine-containing polymers according to the present embodiment include maleic anhydride and Ikon. Anhydride, citraconic anhydride, aconitic anhydride, etc. Among these, maleic anhydride is preferred from the viewpoint of imparting heat resistance to the resin composition. Moreover, if it is maleic anhydride, the balance of heat resistance, affinity with a chlorine-containing polymer, and fluidity can be further improved. The unsaturated acid anhydride monomer unit may be used alone, or two or more types may be used in combination.

Regarding the maleic imine copolymer contained in the heat resistance imparting agent for chlorine-containing polymers of the present embodiment, the total design of the monomer units contained in the maleic imine copolymer is When it is 100 mass %, it is preferable that it contains 0-1.5 mass % of unsaturated acid anhydride monomer units, and it is more preferable that it contains 0-1.0 mass %. Specifically, it is, for example, 0, 0.2, 0.4, 0.6, 0.8, 1.0, 1.2, 1.4, or 1.5% by mass, or it may be in a range between any two of the numerical values illustrated here. By setting the content of the unsaturated acid anhydride monomer unit to 1.5% by mass or less, the balance between the heat resistance and impact strength of the resin composition and the processability (adhesion to the roll) during roll kneading is improved. Moreover, if it is within this range, the balance of heat resistance, affinity with a chlorine-containing polymer, and fluidity can be further improved. In addition, when unsaturated acid anhydride monomer units are used together, the content of unsaturated acid anhydride monomer units means the total amount of unsaturated acid anhydride monomer units used together.

＜(Meth)acrylic acid monomer unit＞ Examples of the (meth)acrylic acid monomer unit that can be used in the maleimide copolymer contained in the heat-resistant 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.

Regarding the maleic imine copolymer contained in the heat resistance imparting agent for chlorine-containing polymers of the present embodiment, the total design of the monomer units contained in the maleic imine copolymer is When it is 100 mass %, it is preferable that it contains 0-1.5 mass % of (meth)acrylic acid monomer units, and it is more preferable that it contains 0-1.0 mass %. Specifically, it is, for example, 0, 0.2, 0.4, 0.6, 0.8, 1.0, 1.2, 1.4, or 1.5% by mass, or it may be in a range between any two of the numerical values illustrated here. By setting the content of the (meth)acrylic acid monomer unit to 1.5% by mass or less, the balance between heat resistance and impact strength of the resin composition is improved. Moreover, if it is within this range, the balance of heat resistance, affinity with a chlorine-containing polymer, and fluidity can be further improved. In addition, when a (meth)acrylic acid monomer unit is used together, the content of a (meth)acrylic acid monomer unit means the total amount of the (meth)acrylic acid monomer unit used together.

<Monomers that can be copolymerized> Methacrylates such as ethyl methacrylate The maleic imine copolymer contained in the heat resistance-imparting agent for chlorine-containing polymers of the present embodiment can also be used in addition to aromatic vinyl monomers and nitrile vinyl within the range that does not hinder the effects of the present invention. copolymerization of copolymerizable monomers other than monomers based on maleic acid groups, maleimide-based monomers, and monomer units having acidic groups. Examples of the monomer copolymerizable with the maleimide copolymer include acrylate monomers such as methyl acrylate, ethyl acrylate, and butyl acrylate, methyl methacrylate, and ethyl methacrylate. Methacrylate monomer, acrylamide and methacrylamide, etc. The monomer copolymerizable with 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 hinder the effects of the present invention. From the viewpoint of imparting heat resistance to the resin composition, the total number of monomer units contained in the maleimide copolymer is When it is 100 mass %, it is preferable that it is 20 mass % or less, and it is further more preferable that it is 10 mass % or less.

＜Additive＞ 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 inhibit the effects of the present invention. After the polymerization of the maleimide copolymer is completed, heat-resistant stabilizers such as hindered phenol compounds, lactone compounds, phosphorus compounds, and sulfur compounds, hindered amine compounds, benzene compounds, etc. may also be added to the polymerization solution as needed. Additives such as light stabilizers such as triazole compounds, lubricants or plasticizers, colorants, antistatic agents, and mineral oils. The added amount is preferably less than 0.3 parts by mass relative to 100 parts by mass of the maleimide copolymer. These additives may be used individually or in combination of 2 or more types. In one embodiment, the heat resistance imparting agent for chlorine-containing polymers may be substantially composed of a maleimide copolymer. Furthermore, in other embodiments, the heat resistance-imparting agent for chlorine-containing polymers may be composed of a maleimide copolymer.

＜Physical properties of maleimide copolymer＞ ＜Melt viscosity of maleimide copolymer＞ The melt viscosity of the maleimide copolymer contained in the heat-resistant imparting agent for chlorine-containing polymers of the present embodiment is 200 to 100,000 Pa·sec, preferably 200 to 70,000 Pa·sec, and more preferably It is 500~70000 Pa·sec. Specifically, it is, for example, 200, 500, 1000, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, 10000, 20000, 30000, 40000, 50000, or 100000 Pa·sec. It may also be exemplified here. is within the range between any two values. By setting the temperature to 200 Pa·sec or more, the heat resistance of the resin composition can be sufficiently improved, and by setting the temperature to 100,000 Pa·sec or less, the heat resistance-imparting agent for chlorine-containing polymers can be suppressed from not melting with the chlorine-containing polymer. Mixed training situation. Moreover, if it is within this range, the dispersibility of the heat resistance-imparting agent for chlorine-containing polymers in the chlorine-containing polymer can also be improved. The melt viscosity was measured using a capillary rheometer 1D manufactured by Toyo Seiki Seisakusho Co., Ltd. using a capillary die with L = 40 mm and D = 1 mm.

The melt viscosity of the maleic imine copolymer contained in the heat resistance imparting agent for chlorine-containing polymers of the present embodiment can be adjusted by adjusting the formulation of the monomer units constituting the maleic imine copolymer. To control. For example, by increasing the content of vinyl cyanide monomer units in the maleimine copolymer or increasing the maleimine monomer units in the maleimine copolymer. The content can increase the melt viscosity. Furthermore, by increasing the weight average molecular weight of the maleimide copolymer, the melt viscosity can also be increased. These adjustment methods can be used together.

＜Acid value of maleimide copolymer＞ The acid value of the maleimide copolymer contained in the heat-resistant imparting agent for chlorine-containing polymers of the present embodiment is 0 to 11 mg/g, preferably 0 to 10 mg/g, and more preferably It is 0~8 mg/g. Specifically, it is, for example, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11 mg/g, or it may be a range between any two of the numerical values illustrated here. within. If the acid value of the maleimide copolymer is within the above range, the resin composition will have an excellent balance between heat resistance, impact strength, and processability during roll kneading (adhesion to the roll). In order to control the acid value of the maleimine copolymer, it can be controlled by adjusting the blending ratio of the monomer units constituting the maleimine copolymer. For example, the acid value can be reduced by reducing the content of unsaturated acid anhydride monomer units or (meth)acrylic acid monomer units in the maleimide copolymer. In addition, in the post-imidation method, the acid value can be reduced by increasing the amount of primary amine added. The acid value can be measured, for example, by dissolving 1 g of maleimide copolymer in 50 mL of methyl ethyl ketone in accordance with JIS K0070, and adding 1.0 w/v% phenolphthalein ethanol solution. 1 mL. For the obtained solution, neutralize and titrate with 0.1 mol/L ethanolic potassium hydroxide solution, and calculate according to the following formula. Acid value (mg/g) = (titer amount (mL) - blank sample volume (mL)) × potassium hydroxide concentration (mol/L) × 56.11 (molar mass of potassium hydroxide g/mol)/male dibutene Amount of imine copolymer (g)

<Weight average molecular weight (Mw) of maleimide copolymer> The weight average molecular weight (Mw) of the maleimide copolymer contained in the heat-resistant imparting agent for chlorine-containing polymers of the present embodiment is preferably 30,000 to 120,000, more preferably 50,000 to 110,000. . Specifically, it is, for example, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 120,000, or it may be in a range between any two of the numerical values illustrated here. When the weight average molecular weight (Mw) of the maleimide copolymer is within the above range, the resin composition will have excellent impact strength. In order to control the weight average molecular weight (Mw) of the maleimide copolymer, in addition to adjusting the polymerization temperature, polymerization time, and the amount of polymerization initiator added, there are also methods such as adjusting the solvent concentration and the amount of chain transfer agent added. . The weight average molecular weight of the maleimide copolymer is a polystyrene converted value measured by gel permeation chromatography (GPC), and can be measured under the following conditions, for example. Device name: SYSTEM-21 Shodex (manufactured by Showa Denko Co., Ltd.) Column: Connect 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 Corporation).

＜Manufacturing of maleimide copolymer＞ The polymerization method of the maleimide copolymer contained in the heat-resistant imparting agent for chlorine-containing polymers according to the present embodiment includes, for example, solution polymerization, block polymerization, and the like. From the viewpoint of obtaining a maleimide-based copolymer with a more uniform copolymerization composition by performing polymerization while performing batch addition or the like, solution polymerization is preferred. The solvent for solution polymerization is preferably non-polymerizable from the viewpoint of being less likely to form by-products and having less adverse effects. Examples include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and acetophenone, ethers such as tetrahydrofuran and 1,4-dioxane, and aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene. , N,N-dimethylformamide, dimethyltrisoxide, N-methyl-2-pyrrolidinone, etc., for easy removal of solvents during devolatization and recovery of maleimide copolymers In terms of properties, methyl ethyl ketone and methyl isobutyl ketone are preferred. The polymerization process can be any of continuous polymerization, batch (batch), and semi-batch.

The method for producing the maleimide copolymer contained in the heat-resistant imparting agent for chlorine-containing polymers of the present embodiment is not particularly limited, but it is preferably obtained by radical polymerization, and the polymerization temperature is relatively high. The preferred range is 80 to 150°C. The polymerization initiator is not particularly limited, and for example, well-known azo compounds such as azobisisobutyronitrile, azobiscyclohexanecarbonitrile, azobismethylpropionitrile, and azobismethylbutyronitrile can be used. Or benzoyl peroxide, tert-butyl peroxybenzoate, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, peroxymonocarbonate O,O -Tertiary butyl-O-isopropyl ester, tert-butyl peroxy 2-ethylhexanoate, di-tert-butyl peroxide, dicumyl peroxide, 3,3-di(tert-butyl peroxide) Well-known organic peroxides such as butyl peroxy)ethyl butyrate can be used alone or in combination of two or more kinds. From the viewpoint of polymerization reaction speed or polymerization rate control, it is preferable to use an azo compound or organic peroxide with a half-life of 70 to 120°C for 10 hours. The usage amount of the polymerization initiator is not particularly limited, but it is preferably 0.1 to 1.5 mass%, more preferably 0.1 to 1.0 mass%, based on 100 mass% of all monomer units. If the usage amount of the polymerization initiator is 0.1% by mass or more, a sufficient polymerization speed can be obtained, so it is preferable. If the usage amount of the polymerization initiator is 1.5% by mass or less, the polymerization speed can be suppressed, so the reaction can be easily controlled and the target molecular weight can be easily obtained.

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 the present embodiment. The chain transfer agent used is not particularly limited, and examples include n-octylmercaptan, n-dodecylmercaptan, tertiary-dodecylmercaptan, α-methylstyrene dimer, sulfur Ethyl glycolate, limonene, terpinene, etc. The amount of chain transfer is not particularly limited as long as it is within the range in which the target molecular weight can be obtained. However, it is preferably 0.01 to 0.8 mass %, and further preferably 0.1 to 0.5 mass % based on 100 mass % of all monomer units. . If the usage amount of the chain transfer agent is 0.01% by mass to 0.8% by mass, the target molecular weight can be easily obtained.

As a method for introducing the maleic imine monomer unit of the maleic imine copolymer contained in the heat resistance imparting agent for chlorine-containing polymers according to the present embodiment, there is the following method: A method of copolymerizing an enedilimide monomer, an aromatic vinyl monomer, and a nitrile vinyl monomer (direct method); or preliminarily making an unsaturated acid anhydride monomer, an aromatic vinyl monomer, and nitrile A method of copolymerizing vinyl monomers and then reacting unsaturated acid anhydride groups with ammonia or primary amine to convert the unsaturated acid anhydride groups into maleimine monomer units (post-imidization method). The post-imidation method is preferable because the amount of residual maleimide monomer in the copolymer is smaller.

Primary amines used in the so-called post-imidation method include, for example, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, n-pentylamine, n-hexylamine, n-octylamine, cyclohexylamine, decylamine and other alkanes. amines and aromatic amines such as chlorine or bromine substituted alkyl amines, aniline, toluidine, naphthylamine, among which aniline and cyclohexylamine are preferred. These primary amines can be used alone or in combination of two or more types. The addition amount of the primary amine is not particularly limited, but it is preferably 0.7 to 1.1 molar equivalents, and more preferably 0.85 to 1.05 molar equivalents based on the unsaturated acid anhydride group. When the amount is 0.7 molar equivalent or more relative to the unsaturated acid anhydride monomer unit in the maleimide copolymer, it is preferable because the thermal stability becomes good. Moreover, if it is 1.1 molar equivalent or less, it is preferable because the amount of the primary amine remaining in the maleimide copolymer will be reduced. Furthermore, if the time of the post-imidization step is prolonged, the content of the unsaturated acid anhydride monomer units in the maleimine copolymer can be reduced.

Catalysts can also be used when introducing maleimide monomer units by post-imidization. The catalyst can promote the dehydration and ring-closure reaction in the reaction between ammonia or primary amine and unsaturated acid anhydride groups, especially the reaction of converting unsaturated acid anhydride groups into maleimide groups. The type of catalyst is not particularly limited, and for example, tertiary amines can be used. The tertiary amine is not particularly limited, and examples thereof include trimethylamine, triethylamine, tripropylamine, tributylamine, N,N-dimethylaniline, N,N-diethylaniline, and the like. The amount of the tertiary amine added is not particularly limited, but is preferably 0.01 molar equivalent or more based on the unsaturated acid anhydride group. The temperature of the imidization reaction in the present invention is preferably 100 to 250°C, and more preferably 120 to 200°C. If the temperature of the imidization reaction is 100° C. or higher, the reaction rate will be sufficiently high, which is preferable in terms of productivity. If the temperature of the imidization reaction is 250° C. or lower, it is preferable because it can suppress the decrease in physical properties caused by thermal deterioration of the maleimide copolymer.

A method for removing volatile components such as solvents used for solution polymerization or unreacted monomers from the solution after solution polymerization of maleimide copolymer or the solution after completion of post-imidization (devolatilization method) Known methods can be used. For example, a vacuum devolatization tank with an attached heater or a devolatilization extruder with a vent can be used. The devolatilized maleimide copolymer in the molten state is transferred to the granulation step and extruded from the porous die in the form of strands. It can be cut by cold cutting, air thermal cutting, or water thermal cutting. Processed into granular form. When the chlorine-containing polymer is in the form of powder, it is preferable to pulverize the maleimide copolymer contained in the resin composition of the present embodiment into a powder form and use it. The grinding method is not particularly limited, and known grinding techniques can be used. As the crushing device that can be suitably used, there are a turbine grinder type grinder, a turbine disk grinder type grinder, a turbine cutter type grinder, a jet mill type grinder, an impact grinder, a hammer grinder, a vibration grinder, Crusher, etc.

＜Chlorine-containing polymer＞ The chlorine-containing polymer contained in the resin composition of this embodiment is a polymer obtained by polymerizing vinyl chloride monomer alone or a mixture of vinyl chloride monomer and one or more monomers copolymerizable therewith, and Chlorine addition polymer is obtained by adding chlorine to the polymer thus obtained. Furthermore, the chlorine-containing polymer may include a complex of the polymer thus obtained and a chlorine addition polymer. Examples of copolymerizable monomers include vinyl esters such as vinyl acetate and vinyl propionate, acrylic esters such as methyl acrylate and butyl acrylate, and methyl esters such as methyl methacrylate and ethyl methacrylate. Acrylates, fumarates such as butyl maleate or diethyl maleate, vinyl ethers such as vinyl methyl ether, vinyl butyl ether and vinyl octyl ether acrylonitriles such as acrylonitrile or methacrylonitrile, α-olefins such as ethylene and propylene, styrenes such as styrene, α-methylstyrene, vinyltoluene, tert-butylstyrene, chlorostyrene and other and its substitutes, vinylidene halides or vinyl halides other than vinyl chloride such as vinylidene chloride or vinyl bromide, and phthalate esters such as diallyl phthalate. From the viewpoint of providing a heat-resistant effect, the chlorine-containing polymer is preferably polyvinyl chloride obtained by polymerizing vinyl chloride monomer.

The average degree of polymerization of the above-mentioned chlorine-containing polymer is 680 to 1900, preferably 700 to 1700. By setting the average degree of polymerization to 680 or more, the maleimine copolymer can be uniformly dispersed, and by setting it to 1,900 or less, the kneadability with the maleimine copolymer can be improved. Excellent.

＜Chlorine content of chlorine-containing polymers＞ The chlorine content rate of the chlorine-containing polymer contained in the resin composition of this embodiment is preferably 50.0 to 60.0%, and more preferably 55.0 to 58.0%. If the chlorine content of the chlorine-containing polymer is within this range, excellent formability and impact resistance can be obtained.

＜Chlorine-containing polymers with high chlorine content＞ The chlorine-containing polymer contained in the resin composition of this embodiment may also contain a chlorine-containing polymer with a higher chlorine content within the range that does not hinder the effect of the present invention. For example, a chlorine-containing polymer having a chlorine content of more than 60.0% may be contained in 100% by mass of the resin composition, preferably less than 70%, more preferably less than 60%, more preferably less than 50%. By controlling the content of the chlorine-containing polymer with a chlorine content exceeding 60.0% within this range, excellent formability and impact resistance can be obtained.

＜Manufacturing of chlorine-containing polymers＞ The polymerization method of the chlorine-containing polymer is not particularly limited, and conventionally known block polymerization, solution polymerization, emulsion polymerization, etc. can be used.

<Resin composition containing heat resistance imparting agent for chlorine-containing polymer and chlorine-containing polymer> The heat resistance imparting agent for the chlorine-containing polymer of this embodiment can be blended into the chlorine-containing polymer to prepare a resin composition. Regarding the blending ratio of the heat resistance imparting agent for chlorine-containing polymers to the chlorine-containing polymer in this embodiment, the maleimide copolymer is 5 to 100 parts by mass relative to 100 parts by mass of the chlorine-containing polymer. Preferably it is 5-80 parts by mass, More preferably, it is 5-60 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 may also be in the range between any two of the numerical values illustrated here. By setting the compounding amount of the maleimide copolymer to 5 parts by mass or more relative to 100 parts by mass of the chlorine-containing polymer, a sufficient heat resistance imparting effect can be obtained, and by setting it to 100 parts by mass. The following can suppress the deterioration of mold releasability during kneading. Moreover, if it is within this range, the balance of heat resistance, affinity with a chlorine-containing polymer, and fluidity can be further improved.

＜Fillers for resin compositions＞ The resin composition of this embodiment may further contain a filler as needed. By blending a filler, an effect of increasing the flexural elastic modulus of a molded article obtained from the resin composition can be expected. Examples of fillers that can be used in this embodiment include silica, diatomaceous earth, aluminum oxide, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, and ferrite. Calcium hydroxide, magnesium hydroxide, aluminum hydroxide, alkaline magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dawsonite, aluminum magnesium carbonate, calcium sulfate, barium sulfate, gypsum fiber, Calcium silicate, talc, clay, mica, montmorillonite, bentonite, activated clay, sepiolite, filamentous aluminite, sericite, glass fiber, glass beads, silica-based hollow spheres, aluminum nitride, nitrogen Boron, silicon nitride, carbon black, graphite, carbon fiber, carbon hollow spheres, charcoal powder, various metal powders, potassium titanate, magnesium sulfate, lead zirconate titanate, aluminum borate, molybdenum sulfide, silicon carbide, stainless steel fiber, Zinc borate, various magnetic powders, slag fibers, fly ash, dewatered sludge, etc. or those obtained by surface treatment. Among these, calcium carbonate, calcium silicate, calcium hydroxide, calcium oxide, magnesium carbonate, magnesium hydroxide, magnesium oxide, barium carbonate, and hydrogen are preferred because they have higher effects on improving mechanical properties and Vickers softening temperature. Alkaline inorganic fillers such as aluminum oxide, zinc oxide, zinc hydroxide, iron oxide, and talc. One type of these fillers may be used alone, or two or more types may be used in combination. The compounding amount of the filler in this embodiment is 1 to 100 parts by mass, preferably 1 to 75 parts by mass, and further preferably 1 to 50 parts by mass relative to 100 parts by mass of the chlorine-containing polymer. Specifically, for example, the compounding amount of the filler is 1, 3, 5, 10, 20, 40, 60, 80, or 100 parts by mass relative to 100 parts by mass of the chlorine-containing polymer, and may also be the numerical value illustrated here. within the range between any two. Furthermore, when a filler is used together, the compounding amount of the filler means the total amount of the fillers used together. By setting the blending amount of the filler to 1 part by mass or more relative to 100 parts by mass of the chlorine-containing polymer, the effect of increasing the flexural elastic modulus can be obtained, and by setting it to 50 parts by mass or less, dispersion can be suppressed. reduce.

＜Impact modifier for resin composition＞ The resin composition of this embodiment may also be further formulated with an impact modifier if necessary. By blending an impact modifier, an effect of improving the impact resistance of molded articles obtained from the resin composition can be expected. Examples of the impact modifier that can be used in this embodiment include ABS (acrylonitrile-butadiene-styrene) resin, MBS (methyl methacrylate-butadiene-styrene) resin, and acrylic resin. Rubber, chlorinated polyethylene, NBR (acrylonitrile butadiene rubber). Among these, MBS resin, acrylic rubber, and chlorinated polyethylene, which are highly effective in improving impact resistance, are preferred. One type of these impact modifiers may be used alone, or two or more types may be used in combination. Regarding the compounding amount of the impact modifier in this embodiment, the impact modifier is 1 to 50 parts by mass, preferably 1 to 40 parts by mass, and further preferably 1 to 30 parts by mass relative to 100 parts by mass of the chlorine-containing polymer. parts by mass. Specifically, for example, the compounding amount of the impact modifier is 1, 3, 5, 8, 10, 15, 20, 25, 30, 35, 40, 45 or 50 parts by mass relative to 100 parts by mass of the chlorine-containing polymer. Parts may also be within the range between any two of the numerical values illustrated here. Furthermore, when an impact modifier is used together, the compounding amount of the impact modifier means the total amount of the impact modifier used together. By setting the compounding amount of the impact modifier to 1 part by mass or more relative 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, bending can be suppressed. The elastic modulus decreases.

＜Processing aids for resin compositions＞ The resin composition of this embodiment may also be formulated with processing aids as needed. By blending a processing aid, effects such as accelerating gelation during processing or improving the formability 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. One type of these processing aids may be used alone, or two or more types may be used in combination. Regarding the compounding amount of the processing aid in this embodiment, the processing aid is 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass relative to 100 parts by mass of the chlorine-containing polymer. Specifically, for example, the blending amount of the processing aid is 0.01, 0.02, 0.05, 0.1, 0.2, 0.5, 1, 2, 5 or 10 parts by mass relative to 100 parts by mass of the chlorine-containing polymer, and may also be as exemplified here. is within the range between any two values. In addition, when processing aids are used together, the compounding amount of processing aids means the total amount of processing aids used together. By setting the blending amount of the processing aid to 0.01 parts by mass or more relative to 100 parts by mass of the chlorine-containing polymer, the effect of improving processability can be obtained, and by setting it to 10 parts by mass or less, the decrease in mechanical properties can be suppressed. .

＜Additives to resin compositions＞ The resin composition of this embodiment may contain additives as described below within a range that does not impede the effects of the present invention, or may consist essentially of a heat resistance imparting agent for chlorine-containing polymers and a chlorine-containing polymer. Furthermore, in one embodiment, the resin composition may be composed of a heat resistance imparting agent for chlorine-containing polymers and a chlorine-containing polymer. In the resin composition of the present invention, if necessary, one type of reinforcing agent, stabilizer, lubricant, plasticizer, etc. may be added alone or two or more types may be added in combination. As other additives, light stabilizers, heat stabilizers, ultraviolet absorbers, antioxidants, pigments, dyes, flame retardants, etc. can be added arbitrarily.

＜Manufacture of resin composition＞ The method of kneading and mixing the heat resistance-imparting agent for chlorine-containing polymer and the chlorine-containing polymer to obtain the resin composition of the present embodiment is not particularly limited, and known melt-kneading technology can be used. As melt-kneading devices that can be suitably used, there are screw extruders such as single-screw extruders, meshing-type co-rotating or meshing-type twin-screw extruders rotating in different directions, non- or incomplete meshing-type twin-screw extruders, etc. , Banbury mixer, reciprocating continuous mixing machine and mixing roller, etc. Furthermore, these extruders can also be used in combination.

The resin composition can be formed by a known method. Examples include injection molding, sheet extrusion molding, vacuum molding, blow molding, foam molding, special-shaped extrusion molding, and the like. During molding, the resin composition is usually heated to 170 to 200°C before processing, preferably 180 to 200°C.

The molded body obtained in the above manner can be used for rain gutters, rain gutter parts, profiles for doors and windows (profiles for doors, windows, sliding doors, partitions, etc.), pipes and joints. [Example]

Hereinafter, the details will be described using examples, but the present invention is not limited to the following examples.

<Production example of maleimide copolymer (A-1)> Add 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 methyl ethylene to an autoclave with a volume of about 120 liters equipped with a mixer. 38 parts by mass of base ketone was replaced with nitrogen gas, and the temperature was raised to 92°C over 40 minutes while stirring. After raising the temperature, while maintaining the temperature at 92°C, 9 parts by mass of maleic anhydride and 0.80 parts by mass of tert-butyl peroxy 2-ethylhexanoate were added continuously for 5 hours while being dissolved in 47 parts by mass of methyl ethyl ketone. into solution. 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 liquid, and the reaction was carried out at 140° C. for 15 hours. The imidization reaction liquid after the reaction is put into a vented screw extruder, and the volatile matter is removed to obtain granular maleimide copolymer A-1. Table 1 shows the analysis results of the obtained maleimide copolymer.

<Production example of maleimide copolymer (A-2)> Add 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 methyl ethylene to an autoclave with a volume of about 120 liters equipped with a mixer. 38 parts by mass of base ketone was replaced with nitrogen gas, and the temperature was raised to 92°C over 40 minutes while stirring. After raising the temperature, while maintaining the temperature at 92°C, 9 parts by mass of maleic anhydride and 0.80 parts by mass of tert-butyl peroxy 2-ethylhexanoate were added continuously for 5 hours while being dissolved in 47 parts by mass of methyl ethyl ketone. into solution. 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 liquid, and the reaction was carried out at 140° C. for 15 hours. The imidization reaction liquid after the reaction is put into a vented screw extruder, and the volatile matter is removed to obtain granular maleimide copolymer A-2. Table 1 shows the analysis results of the obtained maleimide copolymer.

<Production example of maleimide copolymer (A-3)> Add 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 methyl ethylene to an autoclave with a volume of about 120 liters equipped with a mixer. 38 parts by mass of base ketone was replaced with nitrogen gas, and the temperature was raised to 92°C over 40 minutes while stirring. After raising the temperature, while maintaining the temperature at 92°C, 9 parts by mass of maleic anhydride and 0.80 parts by mass of tert-butyl peroxy 2-ethylhexanoate were added continuously for 5 hours while being dissolved in 47 parts by mass of methyl ethyl ketone. into solution. 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 liquid, and the reaction was carried out at 140° C. for 10 hours. The imidization reaction liquid after the reaction is put into a vented screw extruder, and the volatile matter is removed to obtain granular maleimide copolymer A-3. Table 1 shows the analysis results of the obtained maleimide copolymer.

<Production example of maleimide copolymer (A-4)> Add 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 methyl ethylene to an autoclave with a volume of about 120 liters equipped with a mixer. 38 parts by mass of base ketone was replaced with nitrogen gas, and the temperature was raised to 92°C over 40 minutes while stirring. After raising the temperature, while maintaining the temperature at 92°C, 9 parts by mass of maleic anhydride and 0.80 parts by mass of tert-butyl peroxy 2-ethylhexanoate were added continuously for 5 hours while being dissolved in 47 parts by mass of methyl ethyl ketone. into solution. 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 liquid, and the reaction was carried out at 140° C. for 15 hours. The imidization reaction liquid after the reaction is put into a vented screw extruder, and the volatile matter is removed to obtain granular maleimide copolymer A-4. Table 1 shows the analysis results of the obtained maleimide copolymer.

<Production example of maleimide copolymer (A-5)> Add 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 methyl ethylene to an autoclave with a volume of about 120 liters equipped with a mixer. 38 parts by mass of base ketone was replaced with nitrogen gas, and the temperature was raised to 92°C over 40 minutes while stirring. After raising the temperature, while maintaining the temperature at 92°C, 9 parts by mass of maleic anhydride and 0.80 parts by mass of tert-butyl peroxy 2-ethylhexanoate were added continuously for 5 hours while being dissolved in 47 parts by mass of methyl ethyl ketone. into solution. 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 liquid, and the reaction was carried out at 140° C. for 13 hours. The imidization reaction liquid after the reaction is put into a vented screw extruder, and the volatile matter is removed to obtain granular maleimide copolymer A-5. Table 1 shows the analysis results of the obtained maleimide copolymer.

<Production example of maleimide copolymer (A-6)> Add 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 methyl ethylene to an autoclave with a volume of about 120 liters equipped with a mixer. 30 parts by mass of base ketone was replaced with nitrogen gas, and the temperature was raised to 92°C over 40 minutes while stirring. After the temperature was raised, 6 parts by mass of maleic anhydride and 0.70 parts by mass of tert-butyl peroxy 2-ethylhexanoate were added continuously over 4.5 hours while maintaining the temperature at 92°C, and dissolved in 32 parts by mass of methyl ethyl ketone. into solution. 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 part by mass of triethylamine were added to the polymerization liquid, and the reaction was carried out at 140° C. for 7 hours. The imidization reaction liquid after the reaction is put into a vented screw extruder, and the volatile matter is removed to obtain granular maleimide copolymer A-6. Table 1 shows the analysis results of the obtained maleimide copolymer.

<Production example of maleimide copolymer (A-7)> Add 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 methyl ethylene to an autoclave with a volume of about 120 liters equipped with a mixer. 41 parts by mass of base ketone was replaced with nitrogen gas, and the temperature was raised to 92°C over 40 minutes while stirring. After raising the temperature, while maintaining 92°C, 15 parts by mass of maleic anhydride and 0.40 parts by mass of tert-butyl peroxy 2-ethylhexanoate were added continuously over 4.5 hours to dissolve 75 parts by mass of methyl ethyl ketone. into solution. 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 liquid, and the reaction was carried out at 140° C. for 10 hours. The imidization reaction liquid after the reaction is put into a vented screw extruder, and the volatile matter is removed to obtain granular maleimide copolymer A-7. Table 1 shows the analysis results of the obtained maleimide copolymer.

<Production example of maleimide copolymer (A-8)> Add 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 methyl ethylene to an autoclave with a volume of about 120 liters equipped with a mixer. 24 parts by mass of base ketone was replaced with nitrogen gas, and the temperature was raised to 92°C over 40 minutes while stirring. After raising the temperature, while maintaining 92°C, 31 parts by mass of styrene, 7 parts by mass of maleic anhydride and 0.38 parts by mass of tert-butyl peroxy 2-ethylhexanoate were added continuously for 3.5 hours. A solution containing 37 parts by mass of ketone. Furthermore, after the addition of maleic anhydride was completed, a solution in which 0.22 parts by mass of tert-butyl peroxy 2-ethylhexanoate was dissolved in 2 parts by mass of methyl ethyl ketone was added continuously 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 part by mass of triethylamine were added to the polymerization liquid, and the reaction was carried out at 140° C. for 12 hours. The imidization reaction liquid after the reaction is put into a vented screw extruder, and the volatile matter is removed to obtain granular maleimide copolymer A-8. Table 2 shows the analysis results of the obtained maleimide copolymer.

<Production example of maleimide copolymer (A-9)> Add 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 methyl ethylene to an autoclave with a volume of about 120 liters equipped with a mixer. 30 parts by mass of base ketone was replaced with nitrogen gas, and the temperature was raised to 92°C over 40 minutes while stirring. After raising the temperature, while maintaining 92°C, continuously adding 7 parts by mass of maleic anhydride and 0.80 parts by mass of tert-butyl peroxy 2-ethylhexanoate in 33 parts by mass of methyl ethyl ketone for 6 hours. into solution. 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 part by mass of triethylamine were added to the polymerization liquid, and the reaction was carried out at 140° C. for 14 hours. The imidization reaction liquid after the reaction is put into a vented screw extruder, and the volatile matter is removed to obtain granular maleimide copolymer A-9. Table 2 shows the analysis results of the obtained maleimide copolymer.

<Production example of maleimide copolymer (A-10)> Add 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 methyl ethylene to an autoclave with a volume of about 120 liters equipped with a mixer. 34 parts by mass of base ketone was replaced with nitrogen gas, and the temperature was raised to 92°C over 40 minutes while stirring. After raising the temperature, while maintaining 92°C, 34 parts by mass of styrene, 20 parts by mass of maleic anhydride and 0.23 parts by mass of tert-butyl peroxy 2-ethylhexanoate were added continuously for 3 hours. A solution containing 100 parts by mass of ketone. Furthermore, after the addition of maleic anhydride was completed, a solution in which 0.19 parts by mass of tert-butyl peroxy 2-ethylhexanoate was dissolved in 2 parts by mass of methyl ethyl ketone was added continuously 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 liquid, and the reaction was carried out at 140° C. for 10 hours. The imidization reaction liquid after the reaction is put into a vented screw extruder, and the volatile matter is removed to obtain granular maleimide copolymer A-10. Table 2 shows the analysis results of the obtained maleimide copolymer.

<Production example of maleimide copolymer (A-11)> Add 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 to an autoclave with a volume of about 120 liters equipped with a mixer, and replace the gas phase part with nitrogen. , while stirring, it took 40 minutes to heat up to 92°C. After raising the temperature, while maintaining the temperature at 92°C, 9 parts by mass of maleic anhydride and 0.80 parts by mass of tert-butyl peroxy 2-ethylhexanoate were added continuously for 5 hours while being dissolved in 47 parts by mass of methyl ethyl ketone. into solution. 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 liquid, and the reaction was carried out at 140° C. for 13 hours. The imidization reaction liquid after the reaction is put into a vented screw extruder, and the volatile matter is removed to obtain granular maleimide copolymer A-11. Table 2 shows the analysis results of the obtained maleimide copolymer.

<Production example of maleimide copolymer (A-12)> Add 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 methyl ethylene to an autoclave with a volume of about 120 liters equipped with a mixer. 38 parts by mass of base ketone was replaced with nitrogen gas, and the temperature was raised to 92°C over 40 minutes while stirring. After raising the temperature, while maintaining the temperature at 92°C, 9 parts by mass of maleic anhydride and 0.80 parts by mass of tert-butyl peroxy 2-ethylhexanoate were added continuously for 5 hours while being dissolved in 47 parts by mass of methyl ethyl ketone. into solution. 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 liquid, and the reaction was carried out at 140° C. for 15 hours. The imidization reaction liquid after the reaction is put into a vented screw extruder, and the volatile matter is removed to obtain granular maleimide copolymer A-12. Table 2 shows the analysis results of the obtained maleimide copolymer.

<Production example of maleimide copolymer (A-13)> Add 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, and α-methylstyrene dimer to an autoclave with a volume of about 120 liters equipped with a mixer. 0.44 parts by mass and 38 parts by mass of methyl ethyl ketone, the gas phase part was replaced with nitrogen, and the temperature was raised to 92°C over 40 minutes while stirring. After raising the temperature, while maintaining the temperature at 92°C, 9 parts by mass of maleic anhydride and 0.80 parts by mass of tert-butyl peroxy 2-ethylhexanoate were added continuously for 5 hours while being dissolved in 47 parts by mass of methyl ethyl ketone. into solution. 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 liquid, and the reaction was carried out at 140° C. for 15 hours. The imidization reaction liquid after the reaction is put into a vented screw extruder, and the volatile matter is removed to obtain granular maleimide copolymer A-13. Table 2 shows the analysis results of the obtained maleimide copolymer.

<Production example of maleimide copolymer (A-14)> Add 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, and α-methylstyrene dimer to an autoclave with a volume of about 120 liters equipped with a mixer. 0.43 parts by mass and 38 parts by mass of methyl ethyl ketone, the gas phase part was replaced with nitrogen, and the temperature was raised to 92°C over 40 minutes while stirring. After raising the temperature, while maintaining the temperature at 92°C, 9 parts by mass of maleic anhydride and 0.80 parts by mass of tert-butyl peroxy 2-ethylhexanoate were added continuously for 5 hours while being dissolved in 47 parts by mass of methyl ethyl ketone. into solution. 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 liquid, and the reaction was carried out at 140° C. for 15 hours. The imidization reaction liquid after the reaction is put into a vented screw extruder, and the volatile matter is removed to obtain granular maleimide copolymer A-14. Table 2 shows the analysis results of the obtained maleimide copolymer.

<Manufacturing example of maleimide copolymer (B-1)> Add 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 methyl ethylene to an autoclave with a volume of about 120 liters equipped with a mixer. 38 parts by mass of base ketone was replaced with nitrogen gas, and the temperature was raised to 92°C over 40 minutes while stirring. After raising the temperature, while maintaining the temperature at 92°C, 9 parts by mass of maleic anhydride and 0.80 parts by mass of tert-butyl peroxy 2-ethylhexanoate were added continuously for 5 hours while being dissolved in 47 parts by mass of methyl ethyl ketone. into solution. 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 liquid, and the reaction was carried out at 140° C. for 13 hours. The imidization reaction liquid after the reaction is put into a vented screw extruder, and the volatile matter is removed to obtain granular maleimide copolymer B-1. Table 3 shows the analysis results of the obtained maleimide copolymer.

<Production example of maleimide copolymer (B-2)> Add 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, and α-methylstyrene dimer to an autoclave with a volume of about 120 liters equipped with a mixer. 0.43 parts by mass and 38 parts by mass of methyl ethyl ketone, the gas phase part was replaced with nitrogen, and the temperature was raised to 92°C over 40 minutes while stirring. After raising the temperature, while maintaining the temperature at 92°C, 9 parts by mass of maleic anhydride and 0.80 parts by mass of tert-butyl peroxy 2-ethylhexanoate were added continuously for 5 hours while being dissolved in 47 parts by mass of methyl ethyl ketone. into solution. 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 liquid, and the reaction was carried out at 140° C. for 15 hours. The imidization reaction liquid after the reaction is put into a vented screw extruder, and the volatile matter is removed to obtain granular maleimide copolymer B-2. Table 3 shows the analysis results of the obtained maleimide copolymer.

<Production example of maleimide copolymer (B-3)> Add 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 methyl ethylene to an autoclave with a volume of about 120 liters equipped with a mixer. 28 parts by mass of base ketone was replaced with nitrogen gas, and the temperature was raised to 92°C over 40 minutes while stirring. After raising the temperature, while maintaining 92°C, continuously adding 4 parts by mass of maleic anhydride and 0.41 parts by mass of tert-butyl peroxy 2-ethylhexanoate in 18 parts by mass of methyl ethyl ketone for 8 hours. into solution. 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 part by mass of triethylamine were added to the polymerization liquid, and the reaction was carried out at 140° C. for 10 hours. The imidization reaction liquid after the reaction is put into a vented screw extruder, and the volatile matter is removed to obtain granular maleimide copolymer B-3. Table 3 shows the analysis results of the obtained maleimide copolymer.

<Production example of maleimide copolymer (B-4)> Add 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 methyl ethylene to an autoclave with a volume of about 120 liters equipped with a mixer. 37 parts by mass of base ketone was replaced with nitrogen gas, and the temperature was raised to 92°C over 40 minutes while stirring. After raising the temperature, while maintaining 92°C, 36 parts by mass of styrene, 21 parts by mass of maleic anhydride and 0.18 parts by mass of tert-butyl peroxy 2-ethylhexanoate were added continuously for 2.5 hours. A solution containing 105 parts by mass of ketone. Furthermore, after the addition of maleic anhydride was completed, a solution in which 0.18 parts by mass of tert-butyl peroxy 2-ethylhexanoate was dissolved in 1 part by mass of methyl ethyl ketone was added continuously 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 liquid, and the reaction was carried out at 140° C. for 10 hours. The imidization reaction liquid after the reaction is put into a vented screw extruder, and the volatile matter is removed to obtain granular maleimide copolymer B-4. Table 3 shows the analysis results of the obtained maleimide copolymer.

<Production example of maleimide copolymer (B-5)> Add 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 into an autoclave with a volume of about 120 liters equipped with a mixer. After replacing the gas phase part with nitrogen, the temperature was raised to 92°C over 40 minutes while stirring. After raising the temperature, while maintaining 92°C, 11 parts by mass of maleic anhydride and 0.82 parts by mass of tert-butyl peroxy 2-ethylhexanoate were added continuously for 8.5 hours, and dissolved in 56 parts by mass of methyl ethyl ketone. into solution. 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 liquid, and the reaction was carried out at 140° C. for 10 hours. The imidization reaction liquid after the reaction is put into a vented screw extruder, and the volatile matter is removed to obtain granular maleimide copolymer B-5. Table 3 shows the analysis results of the obtained maleimide copolymer.

<Manufacturing example of maleimide copolymer (B-6)> Add 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 methyl ethylene to an autoclave with a volume of about 120 liters equipped with a mixer. 34 parts by mass of base ketone was replaced with nitrogen gas, and the temperature was raised to 92°C over 40 minutes while stirring. After raising the temperature, while maintaining the temperature at 92°C, 40 parts by mass of styrene, 11 parts by mass of maleic anhydride and 0.21 parts by mass of tert-butyl peroxy 2-ethylhexanoate were added continuously for 3 hours. A solution containing 55 parts by mass of ketone. Furthermore, after the addition of maleic anhydride was completed, a solution in which 0.14 parts by mass of tert-butyl peroxy 2-ethylhexanoate was dissolved in 1 part by mass of methyl ethyl ketone was added continuously 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 liquid, and the reaction was carried out at 140° C. for 10 hours. The imidization reaction liquid after the reaction is put into a vented screw extruder, and the volatile matter is removed to obtain granular maleimide copolymer B-6. Table 3 shows the analysis results of the obtained maleimide copolymer.

<Production example of maleimide copolymer (B-7)> Add 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 into an autoclave with a volume of about 120 liters equipped with a mixer, and replace the gas phase part with nitrogen. , while stirring, it took 40 minutes to heat up to 92°C. After raising the temperature, while maintaining the temperature at 92°C, 3 parts by mass of maleic anhydride and 0.82 parts by mass of tert-butyl peroxy 2-ethylhexanoate were added continuously for 4.5 hours, and dissolved in 23 parts by mass of methyl ethyl ketone. into solution. Furthermore, after the addition of maleic anhydride was completed, a solution in which 0.18 parts by mass of tert-butyl peroxy 2-ethylhexanoate was dissolved in 1 part by mass of methyl ethyl ketone was added continuously 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 part by mass of triethylamine were added to the polymerization liquid, and the reaction was carried out at 140° C. for 10 hours. The imidization reaction liquid after the reaction is put into a vented screw extruder, and the volatile matter is removed to obtain granular maleimide copolymer B-7. Table 3 shows the analysis results of the obtained maleimide copolymer.

<Production example of maleimide copolymer (B-8)> Add 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 methyl ethylene to an autoclave with a volume of about 120 liters equipped with a mixer. 39 parts by mass of base ketone was replaced with nitrogen gas, and the temperature was raised to 92°C over 40 minutes while stirring. After raising the temperature, while maintaining 92°C, 41 parts by mass of styrene, 23 parts by mass of maleic anhydride and 0.42 parts by mass of tert-butyl peroxy 2-ethylhexanoate were added continuously for 5 hours. A solution containing 116 parts by mass of ketone. 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 liquid, and the reaction was carried out at 140° C. for 10 hours. The imidization reaction liquid after the reaction is put into a vented screw extruder, and the volatile matter is removed to obtain granular maleimide copolymer B-8. Table 3 shows the analysis results of the obtained maleimide copolymer.

<Production example of maleimide copolymer (B-9)> Add 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 methyl ethylene to an autoclave with a volume of about 120 liters equipped with a mixer. 26 parts by mass of base ketone was replaced with nitrogen gas, and the temperature was raised to 92°C over 40 minutes while stirring. After raising the temperature, while maintaining the temperature at 92°C, 3 parts by mass of maleic anhydride and 0.82 parts by mass of tert-butyl peroxy 2-ethylhexanoate were added continuously over 4.5 hours to dissolve 24 parts by mass of methyl ethyl ketone. into solution. Furthermore, after the addition of maleic anhydride was completed, a solution in which 0.18 parts by mass of tert-butyl peroxy 2-ethylhexanoate was dissolved in 1 part by mass of methyl ethyl ketone was added continuously 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 part by mass of triethylamine were added to the polymerization liquid, and the reaction was carried out at 140° C. for 10 hours. The imidization reaction liquid after the reaction is put into a vented screw extruder, and the volatile matter is removed to obtain granular maleimide copolymer B-9. Table 3 shows the analysis results of the obtained maleimide copolymer.

＜Resin composition＞ (Use of raw materials) The raw materials used in each Example or each Comparative Example are disclosed below. (1)Chlorine-containing polymers ・Product name used: TH-1000 (manufactured by TAIYO VINYL Co., Ltd.). (2) Maleic imine copolymer ・Use those obtained according to the above production examples (A-1 to A-14, B-1 to B-9). (3)Additives ・Sn-based stabilizer: Use TVS#8832 (manufactured by Nitto Chemical Co., Ltd.). ・Lubricant (stearic acid): Use STEARIC ACID CHERRY (manufactured by Nippon Grease Co., Ltd.). ・Impact modifier (MBS): Use Metablen C-223A (Mitsubishi Chemical). ・Impact modifier (chlorinated PE): Use Elaslen 301A (manufactured by Showa Denko Co., Ltd.). ・Impact modifier (acrylic rubber): Use 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) The maleimide copolymers A-1 to A-14, B-1 to B-9, impact modifier, stabilizer and lubricant were added in advance and mixed using a Henschel mixer. Generally, commercially available chlorine-containing polymers (product name: TH-1000, manufactured by TAIYO VINYL Co., Ltd.) are blended according to the mixing ratios shown in Tables 1 to 3, and then a test roller (ϕ6×L15 test roller, manufactured by KANSAI ROLL Co., Ltd.) is used. A rolled sheet of the resin composition is produced, the rolled sheets are stacked and press-molded, a test piece is produced by cutting or punching, and each physical property value is measured. The results are shown in Tables 1 and 2.

(composition analysis) The composition analysis of each monomer unit in the maleimide-based copolymer was measured by the C-13 NMR method under the measurement conditions described below. Device name: FT-NMR AVANCE300 (manufactured by BRUKER) Solvent: Deuterated chloroform Concentration: 14% by mass Temperature: 27℃ Cumulative times: 8000 times

(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 is measured under the following conditions. Device name: SYSTEM-21 Shodex (manufactured by Showa Denko Co., Ltd.) Column: Connect 3 pieces of 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 Corporation).

(melt viscosity) The melt viscosity of the maleimide copolymer was measured at 190°C and a shear rate of 100/sec using a capillary die with L=40 mm and D=1 mm. As the measuring machine, a capillary rheometer 1D manufactured by Toyo Seiki Manufacturing Co., Ltd. was used.

(acid value) The acid value of the maleimide copolymer was measured by dissolving 1 g of the maleimine copolymer in 50 mL of methyl ethyl ketone in accordance with JIS K0070. , add 1 mL of 1.0 w/v% phenolphthalein ethanol solution, and perform neutralization titration on the resulting solution using 0.1 mol/L ethanolic potassium hydroxide solution, and calculate according to the following formula. Acid value (mg/g) = (titer amount (mL) - blank sample volume (mL)) × potassium hydroxide concentration (mol/L) × 56.11 (molar mass of potassium hydroxide g/mol)/male dibutene Amount of imine copolymer (g)

(Adhesion during roller kneading) The adhesion system of the heat-resistant imparting agent during roll kneading was visually observed to determine the adhesion of the chlorine-containing polymer with the heat-resistant imparting agent, TVS#8832 as Sn-based stabilizer, other additives, and the resin composition during roll kneading of the chlorine-containing polymer. The adhesion of the roller is tested and evaluated based on the following criteria. ◎(Excellent): The adhesion of the resin composition to the roller is equivalent to that without adding the heat resistance imparting agent for chlorine-containing polymers. ○ (Good): The adhesion of the resin composition to the roller is stronger than the case where the heat resistance imparting agent for chlorine-containing polymer is not added, but it is to the extent that the rolled sheet can be recycled × (poor): The resin composition adheres strongly to the roller and the rolled sheet cannot be peeled off.

(Charpy impact strength) The Charpy impact strength of the heat-resistant imparting agent is measured in accordance with JIS K-7111, using a notched test piece, with the impact direction along the edge, at a relative humidity of 50% and an ambient temperature of 23°C. In addition, a digital impact testing machine manufactured by Toyo Seiki Co., Ltd. was used as the measuring machine.

(Vickers softening temperature) The Vickers softening temperature of the heat-resistant imparting agent is measured based on JIS K7206:1999 by the B50 method (load 50 N, temperature rise rate 50°C/hour) using a 20 mm × 20 mm, 4 mm thick test piece. In addition, the measuring machine uses the HDT&VSPT testing device manufactured by Toyo Seiki Co., Ltd.

[Table 1] Table 1 unit Reference example Example 1 2 3 4 5 6 7 PVC monomer A-1 A-2 A-3 A-4 A-5 A-6 A-7 Maleic imine copolymer Maleic imine copolymer composition 13CNMR StyreneSt mass % - 70.5 69.5 70.0 69.8 75.6 72.2 64.9 AcrylonitrileAN mass % - 7.5 7.9 7.5 8.2 2.0 12.1 7.0 N-phenylmaleimide NPMI mass % - 22.0 22.0 21.1 20.1 21.5 14.9 27.0 Acid group-containing monomer unit Maleic anhydride MAH mass % - 0.0 0.6 1.4 1.9 0.9 0.8 1.1 Methacrylic acid MAA mass % - 0.0 0.0 0.0 0.0 0.0 0.0 0.0 weight average molecular weight Mw ten thousand - 8.0 7.4 8.2 8.4 7.5 9.1 4.1 Melt viscosity 190℃、100sec ^-1 Pa・sec - 4000 3900 4100 4500 4400 5000 15000 Acid value titration mg/g - 0.0 3.4 8.0 10.9 5.1 4.6 6.3 Resin composition Dispensing amount PVC TH-1000 parts by mass 100 100 100 100 100 100 100 100 Sn stabilizer TVS#8832 parts by mass 2 2 2 2 2 2 2 2 Lubricant stearic acid parts by mass 1 1 1 1 1 1 1 1 Maleic imine copolymer parts by mass 0 15 15 15 15 15 15 15 MBS C-223A parts by mass 0 10 10 10 10 10 10 10 Adhesion during roller kneading Roller temperature 180℃ - ◎ ◎ ◎ ◎ 〇 ◎ ◎ ◎ Charpy impact strength There is a gap kJ/m ² 5 twenty four twenty two 19 16 twenty one twenty two 16 Vickers softening temperature B50 ℃ 75.1 80.0 79.9 79.8 79.6 79.7 78.9 81.0

[Table 2] Table 2 unit Reference example Example 8 9 10 11 12 13 14 15 16 PVC monomer A-8 A-9 A-10 A-11 A-12 A-13 A-14 A-2 A-2 Maleic imine copolymer Maleic imine copolymer composition 13CNMR StyreneSt mass % - 59.4 79.3 46.8 70.2 69.8 70.3 70.3 69.5 69.5 AcrylonitrileAN mass % - 26.9 7.0 22.5 7.5 8.2 7.9 7.9 7.9 7.9 N-phenylmaleimide NPMI mass % - 12.4 13.0 29.8 21.1 20.1 20.4 20.4 22.0 22.0 Acid group-containing monomer unit Maleic anhydride MAH mass % - 1.3 0.7 0.9 1.2 1.9 0.7 0.0 0.6 0.6 Methacrylic acid MAA mass % - 0.0 0.0 0.0 0.0 0.0 0.7 1.4 0.0 0.0 weight average molecular weight Mw ten thousand - 10.1 9.5 3.5 13.9 2.8 7.3 7.4 7.4 7.4 Melt viscosity 190℃、100sec ^-1 Pa・sec - 5300 2000 5200 89000 300 4200 3900 3900 3900 Acid value titration mg/g - 7.4 4.0 5.1 6.9 10.9 8.6 9.1 3.4 3.4 Resin composition Dispensing amount PVC TH-1000 parts by mass 100 100 100 100 100 100 100 100 100 100 Sn stabilizer TVS#8832 parts by mass 2 2 2 2 2 2 2 2 2 2 Lubricant stearic acid parts by mass 1 1 1 1 1 1 1 1 1 1 Maleic imine copolymer parts by mass 0 15 15 15 15 15 15 15 15 15 MBS C-223A parts by mass 0 10 10 10 10 10 10 10 0 0 Acrylic rubber FM-50 parts by mass 0 0 0 0 0 0 0 0 10 0 Chlorinated PE 301A parts by mass 0 0 0 0 0 0 0 0 0 10 Adhesion during roller kneading Roller temperature 180℃ - ◎ ◎ ◎ ◎ ◎ 〇 〇 〇 ◎ ◎ Charpy impact strength There is a gap kJ/m ² 5 18 twenty two 16 19 16 twenty one twenty three twenty one twenty one Vickers softening temperature B50 ℃ 75.1 79.0 78.3 79.8 80.0 78.4 79.5 79.3 79.7 79.5

[table 3] table 3 unit Reference example Comparative example 1 2 3 4 5 6 7 8 9 PVC monomer B-1 B-2 B-3 B-4 B-5 B-6 B-7 B-8 B-9 Maleic imine copolymer Maleic imine copolymer composition 13CNMR StyreneSt mass % - 70.2 69.1 90.8 39.8 81.7 45.1 75.9 51.8 80.4 AcrylonitrileAN mass % - 7.8 7.7 2.0 29.5 0.0 35.0 19.0 8.0 12.3 N-phenylmaleimide NPMI mass % - 20.0 21.2 6.0 29.5 17.5 19.0 4.0 39.0 6.4 Acid group-containing monomer unit Maleic anhydride MAH mass % - 2.0 0.0 1.2 1.2 0.8 0.9 1.1 1.2 0.9 Methacrylic acid MAA mass % - 0.0 2.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 weight average molecular weight Mw ten thousand - 8.0 7.8 11.7 7.0 10.0 8.2 11.3 10.1 2.4 Melt viscosity 190℃、100sec ^-1 Pa・sec - 4500 4300 2800 91000 4800 21000 3900 151000 160 Acid value titration mg/g - 11.4 13.0 6.9 6.9 4.6 5.1 6.3 6.9 5.1 Resin composition Dispensing amount PVC TH-1000 parts by mass 100 100 100 100 100 100 100 100 100 100 Sn stabilizer TVS#8832 parts by mass 2 2 2 2 2 2 2 2 2 2 Lubricant stearic acid parts by mass 1 1 1 1 1 1 1 1 1 1 Maleic imine copolymer parts by mass 0 15 15 15 15 15 15 15 15 15 MBS C-223A parts by mass 0 10 10 10 10 10 10 10 10 10 Adhesion during roller kneading Roller temperature 180℃ - ◎ 〇 × ◎ Cannot be mixed without melting ◎ ◎ ◎ Cannot be mixed without melting ◎ Charpy impact strength There is a gap kJ/m ² 5 14 Unable to rate 16 16 14 17 17 Vickers softening temperature B50 ℃ 75.1 79.6 77.5 77.6 78.5 77.4 77.6

In Examples 1 to 16 using the heat-resistant imparting agent for chlorine-containing polymers of the present invention, the balance between heat resistance and impact strength of the resin composition was fully improved. Furthermore, even when a Sn-based stabilizer is blended, adhesion of the resin composition to the roll hardly occurs in the roll kneading step 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 in which heat resistance-imparting agents for chlorine-containing polymers that do not meet the requirements of the present invention were used, the heat resistance or impact strength of the resin composition was not sufficiently improved. Furthermore, when a Sn-based stabilizer is blended, in the step of roller kneading of the heat resistance imparting agent for chlorine-containing polymer and the chlorine-containing polymer, the adhesion of the resin composition to the roller becomes stronger, or melt-kneading becomes impossible. [Industrial availability]

According to the present invention, there is provided a heat-resistant imparting agent for chlorine-containing polymers, which can improve the balance between heat resistance and impact strength of chlorine-containing polymers, and can also improve chlorine-containing polymerization even when a Sn-based stabilizer is blended. The heat-resistant imparting agent and the chlorine-containing polymer are used in the roller kneading step to reduce the adhesion of the resin composition to the roller, so it is suitable for use in rain gutters, rain gutter parts, door and window profiles, pipes and joints.

Claims (7)

A heat-resistant imparting agent for chlorine-containing polymers, which contains maleic acid imide having at least aromatic vinyl monomer units, vinyl cyanide monomer units and maleimine monomer units. Amine copolymers, When the total number of monomer units contained in the above-mentioned maleimine copolymer is 100% by mass, the above-mentioned maleimine copolymer includes: 40 to 90% by mass of the above aromatic vinyl monomer units, 0.5 to 30% by mass of the above vinyl cyanide monomer unit, and The above-mentioned maleic imine monomer unit is 5 to 30% by mass, and The melt viscosity of the above-mentioned maleimide copolymer measured at 190°C and a shear rate of 100/sec is 200 to 100000 Pa·sec, and the acid value is 0 to 11 mg/g. The heat resistance imparting agent for chlorine-containing polymers as claimed in claim 1, wherein the maleic imine copolymer further contains a monomer unit having an acid group, and the monomer unit having an acid group is selected from the group consisting of unsaturated acid anhydrides. At least one of the group consisting of monomer units and (meth)acrylic acid monomer units. The heat resistance imparting agent for chlorine-containing polymers as claimed in claim 2, wherein the monomer unit having an acid group is a maleic anhydride monomer unit. The heat resistance-imparting agent for chlorine-containing polymers according to claim 1, wherein the weight average molecular weight of the maleimide copolymer is 30,000 to 120,000. 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. A molded article using the resin composition according to Claim 5. For example, the formed body of claim 6 is used as rain gutters, rain gutter parts, profiles for doors and windows, pipes and joints.