KR20230052943A - A maleimide-based copolymer and a chlorine-containing polymer-based resin composition comprising the maleimide-based copolymer and a chlorine-containing polymer - Google Patents

Abstract

An object of the present invention is a maleimide-based copolymer capable of obtaining a chlorine-containing polymer-based resin composition in which coloring is suppressed while improving the heat resistance of the chlorine-containing polymer, and a chlorine-containing polymer comprising the maleimide-based copolymer and the chlorine-containing polymer. A resin composition and a molded product thereof are provided. Another object is to provide a chlorine-containing polymer-based resin composition having excellent extrusion moldability. According to the present invention, 50 to 90% by mass of the aromatic vinyl-based monomer unit, when the total of the aromatic vinyl-based monomer unit, vinyl cyanide-based monomer unit, unsaturated acid anhydride monomer unit, and maleimide-based monomer unit is 100 mass% and 0.5 to 25% by mass of the vinyl cyanide-based monomer unit, 0 to 10% by mass of the unsaturated acid anhydride monomeric unit, and 5 to 25% by mass of the maleimide-based monomeric unit, 190 ° C., shear rate 100 / sec A maleimide-based copolymer for a chlorine-containing polymer having a melt viscosity of 200 to 100,000 Pa·sec and a weight average molecular weight of 2.5 to 120,000, measured under the conditions of, is provided.

Description

A maleimide-based copolymer and a chlorine-containing polymer-based resin composition comprising the maleimide-based copolymer and a chlorine-containing polymer

The present invention relates to a maleimide-based copolymer and a chlorine-containing polymer-based resin composition comprising the maleimide-based copolymer and a chlorine-containing polymer.

Chlorine-containing polymer-based resins are inexpensive and have excellent chemical, physical, and mechanical properties, so they are mass-produced and used for various purposes.

However, chlorine-containing polymers have the disadvantage of lacking heat resistance (thermal softening temperature), and, for example, based on JIS K7206: 1999, the Vikat softening measured by the 50 method (load 50 N, temperature increase rate 50°C/hour) The temperature is around 82°C, and the softening temperature is further lowered by a stabilizer and a plasticizer usually blended during molding.

As a method of improving the heat resistance of a chlorine-containing polymer-based resin, a method of mixing a resin that imparts heat resistance with a chlorine-containing polymer (Patent Documents 1 and 2) is known.

Japanese Patent 06475501 Japanese Patent Publication 2006-265373

The present invention provides a maleimide-based copolymer capable of obtaining a chlorine-containing polymer-based resin composition in which coloring is suppressed while improving the heat resistance of the chlorine-containing polymer, and a chlorine-containing polymer-based resin composition comprising the maleimide-based copolymer and the chlorine-containing polymer. And it is intended to provide a molded body thereof. In addition, it is intended to provide a chlorine-containing polymer-based resin composition excellent in extrusion moldability.

As a result of examination by the present inventors, heat resistance can be imparted to a chlorine-containing polymer by employing a maleimide-based copolymer having a specific monomer unit composition, a melt viscosity within a specific range, and a weight average molecular weight within a specific range, and having a controlled yellowness to a low level. It was discovered that coloring in a resin composition and its molded object could be suppressed while existing. In addition, it was found that the extrusion moldability of the resin composition was good.

That is, the present invention

(1) 50 to 90% by mass of the aromatic vinylic monomeric unit, when the total of the aromatic vinylic monomer unit, the vinylcyanide monomeric unit, the unsaturated acid anhydride monomeric unit, and the maleimide-based monomeric unit is 100% by mass; 0.5 to 25% by mass of the vinyl cyanide monomer units, 0 to 10% by mass of the unsaturated acid anhydride monomer units, and 5 to 25% by mass of the maleimide monomer units, and conditions of 190° C. and a shear rate of 100/sec A maleimide-based copolymer for chlorine-containing polymers having a melt viscosity of 200 to 100000 Pa sec and a weight average molecular weight of 2.5 to 120,000, as measured by

(2) A chlorine-containing polymer-based resin composition containing 5 to 50% by mass of the maleimide-based copolymer described in (1) and 50 to 95% by mass of a chlorine-containing polymer;

(3) The chlorine-containing polymer-based resin composition according to (2), wherein the melt viscosity is 200 to 70000 Pa sec;

(4) The chlorine-containing polymer-based resin composition according to (2) or (3), wherein the maleimide-based copolymer has a weight average molecular weight of 50,000 to 100,000;

(5) The chlorine-containing polymer-based resin composition according to any one of (2) to (4), wherein the maleimide-based copolymer has 50 to 80% by mass of an aromatic vinyl-based monomer unit;

(6) The chlorine-containing polymer-based resin composition according to any one of (2) to (5), wherein the maleimide-based copolymer has 5 to 20% by mass of vinyl cyanide-based monomer units;

(7) The chlorine-containing polymer-based resin composition according to any one of (2) to (6), wherein the maleimide-based copolymer has 0.3 to 5% by mass of unsaturated acid anhydride monomer units;

(8) The chlorine-containing polymer-based resin composition according to any one of (2) to (7), wherein the maleimide-based copolymer has 5 to 24% by mass of maleimide-based monomer units;

(9) The chlorine-containing polymer-based resin composition according to any one of (2) to (8), wherein the maleimide-based monomer unit is N-arylmaleimide;

(10) A molded article characterized by being molded from the chlorine-containing polymer-based resin composition according to any one of (2) to (9);

It is about.

When the maleimide-based copolymer of the present invention is employed, heat resistance can be imparted to the chlorine-containing polymer, and coloring in the resin composition and its molded article can be suppressed. For this reason, it is suitably used for applications requiring heat resistance and applications requiring good appearance. Moreover, since it is excellent in kneading|mixing property, it is used suitably also for extrusion molding.

<Explanation of terms>

In the specification of the present application, the description of "A to B" means more than A and less than B.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described in detail. Also, each embodiment may be combined with each other, respectively.

(1. Monomer unit contained in maleimide copolymer)

The maleimide-based copolymer in the present invention contains an aromatic vinyl-based monomer unit, a vinyl cyanide-based monomer unit, an unsaturated acid anhydride monomer unit, and a maleimide-based monomer unit. The monomer units contained in the maleimide-based copolymer are described below.

(1-1. Aromatic vinyl monomer unit)

Examples of the aromatic vinyl monomer that can be used in the maleimide-based copolymer according to the present invention include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, ethylstyrene, p- tert-butyl styrene, α-methyl styrene, α-methyl-p-methyl styrene, and the like. Among these, styrene having a high color-improving effect is preferable. A styrenic monomer may be used alone or in combination of two or more.

The maleimide-based copolymer according to the present invention contains 50% of the aromatic vinyl-based monomer unit when the total of the aromatic vinyl-based monomer unit, the cyanide-based monomer unit, the unsaturated acid anhydride monomer unit and the maleimide-based monomer unit is 100% by mass. It contains -90 mass %, Preferably it contains 50-80 mass %, More preferably, it contains 60-70 mass %. Specifically, it is 50, 45, 50, 55, 60, 65, 70, 75, 80, 85, or 90% by mass, for example, and may be within the range between any two of the numerical values exemplified here. When the amount of the aromatic vinyl monomer unit is less than 50% by mass, other monomer components contained in the maleimide-based copolymer are relatively increased, resulting in the maleimide-based copolymer not melting and kneading with the chlorine-containing polymer. However, coloring of the chlorine-containing polymer-based resin composition and its molded product may become a problem due to the increase in yellowness (YI) of the maleimide-based copolymer, and when it exceeds 90% by mass, the chlorine-containing polymer-based resin composition There are cases in which the heat resistance of can not be sufficiently improved.

(1-2. Vinyl cyanide monomer unit)

Examples of the vinyl cyanide-based monomer unit that can be used in the maleimide-based copolymer according to the present invention include acrylonitrile, methacrylonitrile, ethacrylonitrile, and fumaronitrile. Among these, acrylonitrile is preferable from the viewpoint of imparting color and heat resistance to the chlorine-containing polymer-based resin composition. The vinyl cyanide monomer may be used alone or in combination of two or more.

The maleimide-based copolymer according to the present invention contains 0.5% of vinyl cyanide-based monomer unit when the total of the aromatic vinyl-based monomer unit, vinyl cyanide-based monomer unit, unsaturated acid anhydride monomer unit, and maleimide-based monomer unit is 100% by mass. It contains -25 mass %, Preferably it contains 1-20 mass %, More preferably, it contains 5-20 mass %. Specifically, it is 0.5, 1, 5, 10, 15, 20, or 25% by mass, for example, and may be within the range between any two of the numerical values exemplified here. When the amount of the vinyl cyanide-based monomer unit is less than 0.5% by mass, the heat resistance of the chlorine-containing polymer-based resin composition may not be sufficiently improved, and when it exceeds 25% by mass, the yellowness (YI) of the maleimide-based copolymer increases. There are cases.

(1-3. Unsaturated Acid Anhydride Monomer Unit)

Examples of the unsaturated acid anhydride monomer unit that can be used in the maleimide-based copolymer of the present invention include maleic anhydride, itaconic anhydride, citraconic anhydride and aconitic anhydride. Among these, maleic anhydride is preferable from the viewpoint of imparting heat resistance to the chlorine-containing polymer-based resin composition. The unsaturated acid anhydride monomer unit may be used alone or in combination of two or more.

In the maleimide-based copolymer according to the present invention, when the sum of the aromatic vinyl-based monomer unit, the cyanide-based monomer unit, the unsaturated acid anhydride monomer unit, and the maleimide-based monomer unit is 100% by mass, the unsaturated acid anhydride monomer unit is 0 It contains -10 mass %, Preferably it contains 0.3-5 mass %, It contains 0.5-5 mass % more preferably. Specifically, for example, 0, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10% by mass, any of the numerical values exemplified herein may be within the range between the two of When the amount of the unsaturated acid anhydride monomer unit exceeds 10% by mass, the fluidity may decrease and the kneadability with the chlorine-containing polymer may decrease.

(1-4. Maleimide Monomer Unit)

Examples of the maleimide-based monomer units that can be used in the maleimide-based copolymer according to the present invention include N-alkylmaleimides such as N-methylmaleimide, N-butylmaleimide, and N-cyclohexylmaleimide; and and N-aryl maleimides such as N-phenyl maleimide, N-chlorophenyl maleimide, N-methylphenyl maleimide, N-methoxyphenyl maleimide, and N-tribromophenyl maleimide. Among these, from the viewpoint of imparting heat resistance to the chlorine-containing polymer-based resin composition, N-arylmaleimide is preferred, and N-phenylmaleimide is more preferred. Maleimide type monomers may be used alone or in combination of two or more.

In order to make the maleimide copolymer contain the maleimide monomer unit, for example, a copolymer prepared by copolymerizing a raw material comprising an unsaturated dicarboxylic acid monomer unit with other monomers may be imidized with ammonia or a primary amine. Alternatively, a raw material composed of maleimide monomers may be copolymerized with other monomers.

The maleimide-based copolymer according to the present invention contains 5 maleimide-based monomer units when the total of the aromatic vinyl-based monomer unit, the cyanide-based monomer unit, the unsaturated acid anhydride monomer unit and the maleimide-based monomer unit is 100% by mass. It contains -25 mass%, Preferably it contains 5 mass% or more and less than 25 mass%, More preferably, it contains 5-24 mass%, More preferably, it contains 10-24 mass%. Specifically, for example, 5, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, or 25% by mass, any of the numerical values exemplified here It may be within the range between the two. If the amount of the maleimide-based monomer unit is less than 5% by mass, the heat resistance of the chlorine-containing polymer-based resin composition may not be sufficiently improved, and if it exceeds 25% by mass, the maleimide-based copolymer will not melt with the chlorine-containing polymer. In some cases, it may become impossible to knead.

(1-5. Copolymerizable Monomers)

In the maleimide-based copolymer according to the present invention, copolymerizable monomers other than an aromatic vinyl monomer, a vinyl cyanide monomer, an unsaturated acid anhydride monomer unit, and a maleimide monomer may be copolymerized within a range that does not impair the effect of the present invention. The monomers copolymerizable with the maleimide-based copolymer include acrylic acid ester monomers such as methyl acrylic acid ester, ethyl acrylic acid ester and butyl acrylic acid ester, methacrylic acid ester monomers such as methyl methacrylic acid ester and ethyl methacrylic acid ester, acrylic acid, meta Vinyl carboxylic acid monomers, such as acrylic acid, acrylic acid amide, methacrylic acid amide, etc. are mentioned. The monomer copolymerizable with the maleimide copolymer may be used alone or in combination of two or more.

These monomers can be copolymerized within a range that does not impair the effect of the present invention, but from the viewpoint of imparting heat resistance to the chlorine-containing polymer-based resin composition, it is preferably 20% by mass or less, more preferably 10% by mass or less. .

(1-6. Additives)

After completion of the polymerization, the polymerization solution, if necessary, heat-resistant stabilizers such as hindered phenol-based compounds, lactone-based compounds, phosphorus-based compounds and sulfur-based compounds, light stabilizers such as hindered amine-based compounds and benzotriazole-based compounds, lubricants and plasticizers, You may add additives, such as a coloring agent, an antistatic agent, and mineral oil. It is preferable that the addition amount is less than 0.2 mass part with respect to 100 mass parts of all monomer units. These additives may be used alone or in combination of two or more.

(2. Physical properties of maleimide-based copolymer)

(2-1. Melt viscosity of maleimide copolymer)

The melt viscosity of the maleimide-based copolymer in the present invention is 200 to 100000 Pa·sec, preferably 200 to 70000 Pa·sec, and more preferably 500 to 70000 Pa·sec. Specifically, for example, 200, 500, 1000, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, 10000, 20000, 30000, 40000, 50000, or 100000 Pa sec, the numerical values exemplified here It may be within the range between any two. If it is less than 200 Pa·sec, the heat resistance of the chlorine-containing polymer-based resin composition may not be sufficiently improved, and if it exceeds 100000 Pa·sec, it becomes impossible to knead the maleimide-based copolymer of the mixed resin without melting with the chlorine-containing polymer. There are cases.

The melt viscosity was measured using a capillary rheometer 1D manufactured by Toyo Seiki Seisakusho Co., Ltd. with a capillary die with L = 40 mm and D = 1 mm.

The melt viscosity of the maleimide-based copolymer can be adjusted by adjusting the compounding ratio of the monomer units constituting the maleimide-based copolymer. For example, it is possible to increase the melt viscosity by increasing the content of the vinyl cyanide-based monomer unit in the maleimide-based copolymer or by increasing the content of the maleimide-based monomer unit in the maleimide-based copolymer. In addition, the melt viscosity can be increased also by increasing the weight average molecular weight of the maleimide-based copolymer. It is possible to use these adjustment methods together.

(2-2. Weight average molecular weight of maleimide copolymer)

The weight average molecular weight of the maleimide copolymer in the present invention is 25,000 to 120,000, preferably 50,000 to 100,000. Specifically, for example, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9. 5, 10, 10.5, 11, 11.5 or 12 only, It may be within the range between two of the numerical values illustrated here. If the weight average molecular weight is less than 2.50,000, the heat resistance of the chlorine-containing polymer-based resin composition may not be sufficiently improved, and if it exceeds 120,000, the torque during kneading of the chlorine-containing polymer-based resin composition may increase. there is.

The weight average molecular weight is a value in terms of polystyrene measured by gel permeation chromatography (GPC), and can be measured under the following conditions.

Measurement name: SYSTEM-21 Shodex (manufactured by Showa Denko Co., Ltd.)

Column: 3 PL gel MIXED-B (manufactured by Polymer Laboratories) in series

Temperature: 40℃

Detection: Differential Refractive Index

Solvent: tetrahydrofuran

Concentration: 2% by mass

Calibration curve: Created using standard polystyrene (PS) (manufactured by Polymer Laboratories)

As a method for obtaining a maleimide-based copolymer having a preferable weight average molecular weight (Mw) of 25,000 to 120,000, in addition to the method of adjusting the polymerization temperature, polymerization time, and polymerization initiator addition amount, the addition amount of the solvent and the addition amount of the chain transfer agent are adjusted. There are ways to adjust. In addition, a method of reducing the molecular weight of the obtained copolymer by decomposition is known.

(3. Preparation of maleimide-based copolymer)

Polymerization modes of the maleimide-based copolymer include, for example, solution polymerization and bulk polymerization. Solution polymerization is preferable from the viewpoint that a maleimide-based copolymer having a more uniform copolymerization composition can be obtained by polymerization while performing branching or the like. The solvent for solution polymerization is preferably non-polymeric from the viewpoint of less likely to produce by-products and less 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, dimethyl sulfoxide, N-methyl-2-pyrrolidone, etc., and methyl ethyl ketone and methyl isobutyl ketone from the ease of solvent removal during devolatilization recovery of the maleimide copolymer. desirable. As the polymerization process, any one of continuous polymerization, batch (batch), and semi-batch may be applied.

The method for producing the maleimide-based copolymer is not particularly limited, but it is preferably obtained by radical polymerization, and the polymerization temperature is preferably in the range of 80 to 150°C. The polymerization initiator is not particularly limited, and examples thereof include 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- Known organic peroxides such as ethyl hexanoate, di-t-butyl peroxide, dicumyl peroxide, and ethyl-3,3-di-(t-butylperoxy)butylate can be used, and one or two of these You can use more than one type in combination. From the viewpoint of the polymerization reaction rate or 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 is preferably 0.1 to 1.5% by mass, more preferably 0.1 to 1.0% by mass, based on 100% by mass of all monomer units. When the amount of the polymerization initiator is 0.1% by mass or more, a sufficient polymerization rate is obtained, which is preferable. When the usage amount of the polymerization initiator 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 for the manufacture of maleimide-based copolymers. The chain transfer agent used is not particularly limited, and examples thereof include n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, α-methylstyrene dimer, ethyl thioglycolate, limonene, and terpinolene. etc. The amount of chain transfer agent used is not particularly limited as long as the target molecular weight can be obtained, but is preferably 0.01 to 0.8% by mass, more preferably 0.1 to 0.5% by mass, based on 100% by mass of all monomer units. A target molecular weight can be easily obtained if the usage-amount of a chain transfer agent is 0.01 mass % - 0.8 mass %.

As a method for introducing the maleimide monomer unit into the maleimide copolymer, a method of copolymerizing a maleimide monomer, an aromatic vinyl monomer, or a vinyl cyanide monomer (direct method), or a method using an unsaturated dicarboxylic acid anhydride, an aromatic vinyl monomer, or a vinyl cyanide monomer There is a method of converting the unsaturated dicarboxylic acid anhydride group into a maleimide monomer unit by copolymerizing in advance and further reacting the unsaturated dicarboxylic acid anhydride group with ammonia or a primary amine (post-imidation method). The post-imidation method is preferable because the amount of residual maleimide-based monomers in the copolymer is reduced.

The primary amine used in the post-imidation method is, for example, methylamine, ethylamine, n-propylamine, iso-propylamine, n-butylamine, n-pentylamine, n-hexylamine, n- There are alkylamines such as octylamine, cyclohexylamine, and decylamine, chloro- or bromine-substituted alkylamines, and aromatic amines such as aniline, toluidine, and naphthylamine. Among them, aniline and cyclohexylamine are preferable. 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 equivalents, more preferably 0.85 to 1.05 molar equivalents, relative to the unsaturated dicarboxylic acid anhydride group. When it is 0.7 molar equivalent or more with respect to the unsaturated dicarboxylic acid anhydride monomer unit in the maleimide-type copolymer, since thermal stability becomes favorable, it is preferable. Moreover, if it is 1.1 molar equivalent or less, since the amount of primary amines remaining in a maleimide-type copolymer will reduce, it is preferable.

A catalyst may be used when introducing a maleimide monomeric unit by post-imidation. The catalyst can improve the dehydration ring closure reaction in the reaction between ammonia or primary amine and an unsaturated dicarboxylic acid anhydride group, particularly in the reaction of converting an unsaturated dicarboxylic acid anhydride group into a maleimide group. Although the kind of catalyst is not specifically limited, For example, tertiary amine can be used. The tertiary amine is not particularly limited, and examples thereof include trimethylamine, triethylamine, tripropylamine, tributylamine, N,N-dimethylaniline, and N,N-diethylaniline. The addition amount of the tertiary amine is not particularly limited, but is preferably 0.01 molar equivalent or more relative to the unsaturated dicarboxylic acid anhydride group. The temperature of the imidation reaction in the present invention is preferably 100 to 250°C, more preferably 120 to 200°C. When the temperature of the imidation reaction is 100°C or higher, the reaction rate is sufficiently fast, which is preferable from the viewpoint of productivity. If the temperature of the imidation reaction is 250°C or less, it is preferable because the decrease in physical properties due to thermal deterioration of the maleimide-based copolymer can be suppressed.

As a method for removing volatile components such as solvents used in solution polymerization or unreacted monomers from the solution after solution polymerization of the maleimide copolymer or the solution after post-imidation (devolatilization method), a known method can be employed. . For example, a vacuum devolatilization tank equipped with a heater or a devolatilization extruder with a vent can be used. The maleimide-based copolymer in a devolatilized molten state is transferred to a granulation process, extruded in a strand shape from a perforated die, and processed into pellets by a cold cut method, an air hot cut method, or an underwater hot cut method.

When the chlorine-containing polymer is in powder form, the maleimide-based copolymer of the present invention is also preferably pulverized into powder form before use. The grinding method is not particularly limited, and a known grinding technique can be used. Preferable grinding apparatuses include a turbo mill type grinder, a turbo disc mill type grinder, a turbo cutter type grinder, a jet mill type grinder, an impact type grinder, a hammer type grinder, and a vibration type grinder.

(4. Chlorine-Containing Polymer)

The chlorine-containing polymer in the present invention is a polymer obtained by polymerizing a vinyl chloride monomer alone or a mixture of a vinyl chloride monomer and at least one monomer copolymerizable therewith, and a chlorine addition polymer obtained by adding chlorine to the polymer thus obtained. Moreover, the compound of the polymer obtained by doing in this way and a chlorine addition polymer may also be contained in the chlorine containing polymer. Examples of copolymerizable monomers include vinyl esters such as vinyl acetate and vinyl propionate, acrylic acid esters such as methyl acrylate and butyl acrylate, methacrylic acid esters such as methyl methacrylate and ethyl methacrylate, butyl maleate, and the like. fumaric acid esters such as diethyl maleate, vinyl ethers such as vinylmethyl ether, vinylbutyl ether and vinyloctyl ether, vinyl cyanides such as acrylonitrile and methacrylonitrile, α-olefins such as ethylene and propylene, Styrene such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, and chlorostyrene and their substitutes, vinylidene halides and vinyl halides other than vinyl chloride such as vinylidene chloride and vinyl bromide, and phthalic acid such as diallylphthalate Ester can be mentioned.

The chlorine-containing polymer is preferably polyvinyl chloride obtained by polymerizing a vinyl chloride monomer from the viewpoint of affinity with the maleimide copolymer.

The average polymerization degree of the chlorine-containing polymer is 680 to 1900, preferably 700 to 1700. By setting the average degree of polymerization to 680 or more, the maleimide-based copolymer can be uniformly dispersed, and by setting the average degree of polymerization to 1900 or less, the kneadability with the maleimide-based copolymer is excellent.

(4-1. Preparation of chlorine-containing polymer)

The polymerization method of the chlorine-containing polymer is not particularly limited, and conventionally known bulk polymerization, solution polymerization, emulsion polymerization, or the like is used.

(5. Chlorine-Containing Polymer-Based Resin Composition Containing Maleimide-Based Copolymer and Chlorine-Containing Polymer)

The blending ratio of the maleimide copolymer and the chlorine-containing polymer in the present invention is preferably 5 to 50% by mass of the maleimide copolymer and 50 to 95% by mass of the chlorine-containing polymer, more preferably maleimide They are 5-30 mass % of system copolymers, and 70-95 mass % of chlorine-containing polymers. By setting the blending ratio of the maleimide-based copolymer to 5% by mass or more, sufficient heat resistance imparting effect is obtained, and by setting to 50% by mass or less, deterioration of releasability during kneading is suppressed.

(5-1. Additives of chlorine-containing polymer-based resin composition)

The chlorine-containing polymer-based resin composition in the present invention may contain additives described below within a range that does not impair the effects of the present invention, but may also consist substantially of a maleimide-based copolymer and a chlorine-containing polymer.

To the chlorine-containing polymer-based resin composition of the present invention, if necessary, a reinforcing agent, a workability improver, a heat stabilizer, a lubricant, a plasticizer, and the like may be further added alone or in combination of two or more.

As other additives, light stabilizers, ultraviolet absorbers, antioxidants, pigments, dyes and the like can be optionally added.

(5-2. Preparation of chlorine-containing polymer-based resin composition)

The method for obtaining the chlorine-containing polymer-based resin composition according to the present invention by kneading and mixing the maleimide-based copolymer and the chlorine-containing polymer is not particularly limited, and a known melt-kneading technique can be used. As the melt kneading apparatus that can be suitably used, screw extruders such as a single screw extruder, an intermeshing type co-rotating or intermeshing type bi-rotating twin screw extruder, a non- or incomplete intermeshing type twin screw extruder, a banbury mixer, a cornier, and a mixer rolls, etc. Moreover, it is also possible to use these extruders in combination of a plurality of them.

The extruder is composed of a kneading unit for melt-kneading the maleimide-based copolymer and the chlorine-containing polymer and at least one devolatilizing unit. The maleimide-based copolymer and the chlorine-containing polymer supplied to the extruder are first melted in a kneading unit and kneaded to a uniform composition. The kneading unit is configured by combining known mixing elements such as kneading disks. From the viewpoint of kneading performance, it is preferable to use an element having an action of pushing and turning the molten resin on the upstream side downstream of the kneading unit, and to bring the kneading unit into a full state. Examples of the element include reverse lead full flight, reverse lift kneading, and sealing.

As a method for molding the chlorine-containing polymer-based resin composition, a known method can be employed. For example, injection molding, sheet extrusion molding, vacuum molding, blow molding, foam molding, profile extrusion molding, etc. are mentioned. In the case of molding, the chlorine-containing polymer-based resin composition is usually processed after being heated to 170 to 200°C, but it is preferably 190 to 200°C. Molded products can be used for rainwater drainage pipes, air conditioner pipe covers, plant pipes, pipes, fittings, sprinkler pipes, window frames, sashes, and industrial products.

(5-3. Maximum torque during melt-kneading of chlorine-containing polymer-based resin composition)

When performing extrusion molding of the chlorine-containing polymer-based resin composition, it is advantageous in melt-kneading to keep the maximum torque at the time of melt-kneading of the chlorine-containing polymer-based resin composition low. As an index, for example, the maximum torque at the time of adding 20 parts by mass of the maleimide-based copolymer to 100 parts by mass of the chlorine-containing polymer and performing melt kneading can be used. Although the preferable range of the maximum torque at the time of melt kneading can be replaced according to the actual extrusion conditions, for example, using a lab blast mill (4C150, mixer type R60) of Toyo Seiki Seisakusho Co., Ltd. It is preferable that the value of the maximum torque measured under conditions of 190°C, charging amount of 60.0 g, and 60 rpm is 50 N·m or less.

[Example]

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

<Manufacture example of maleimide copolymer (A-1)>

In an autoclave with a volume of about 120 liters equipped with a stirrer, 73 parts by mass of styrene, 18 parts by mass of acrylonitrile, 1 part by mass of maleic anhydride, 0.22 parts by mass of α-methylstyrene dimer, and 26 parts by mass of methyl ethyl ketone were added, After substituting the gas phase part with nitrogen gas, it heated up to 92 degreeC over 40 minutes, stirring. A solution obtained by dissolving 7 parts by mass of maleic anhydride and 1.0 part by mass of t-butylperoxy-2-ethylhexanoate in 35 parts by mass of methyl ethyl ketone was continuously added over 4.5 hours while maintaining 92°C after the temperature was raised. After completion of the addition, the temperature was raised to 120° C. and the reaction was performed for 1 hour to complete polymerization. Thereafter, 6 parts by mass of aniline and 0.1 part by mass of triethylamine were added to the polymerization liquid, and the mixture was reacted at 140°C for 7 hours. After completion of the reaction, the imidation reaction liquid was introduced into a vented screw type extruder, and volatile components were removed to obtain a pellet-shaped maleimide copolymer (A-1). Table 1 shows the analysis results of the obtained maleimide-based copolymer. In Tables 1 and 2, Sty represents a styrene monomer unit, AN represents an acrylonitrile monomer unit, MAH represents a maleic anhydride monomer unit, NPMI represents an N-phenylmaleimide monomer unit, and PVC represents polyvinyl chloride.

<Production example of maleimide copolymer (A-2)>

In an autoclave with a volume of about 120 liters equipped with a stirrer, 64 parts by mass of styrene, 20 parts by mass of acrylonitrile, 2 parts by mass of maleic anhydride, 0.5 parts by mass of α-methylstyrene dimer, and 31 parts by mass of methyl ethyl ketone were added, After substituting the gas phase part with nitrogen gas, it heated up to 92 degreeC over 40 minutes, stirring. A solution obtained by dissolving 14 parts by mass of maleic anhydride and 0.60 part by mass of t-butylperoxy-2-ethylhexanoate in 69 parts by mass of methyl ethyl ketone was continuously added over 5.5 hours while maintaining 92°C after the temperature was raised. After completion of the addition, the temperature was raised to 120° C., and the mixture was reacted for 1 hour to complete polymerization. Thereafter, 12 parts by mass of aniline and 0.2 part by mass of triethylamine were added to the polymerization liquid, and the mixture was reacted at 140°C for 7 hours. After completion of the reaction, the imidation reaction liquid was introduced into a vented screw type extruder, and volatile components were removed to obtain a pellet-shaped maleimide copolymer (A-2). Table 1 shows the analysis results of the obtained maleimide-based copolymer.

<Production example of maleimide copolymer (A-3)>

In an autoclave with a volume of about 120 liters equipped with a stirrer, 79 parts by mass of styrene, 9 parts by mass of acrylonitrile, 2 parts by mass of maleic anhydride, 0.52 parts by mass of α-methylstyrene dimer, and 33 parts by mass of methyl ethyl ketone were added, After substituting the gas phase part with nitrogen gas, it heated up to 92 degreeC over 40 minutes, stirring. A solution obtained by dissolving 9 parts by mass of maleic anhydride and 0.60 part by mass of t-butylperoxy-2-ethylhexanoate in 47 parts by mass of methyl ethyl ketone was continuously added over 5 hours while maintaining 92°C after the temperature was raised. After completion of the addition, the temperature was raised to 120° C., and the reaction was performed for 1.5 hours to terminate the polymerization. Thereafter, 9 parts by mass of aniline and 0.2 part by mass of triethylamine were added to the polymerization solution, and the mixture was reacted at 140°C for 7 hours. After completion of the reaction, the imidation reaction liquid was introduced into a vented screw type extruder, and volatile components were removed to obtain a pellet-shaped maleimide copolymer (A-3). Table 1 shows the analysis results of the obtained maleimide-based copolymer.

<Production example of maleimide copolymer (A-4)>

In an autoclave having a volume of about 120 liters equipped with a stirrer, 85 parts by mass of styrene, 7 parts by mass of acrylonitrile, 1 part by mass of maleic anhydride, 0.72 parts by mass of α-methylstyrene dimer, and 30 parts by mass of methyl ethyl ketone were added, After substituting the gas phase part with nitrogen gas, it heated up to 92 degreeC over 40 minutes, stirring. A solution obtained by dissolving 7 parts by mass of maleic anhydride and 0.80 part by mass of t-butylperoxy-2-ethylhexanoate in 33 parts by mass of methyl ethyl ketone was continuously added over 6 hours while maintaining 92°C after the temperature was raised. After completion of the addition, the temperature was raised to 120° C., and the mixture was reacted for 1 hour to complete polymerization. Thereafter, 5 parts by mass of aniline and 0.1 part by mass of triethylamine were added to the polymerization solution, and the mixture was reacted at 140°C for 7 hours. After completion of the reaction, the imidation reaction liquid was introduced into a vented screw type extruder, and volatile components were removed to obtain a pellet-shaped maleimide copolymer (A-4). Table 1 shows the analysis results of the obtained maleimide-based copolymer.

<Production example of maleimide copolymer (A-5)>

In an autoclave having a volume of about 120 liters equipped with a stirrer, 25 parts by mass of styrene, 26 parts by mass of acrylonitrile, 2 parts by mass of maleic anhydride, 0.53 parts by mass of α-methylstyrene dimer, and 30 parts by mass of methyl ethyl ketone were added, After substituting the gas phase part with nitrogen gas, it heated up to 92 degreeC over 40 minutes, stirring. After the temperature was raised, a solution in which 34 parts by mass of styrene, 13 parts by mass of maleic anhydride, and 0.22 parts by mass of t-butylperoxy-2-ethylhexanoate were dissolved in 67 parts by mass of methyl ethyl ketone was continuously dissolved over 3 hours while maintaining 92°C. added. Further, after completion of the addition of maleic anhydride, a solution obtained by dissolving 0.18 parts by mass of t-butylperoxy-2-ethylhexanoate in 1 part by mass of methyl ethyl ketone was continuously added over 2.5 hours. After completion of the addition, the temperature was raised to 120° C., and the mixture was reacted for 1 hour to complete polymerization. Thereafter, 12 parts by mass of aniline and 0.2 part by mass of triethylamine were added to the polymerization liquid, and the mixture was reacted at 140°C for 7 hours. After completion of the reaction, the imidation reaction liquid was introduced into a vented screw type extruder, and volatile components were removed to obtain a pellet-shaped maleimide copolymer (A-5). Table 1 shows the analysis results of the obtained maleimide-based copolymer.

<Production example of maleimide copolymer (A-6)>

In an autoclave having a volume of about 120 liters equipped with a stirrer, 23 parts by mass of styrene, 26 parts by mass of acrylonitrile, 2 parts by mass of maleic anhydride, 0.32 parts by mass of α-methylstyrene dimer, and 32 parts by mass of methyl ethyl ketone were added, After substituting the gas phase part with nitrogen gas, it heated up to 92 degreeC over 40 minutes, stirring. A solution of 33 parts by mass of styrene, 16 parts by mass of maleic anhydride, and 0.22 part by mass of t-butylperoxy-2-ethylhexanoate dissolved in 81 parts by mass of methyl ethyl ketone was continuously dissolved over 3 hours while maintaining 92° C. after the temperature was raised. added. Further, after completion of the addition of maleic anhydride, a solution obtained by dissolving 0.18 parts by mass of t-butylperoxy-2-ethylhexanoate in 1 part by mass of methyl ethyl ketone was continuously added over 2.5 hours. After completion of the addition, the temperature was raised to 120° C., and the mixture was reacted for 1 hour to complete polymerization. Thereafter, 14 parts by mass of aniline and 0.3 part by mass of triethylamine were added to the polymerization liquid, and the mixture was reacted at 140°C for 7 hours. After completion of the reaction, the imidation reaction liquid was introduced into a vented screw type extruder, and volatile components were removed to obtain a pellet-shaped maleimide copolymer (A-6). Table 1 shows the analysis results of the obtained maleimide-based copolymer.

<Manufacture example of maleimide copolymer (B-1)>

In an autoclave with a volume of about 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, 0.58 parts by mass of α-methylstyrene dimer, and 28 parts by mass of methyl ethyl ketone were added, After substituting the gas phase part with nitrogen gas, it heated up to 92 degreeC over 40 minutes, stirring. A solution obtained by dissolving 4 parts by mass of maleic anhydride and 1.0 part by mass of t-butylperoxy-2-ethylhexanoate in 18 parts by mass of methyl ethyl ketone was continuously added over 7.5 hours while maintaining 92°C after the temperature was raised. After completion of the addition, the temperature was raised to 120° C., and the mixture was reacted for 1 hour to complete polymerization. Thereafter, 3 parts by mass of aniline and 0.1 part by mass of triethylamine were added to the polymerization solution, and the mixture was reacted at 140°C for 7 hours. After completion of the reaction, the imidation reaction liquid was introduced into a vented screw type extruder, and volatile components were removed to obtain a pellet-shaped maleimide copolymer (B-1). Table 2 shows the analysis results of the obtained maleimide-based copolymer.

<Production example of maleimide copolymer (B-2)>

88 parts by mass of styrene, 1 part by mass of maleic anhydride, 0.48 parts by mass of α-methylstyrene dimer, and 29 parts by mass of methyl ethyl ketone were introduced into an autoclave having a volume of about 120 liters equipped with an agitator, and the gas phase part was substituted with nitrogen gas. Then, while stirring, the temperature was raised to 92°C over 40 minutes. A solution in which 11 parts by mass of maleic anhydride and 1.20 parts by mass of t-butylperoxy-2-ethylhexanoate were dissolved in 56 parts by mass of methyl ethyl ketone was continuously added over 8.5 hours while maintaining 92°C after the temperature was raised. After completion of the addition, the temperature was raised to 120° C., and the mixture was reacted for 1 hour to complete polymerization. Thereafter, 9 parts by mass of aniline and 0.2 part by mass of triethylamine were added to the polymerization solution, and the mixture was reacted at 140°C for 7 hours. After completion of the reaction, the imidation reaction liquid was introduced into a vented screw type extruder, and volatile components were removed to obtain a pellet-shaped maleimide copolymer (B-2). Table 2 shows the analysis results of the obtained maleimide-based copolymer.

<Manufacture example of maleimide copolymer (B-3)>

In an autoclave having a volume of about 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, 0.11 parts by mass of α-methylstyrene dimer, and 24 parts by mass of methyl ethyl ketone were added, After substituting the gas phase part with nitrogen gas, it heated up to 92 degreeC over 40 minutes, stirring. After the temperature was raised, a solution in which 31 parts by mass of styrene, 7 parts by mass of maleic anhydride, and 0.38 parts by mass of t-butylperoxy-2-ethylhexanoate were dissolved in 37 parts by mass of methyl ethyl ketone was continuously dissolved over 3.5 hours while maintaining 92°C. added. Further, after completion of the addition of maleic anhydride, a solution obtained by dissolving 0.22 parts by mass of t-butylperoxy-2-ethylhexanoate in 2 parts by mass of methyl ethyl ketone was continuously added over 2 hours. After completion of the addition, the temperature was raised to 120° C., and the mixture was reacted for 1 hour to complete polymerization. Thereafter, 6 parts by mass of aniline and 0.1 part by mass of triethylamine were added to the polymerization liquid, and the mixture was reacted at 140°C for 7 hours. After completion of the reaction, the imidation reaction liquid was introduced into a vented screw type extruder, and volatile components were removed to obtain a pellet-shaped maleimide copolymer (B-3). Table 2 shows the analysis results of the obtained maleimide-based copolymer.

<Production example of maleimide copolymer (B-4)>

In an autoclave with a volume of about 120 liters equipped with a stirrer, 63 parts by mass of styrene, 22 parts by mass of acrylonitrile, 2 parts by mass of maleic anhydride, 0.59 parts by mass of α-methylstyrene dimer, and 30 parts by mass of methyl ethyl ketone were added, After substituting the gas phase part with nitrogen gas, it heated up to 92 degreeC over 40 minutes, stirring. A solution obtained by dissolving 13 parts by mass of maleic anhydride and 0.44 part by mass of t-butylperoxy-2-ethylhexanoate in 69 parts by mass of methyl ethyl ketone was continuously added over 4 hours while maintaining 92°C after the temperature rise. Further, after completion of the maleic anhydride addition, a solution obtained by dissolving 0.16 parts by mass of t-butylperoxy-2-ethylhexanoate in 1 part by mass of methyl ethyl ketone was continuously added over 1.5 hours. After completion of the addition, the temperature was raised to 120° C., and the mixture was reacted for 1 hour to complete polymerization. Thereafter, 3 parts by mass of aniline and 0.2 part by mass of triethylamine were added to the polymerization solution, and the mixture was reacted at 140°C for 7 hours. After completion of the reaction, the imidation reaction liquid was introduced into a vented screw type extruder, and volatile components were removed to obtain a pellet-shaped maleimide copolymer (B-4). Table 2 shows the analysis results of the obtained maleimide-based copolymer.

<Production example of maleimide copolymer (B-5)>

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 introduced into an autoclave having a volume of about 120 liters equipped with an agitator, and the gas phase was substituted with nitrogen gas, followed by stirring While the temperature was raised to 92 ℃ over 40 minutes. A solution obtained by dissolving 3 parts by mass of maleic anhydride and 0.82 parts by mass of t-butylperoxy-2-ethylhexanoate in 23 parts by mass of methyl ethyl ketone was added continuously over 4.5 hours while maintaining 92°C after the temperature was raised. Further, after completion of the maleic anhydride addition, a solution obtained by dissolving 0.18 parts by mass of t-butylperoxy-2-ethylhexanoate in 1 part by mass of methyl ethyl ketone was continuously added over 1 hour. After completion of the addition, the temperature was raised to 120° C. and the reaction was performed for 1 hour to complete polymerization. Thereafter, 2 parts by mass of aniline and 0.1 part by mass of triethylamine were added to the polymerization solution, and the mixture was reacted at 140°C for 7 hours. After completion of the reaction, the imidation reaction liquid was introduced into a vented screw type extruder, and volatile components were removed to obtain a pellet-shaped maleimide copolymer (B-5). Table 2 shows the analysis results of the obtained maleimide-based copolymer.

<Production example of maleimide copolymer (B-6)>

In an autoclave having a volume of about 120 liters equipped with a stirrer, 24 parts by mass of styrene, 24 parts by mass of acrylonitrile, 2 parts by mass of maleic anhydride, 0.53 parts by mass of α-methylstyrene dimer, and 33 parts by mass of methyl ethyl ketone were added, After substituting the gas phase part with nitrogen gas, it heated up to 92 degreeC over 40 minutes, stirring. After the temperature was raised, a solution in which 33 parts by mass of styrene, 17 parts by mass of maleic anhydride, and 0.22 parts by mass of t-butylperoxy-2-ethylhexanoate were dissolved in 85 parts by mass of methyl ethyl ketone was continuously dissolved over 3 hours while maintaining 92°C. added. Further, after completion of the addition of maleic anhydride, a solution obtained by dissolving 0.18 parts by mass of t-butylperoxy-2-ethylhexanoate in 1 part by mass of methyl ethyl ketone was continuously added over 2.5 hours. After completion of the addition, the temperature was raised to 120° C., and the mixture was reacted for 1 hour to complete polymerization. Thereafter, 16 parts by mass of aniline and 0.3 part by mass of triethylamine were added to the polymerization liquid, and the mixture was reacted at 140°C for 7 hours. After completion of the reaction, the imidation reaction liquid was introduced into a vented screw type extruder, and volatile components were removed to obtain a pellet-shaped maleimide copolymer (B-6). Table 2 shows the analysis results of the obtained maleimide-based copolymer.

<Production example of maleimide copolymer (B-7)>

In an autoclave having a volume of about 120 liters equipped with a stirrer, 22 parts by mass of styrene, 10 parts by mass of acrylonitrile, 3 parts by mass of maleic anhydride, 0.45 parts by mass of α-methylstyrene dimer, and 39 parts by mass of methyl ethyl ketone were added, After substituting the gas phase part with nitrogen gas, it heated up to 92 degreeC over 40 minutes, stirring. After the temperature was raised, 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 continuously dissolved over 5 hours while maintaining 92°C. was added. After completion of the addition, the temperature was raised to 120° C., and the mixture was reacted for 1 hour to complete polymerization. Then, 23 mass parts of aniline and 0.4 mass part of triethylamine were added to the polymerization liquid, and it was made to react at 140 degreeC for 7 hours. After completion of the reaction, the imidation reaction liquid was introduced into a vented screw type extruder, and volatile components were removed to obtain a pellet-shaped maleimide copolymer (B-7). Table 2 shows the analysis results of the obtained maleimide-based copolymer.

<Production example of maleimide copolymer (B-8)>

In an autoclave having a volume of about 120 liters equipped with a stirrer, 79 parts by mass of styrene, 9 parts by mass of acrylonitrile, 2 parts by mass of maleic anhydride, 1.00 parts by mass of α-methylstyrene dimer, and 33 parts by mass of methyl ethyl ketone were added, After substituting the gas phase part with nitrogen gas, it heated up to 92 degreeC over 40 minutes, stirring. A solution obtained by dissolving 9 parts by mass of maleic anhydride and 0.60 part by mass of t-butylperoxy-2-ethylhexanoate in 47 parts by mass of methyl ethyl ketone was continuously added over 5 hours while maintaining 92°C after the temperature was raised. After completion of the addition, the temperature was raised to 120° C. and the reaction was performed for 1.5 hours to complete polymerization. Thereafter, 9 parts by mass of aniline and 0.2 part by mass of triethylamine were added to the polymerization solution, and the mixture was reacted at 140°C for 7 hours. After completion of the reaction, the imidation reaction liquid was introduced into a vented screw type extruder, and volatile components were removed to obtain a pellet-shaped maleimide copolymer (B-8). Table 2 shows the analysis results of the obtained maleimide-based copolymer.

<Manufacture example of maleimide copolymer (B-9)>

79 parts by mass of styrene, 9 parts by mass of acrylonitrile, 2 parts by mass of maleic anhydride, and 33 parts by mass of methyl ethyl ketone were introduced into an autoclave having a volume of about 120 liters equipped with an agitator, and the gas phase was substituted with nitrogen gas, followed by stirring While the temperature was raised to 92 ℃ over 40 minutes. A solution obtained by dissolving 9 parts by mass of maleic anhydride and 0.60 part by mass of t-butylperoxy-2-ethylhexanoate in 47 parts by mass of methyl ethyl ketone was continuously added over 5 hours while maintaining 92°C after the temperature was raised. After completion of the addition, the temperature was raised to 120° C., and the reaction was performed for 1.5 hours to terminate the polymerization. Thereafter, 9 parts by mass of aniline and 0.2 part by mass of triethylamine were added to the polymerization solution, and the mixture was reacted at 140°C for 7 hours. After completion of the reaction, the imidation reaction liquid was introduced into a vented screw type extruder, and volatile components were removed to obtain a pellet-shaped maleimide copolymer (B-9). Table 2 shows the analysis results of the obtained maleimide-based copolymer.

<Production example of maleimide copolymer (B-10)>

In an autoclave with a volume of about 120 liters equipped with a stirrer, 84 parts by mass of styrene, 12 parts by mass of acrylonitrile, 1 part by mass of maleic anhydride, 0.57 parts by mass of α-methylstyrene dimer, and 26 parts by mass of methyl ethyl ketone were added, After substituting the gas phase part with nitrogen gas, it heated up to 92 degreeC over 40 minutes, stirring. A solution obtained by dissolving 3 parts by mass of maleic anhydride and 0.82 parts by mass of t-butylperoxy-2-ethylhexanoate in 24 parts by mass of methyl ethyl ketone was continuously added over 4.5 hours while maintaining 92°C after the temperature was raised. Further, after completion of the maleic anhydride addition, a solution obtained by dissolving 0.18 parts by mass of t-butylperoxy-2-ethylhexanoate in 1 part by mass of methyl ethyl ketone was continuously added over 1 hour. After completion of the addition, the temperature was raised to 120° C., and the mixture was reacted for 1 hour to complete polymerization. Thereafter, 3 parts by mass of aniline and 0.1 part by mass of triethylamine were added to the polymerization solution, and the mixture was reacted at 140°C for 7 hours. After completion of the reaction, the imidation reaction liquid was introduced into a vented screw type extruder, and volatile components were removed to obtain a pellet-shaped maleimide copolymer (B-10). Table 2 shows the analysis results of the obtained maleimide-based copolymer.

<Chlorine-containing polymer-based resin composition>

(Raw materials used) The raw materials used for each example and each comparative example are shown below.

(1) Chlorine-containing polymer (PVC)

· Product name: TH-1000 (manufactured by Daiyoyeombi Co., Ltd.) was used.

(2) maleimide-based copolymer

· Obtained according to the above preparation example (A-1 to A-6, B-1 to B-10) were used.

Examples 1 to 6, Comparative Examples 1 to 10 (mixing by kneading of maleimide-based copolymer and chlorine-containing polymer)

A generally commercially available chlorine-containing polymer (product name: TH-1000) obtained by mixing maleimide-based copolymers (A-1 to A-6, B-1 to B-10) with a Henschel mixer after adding a stabilizer and a lubricant in advance. , Daiyoshibi Co., Ltd.) was blended in the blending ratio shown in Tables 1 and 2, and then a roll sheet was prepared using a test roll (φ6 × L15 test roll, manufactured by Kansai Roll Co., Ltd.), and the roll sheet was overlapped and press-molded, , A test piece was prepared by cutting or punching, and each physical property value was measured. A result is shown to Tables 1-2.

(composition analysis)

Composition analysis of each monomer unit was measured by the C-13 NMR method under the measurement conditions described below.

Device name: FT-NMR AVANCE300 (manufactured by BRUKER)

Solvent: Deuterated chloroform

Concentration: 14% by mass

Temperature: 27℃

Number of integrations: 8000 times

(weight average molecular weight)

The weight average molecular weight is a value in terms of polystyrene measured by gel permeation chromatography (GPC), and was measured under the following conditions.

Measurement name: SYSTEM-21 Shodex (manufactured by Showa Denko Co., Ltd.)

Column: 3 PL gel MIXED-B (manufactured by Polymer Laboratories) in series

Temperature: 40℃

Detection: Differential Refractive Index

Solvent: tetrahydrofuran

Concentration: 2% by mass

Calibration curve: Created using standard polystyrene (PS) (manufactured by Polymer Laboratories)

(melt viscosity)

Melt viscosity was measured under conditions of 190°C and a shear rate of 100/sec using a capillary die with L = 40 mm and D = 1 mm. A capillary rheometer 1D manufactured by Toyo Seiki Seisakusho Co., Ltd. was used as the measurement instrument.

(Bikat softening point)

Based on JIS K7206:1999, the Vicat softening point was measured using the 50 method (load 50N, temperature increase rate 50°C/hour) using a test piece having a size of 20 mm x 20 mm and a thickness of 4 mm. In addition, a HDT & VSPT tester manufactured by Toyo Seiki Seisakusho Co., Ltd. was used as the measuring instrument.

(yellowness index (YI))

It was measured based on JIS K-7373. The specific procedure is as follows.

1 g of the maleimide-based copolymer was dissolved in 25 mL of tetrahydrofuran. After dissolution, it was transferred to a corner cell for measurement. Under conditions of a temperature of 23°C and a humidity of 50%, a color difference was determined using a corner cell of a tetrahydrofuran solution as a blank by a transmission method using a CIE standard D65 light source, and the value was determined as yellowness.

Device name: SE7700 Spectrocolorimeter (manufactured by Nippon Denshoku Industrial Co., Ltd.)

Corner cell: A02277A 10×36×55H corner cell 2 sides transmission

(maximum torque)

The maximum torque of each Example and Comparative Example was measured as follows.

20 parts by mass of the maleimide-based copolymers of Examples and Comparative Examples were added to 80 parts by mass of the chlorine-containing polymer (TH-1000, manufactured by Daiyoshibi Co., Ltd.) mixed with a Henschel mixer after adding additives such as a stabilizer and a lubricant in advance. . In the melt-kneading of the maleimide-based copolymer and the chlorine-containing polymer, a labplast mill (type 4C150, mixer type R60, manufactured by Toyo Seiki Seisakusho Co., Ltd.) was used, with a filling amount of 60.0 g, a temperature of 190 ° C., and a rotation speed of 60 rpm. Under the conditions, the maximum torque (kneading torque, unit: N m) during kneading was measured.

When the value of the maximum torque is low, since it is advantageous for melt kneading, it becomes possible to preferably perform extrusion molding.

In Examples 1 to 6 using the chlorine-containing polymer-based resin composition employing the maleimide-based copolymer according to the present invention, the heat resistance of the chlorine-containing polymer was sufficiently improved. In addition, the yellowness of the maleimide-based copolymer used can be controlled low, and coloring in the resin composition and its molded product can be suppressed. In addition, the maximum torque at the time of melt-kneading of the maleimide-based copolymer and the chlorine-containing polymer was suppressed to a low level. It is expected that extrusion molding of molded articles can be carried out without problems.

In contrast, in Comparative Examples 1 to 10 using a chlorine-containing polymer-based resin composition employing a maleimide-based copolymer that does not satisfy the provisions of the present invention, there are cases where the heat resistance of the chlorine-containing polymer is not sufficiently improved. In addition, when the yellowness of the maleimide-based copolymer used is high, coloring of the resin composition and its molded body may become a problem. In addition, there were cases where it became impossible to knead the maleimide-based copolymer without melting with the chlorine-containing polymer, or the maximum torque at the time of melt-kneading increased.

According to the present invention, a maleimide-based copolymer capable of obtaining a chlorine-containing polymer-based resin composition in which coloration is suppressed while improving the heat resistance of the chlorine-containing polymer, and a chlorine-containing polymer system comprising the maleimide-based copolymer and the chlorine-containing polymer. A resin composition and a molded article thereof are provided, and are suitably used for molded articles requiring heat resistance and appearance performance, for example, a rainwater drain pipe or a pipe cover for an air conditioner. In addition, the chlorine-containing polymer-based resin composition according to the present invention is suitably used for extrusion molding.

Claims (10)

50 to 90% by mass of the aromatic vinyl-based monomer unit and the vinyl cyanide 0.5 to 25% by mass of monomer units, 0 to 10% by mass of the unsaturated acid anhydride monomer units, and 5 to 25% by mass of the maleimide monomer units,
The melt viscosity measured under the conditions of 190 ° C. and a shear rate of 100 / sec is 200 to 100000 Pa sec,
The weight average molecular weight is 2.5 to 120,000,
Maleimide-based copolymer for chlorine-containing polymers. A chlorine-containing polymer-based resin composition comprising 5 to 50% by mass of the maleimide-based copolymer according to claim 1 and 50 to 95% by mass of a chlorine-containing polymer. According to claim 2,
The melt viscosity is 200 ~ 70000 Pa · sec, chlorine-containing polymer-based resin composition. According to claim 2 or 3,
The weight average molecular weight of the maleimide-based copolymer is 5 to 100,000, chlorine-containing polymer-based resin composition. According to any one of claims 2 to 4,
The chlorine-containing polymer-type resin composition in which the said maleimide-type copolymer has 50-80 mass % of aromatic vinyl-type monomer units. According to any one of claims 2 to 5,
The chlorine-containing polymer-type resin composition in which the said maleimide-type copolymer has 5-20 mass % of vinyl cyanide-type monomer units. According to any one of claims 2 to 6,
The chlorine-containing polymer-type resin composition in which the said maleimide-type copolymer has 0.3-5 mass % of unsaturated acid anhydride monomeric units. According to any one of claims 2 to 7,
The chlorine-containing polymer-type resin composition in which the said maleimide-type copolymer has 5-24 mass % of maleimide-type monomer units. The chlorine-containing polymer-based resin composition according to any one of claims 2 to 8, wherein the maleimide-based monomer unit is N-aryl maleimide. A molded article characterized by being molded from the chlorine-containing polymer-based resin composition according to any one of claims 2 to 9.