JP2023149057A - Antibacterial heat-resistant resin composition - Google Patents

Abstract

To provide an antibacterial heat-resistant resin composition which is excellent in a balance among impact resistance, heat resistance and antibacterial property.SOLUTION: An antibacterial heat-resistant resin composition contains a maleimide-based copolymer (A) containing a first aromatic vinyl-based monomer unit and a first maleimide-based monomer unit, and an ABS-based resin (B), wherein in 100 pts.mass of the antibacterial heat-resistant resin composition, the content of the ABS-based resin (B) is 50.0-98.0 pts.mass, at least a part of the first maleimide-based monomer unit is a maleimide-based monomer unit having a tertiary amino group on a side chain, and in 100 pts.mass of the antibacterial heat-resistant resin composition, the content of the maleimide-based monomer unit having the tertiary amino group on the side chain is 0.80 pts.mass or more.SELECTED DRAWING: None

Description

The present invention relates to an antibacterial heat-resistant resin composition that has an excellent balance of impact resistance, heat resistance, and antibacterial properties.

In a maleimide copolymer containing an aromatic vinyl monomer unit and a maleimide monomer unit, a maleimide in which the NH site of the maleimide monomer unit is substituted with a tertiary amino group or a secondary amino group. It is known that there are copolymers based on these, which provide effects such as stain resistance, weather resistance, alkali resistance, and antibacterial properties (Patent Documents 1 to 3).

Japanese Unexamined Patent Publication No. 188407/1983 Special Publication No. 2013-518964 Patent No. 6730439

An object of the present invention is to provide an antibacterial heat-resistant resin composition that has an excellent balance of impact resistance, heat resistance, and antibacterial properties.

As a result of studies by the present inventors, a maleimide copolymer (A) containing a first aromatic vinyl monomer unit and a first maleimide monomer unit, and an ABS resin (B). An antibacterial heat-resistant resin composition containing 50.0 to 98.0 parts by mass of the ABS resin (B) in 100 parts by mass of the antibacterial heat-resistant resin composition, and at least one The first maleimide monomer unit in the part is a maleimide monomer unit having a tertiary amino group in the side chain, and the first maleimide monomer unit in the side chain is a maleimide monomer unit having a tertiary amino group in the side chain, and By using an antibacterial heat-resistant resin composition containing 0.80 parts by mass or more of a maleimide monomer unit having an amino group, the antibacterial resin composition has an excellent balance of impact resistance, heat resistance, and antibacterial properties. It has been found that a heat-resistant resin composition with high heat resistance can be obtained.
That is, the present invention
(1) An antibacterial heat-resistant copolymer containing a maleimide copolymer (A) containing a first aromatic vinyl monomer unit and a first maleimide monomer unit, and an ABS resin (B). A resin composition,
The content of the ABS resin (B) in 100 parts by mass of the antibacterial heat-resistant resin composition is 50.0 to 98.0 parts by mass,
At least some of the first maleimide monomer units are maleimide monomer units having a tertiary amino group in the side chain,
An antibacterial heat-resistant resin composition, wherein the content of a maleimide monomer unit having a tertiary amino group in a side chain is 0.80 parts by mass or more in 100 parts by mass of the antibacterial heat-resistant resin composition.
(2) The antibacterial resin composition according to (1), wherein the content of the maleimide copolymer (A) is 2.0 to 50.0 parts by mass in 100 parts by mass of the antibacterial heat-resistant resin composition. thing.
(3) The antibacterial heat-resistant resin composition according to (1) or (2), wherein the antibacterial heat-resistant resin composition has a Vicat softening temperature of 105° C. or higher based on JIS K7206:1999.
(4) Any one of (1) to (3), whose Charpy impact strength is 8.0 kJ/m ² or more, as measured using a notched test piece by the method described in JIS K7111-1. The antibacterial heat-resistant resin composition described in .
(5) The content of the maleimide monomer unit having a tertiary amino group in the side chain in 100 parts by mass of the antibacterial heat-resistant resin composition is 1.25 parts by mass or more, (1) to (4) ) The antibacterial heat-resistant resin composition according to any one of
(6) The content of maleimide monomer units having a tertiary amino group in the side chain is 20 parts by mass of the total amount of maleimide monomer units contained in the antibacterial heat-resistant resin composition. -80 parts by mass of the antibacterial heat-resistant resin composition according to any one of (1) to (5).
(7) The antibacterial heat-resistant resin composition further contains a maleimide copolymer (C) having a glass transition temperature of 150° C. to 190° C. and containing a second maleimide monomer unit, and The antibacterial property according to any one of (1) to (6), wherein the content of the maleimide copolymer (C) in 100 parts by mass of the antibacterial heat-resistant resin composition is 20.0 parts by mass or less. Heat-resistant resin composition.
(8) A method for producing the antibacterial heat-resistant resin composition according to any one of (1) to (6), wherein the maleimide copolymer (A) and the ABS resin (B) are combined in an extruder. ), wherein the extruder is a twin-screw extruder.
(9) A method for producing the antibacterial heat-resistant resin composition according to (7), wherein the maleimide copolymer (A), the ABS resin (B), and the maleimide copolymer are combined in an extruder. A manufacturing method comprising the step of melt-kneading (C), wherein the extruder is a twin-screw extruder.
(10) A molded article formed from the antibacterial heat-resistant resin composition according to any one of (1) to (7).
(11) The molded article according to (10), which is used as an interior or exterior member of an automobile.
Regarding.

The antibacterial heat-resistant resin composition according to this embodiment has an excellent balance of impact resistance, heat resistance, and antibacterial properties.

<Antibacterial heat-resistant resin composition>
The antibacterial heat-resistant resin composition according to one embodiment of the present invention comprises a maleimide copolymer (A) containing a first aromatic vinyl monomer unit and a first maleimide monomer unit; Contains ABS resin (B). Further, it may further contain a maleimide copolymer (C) having a glass transition temperature (Tmg) of 150° C. to 190° C. and containing a second maleimide monomer unit.
Each component will be explained in detail below.

<Maleimide copolymer (A)>
The maleimide copolymer (A) according to one embodiment of the present invention is a copolymer containing a first aromatic vinyl monomer unit and a first maleimide monomer unit. In one embodiment, it may further include a first unsaturated dicarboxylic anhydride monomer unit. The maleimide copolymer (A) may be used alone, or two or more types may be used in combination.

<First maleimide monomer unit>
Examples of the maleimide monomer from which the first maleimide monomer unit is derived include N-3-dimethylaminopropylmaleimide, N-3-diethylaminopropylmaleimide, N-3-dipropylaminopropylmaleimide, - N-tertiary amino group maleimide such as dimethylaminoethylmaleimide, N-diethylaminoethylmaleimide, N-dipropylaminoethylmaleimide, N-alkylmaleimide such as N-methylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, and N-phenylmaleimide, N-chlorophenylmaleimide, N-methylphenylmaleimide, N-methoxyphenylmaleimide, N-tribromophenylmaleimide, and the like. Among these, N-3-dimethylaminopropylmaleimide and N-phenylmaleimide are preferred from the viewpoint of economy, antibacterial effect, or heat resistance imparting properties. The first maleimide monomer unit may be used alone or in combination of two or more types. For the first maleimide monomer unit, for example, a raw material made of a maleimide monomer can be used. Alternatively, it can be obtained by imidizing a raw material consisting of unsaturated dicarboxylic anhydride monomer units with ammonia or a primary amine.

The maleimide copolymer (A) preferably contains 10 to 60 mass% of the first maleimide monomer unit in 100 mass% of the maleimide copolymer (A), and preferably contains 20 to 50 mass%. It is more preferable to do so. Specifically, the content of the first maleimide monomer unit is, for example, 10, 15, 20, 25, 30, 35, 40, 41, 42, 43, 44, 45, 50, 55, or 60 It is mass %, and may be within a range between any two of the numerical values exemplified here. If the content of the first maleimide monomer unit is within this range, the compatibility with the later-described ABS resin (B) will improve, and the antibacterial heat-resistant resin composition will have excellent impact strength. The content of the first maleimide monomer unit is a value measured by 13C-NMR. In addition, when the first maleimide monomer unit is used in combination, the content of the first maleimide monomer unit means the total amount of the first maleimide monomer unit used in combination.

At least some of the first maleimide monomer units according to this embodiment have a tertiary amino group in the side chain. That is, when using the first maleimide monomer unit in combination, the first maleimide monomer is N-tertiary amino group maleimide and the NH part is substituted with a substituent other than the tertiary amino group. Maleimide monomers may be used in combination. Moreover, in one embodiment of the present invention, all the first maleimide monomer units may have a tertiary amino group in the side chain.

<First aromatic vinyl monomer unit>
Examples of the aromatic vinyl monomer from which the first aromatic vinyl monomer unit is derived include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, Examples include ethylstyrene, p-tert-butylstyrene, α-methylstyrene, α-methyl-p-methylstyrene, and the like. Among these, styrene is preferred because it is industrially easily available, can be used at low cost, can be copolymerized with various monomers, and is lightweight and has excellent moldability. The first aromatic vinyl monomer unit may be used alone or in combination of two or more types.

The maleimide copolymer (A) preferably contains 40 to 90 mass% of the first aromatic vinyl monomer unit in 100 mass% of the maleimide copolymer (A), and preferably contains 50 to 80 mass% of the first aromatic vinyl monomer unit. % is more preferable. Specifically, for example, it is 40, 45, 50, 55, 56, 57, 58, 59, 60, 65, 70, 75, 80, 85 or 90% by mass, and any two of the numerical values exemplified here. It may be within the range between. If the content of the first aromatic vinyl monomer unit is within this range, the compatibility with the later-described ABS resin (B) will improve, and the antibacterial heat-resistant resin composition will have excellent impact strength. The content of the first aromatic vinyl monomer unit is a value measured by 13C-NMR. In addition, when the first aromatic vinyl monomer unit is used in combination, the content of the first aromatic vinyl monomer unit is equal to the content of the first aromatic vinyl monomer unit used in combination. means the total amount.

<First unsaturated dicarboxylic anhydride monomer unit>
Examples of the unsaturated dicarboxylic anhydride monomer from which the first unsaturated dicarboxylic anhydride monomer unit is derived include maleic anhydride, itaconic anhydride, citraconic anhydride, and aconitic anhydride. Examples include things. Among these, maleic anhydride is preferred from the viewpoint of industrial availability. The first unsaturated dicarboxylic anhydride monomer unit may be used alone, or two or more types may be used in combination.

The maleimide copolymer (A) preferably contains 0 to 10% by mass of the first unsaturated dicarboxylic anhydride monomer unit in 100% by mass of the maleimide copolymer (A), It is more preferable to contain up to 5% by mass. Specifically, for example, it is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10% by mass, and is within the range between any two of the numerical values exemplified here. Good too. If the content of the first unsaturated dicarboxylic acid anhydride monomer unit is within this range, the maleimide copolymer (A) will have excellent thermal stability. The content of the first unsaturated dicarboxylic anhydride monomer unit is a value measured by a titration method. In addition, when the first unsaturated dicarboxylic anhydride monomer unit is used together, the content of the first unsaturated dicarboxylic anhydride monomer unit is the same as the content of the first unsaturated dicarboxylic anhydride monomer unit used together. It means the total amount of acid anhydride monomer units.

In one aspect of the present invention, the maleimide copolymer (A) contains 10 to 60% by mass of the first maleimide monomer unit in 100% by mass of the maleimide copolymer (A), and the first aromatic monomer unit. It is preferable to contain 40 to 90% by mass of vinyl monomer units and 0 to 10% by mass of unsaturated dicarboxylic anhydride monomer units. More preferably, 20 to 50% by mass of the first maleimide monomer unit and 50 to 80% by mass of the first aromatic vinyl monomer unit are contained in 100% by mass of the maleimide copolymer (A). , contains 0 to 5% by mass of unsaturated dicarboxylic anhydride monomer units. If the structural unit is within the above range, the maleimide copolymer (A) will have excellent fluidity, heat resistance, and thermal stability.

<Other monomer units>
The maleimide copolymer (A) according to the present embodiment includes a first maleimide monomer unit, a first aromatic vinyl monomer, and a first unsaturated dicarboxylic anhydride monomer unit. Other monomer units may be copolymerized within a range that does not impede the effects of the present invention. Examples of monomers providing other monomer units include vinyl cyanide monomers such as acrylonitrile, methacrylonitrile, ethacrylonitrile, fumaronitrile, methyl acrylate, ethyl acrylate, Examples include acrylic ester monomers such as butyl acrylic ester, methacrylic ester monomers such as methyl methacrylic ester and ethyl methacrylic ester, acrylic amide, and methacrylic amide. Other monomer units may be used alone or in combination of two or more types.
Other monomer units can be copolymerized within a range that does not impede the effects of the present invention, but from the viewpoint of imparting heat resistance to the resin composition, the monomer units contained in the maleimide copolymer (A) are It is preferably 20% by mass or less, more preferably 10% by mass or less, when the total of 100% by mass is taken as 100% by mass.

<Intermediate glass transition temperature (Tmg) of maleimide copolymer (A)>
From the viewpoint of heat resistance imparting properties, the intermediate glass transition temperature (Tmg) of the maleimide copolymer (A) is preferably 105°C to 150°C, more preferably 115°C to 150°C. The glass transition temperature is a value measured by DSC, and is a value measured under the measurement conditions described below.
Device name: Robot DSC6200 manufactured by Seiko Instruments Co., Ltd.
Heating rate: 10℃/min

<Content of maleimide copolymer (A)>
The content of the maleimide copolymer (A) in one embodiment of the present invention is preferably 2.0 to 50.0 parts by mass, more preferably 2.0 parts by mass based on 100 parts by mass of the antibacterial heat-resistant resin composition. ~25.0 parts by mass. Preferred content of the maleimide copolymer (A) is, for example, 2.0, 3.0, 4.0, 5.0, 10.0, 15.0, 20.0, 25. 0, 30.0, 35.0, 40.0, 45.0, or 50.0 parts by mass, and may be within a range between any two of the numerical values exemplified here. If the content of the maleimide copolymer (A) is within this range, the physical properties of heat resistance and antibacterial properties can be balanced. In addition, when a maleimide copolymer (A) is used together, the content of the maleimide copolymer (A) means the total amount of the maleimide copolymer (A) used together.

<Maleimide copolymer (C)>
The maleimide copolymer (C) according to one embodiment of the present invention is different from the maleimide copolymer (A) and contains a second maleimide monomer unit. Moreover, it may further contain a second aromatic vinyl monomer unit and a second unsaturated dicarboxylic anhydride monomer unit. The maleimide copolymer (C) may be used alone, or two or more types may be used in combination.

<Second maleimide monomer unit>
As the maleimide monomer from which the second maleimide monomer unit is derived, for example, those exemplified as the above-mentioned first maleimide monomer unit can be used. Among these, N-3-dimethylaminopropylmaleimide and N-phenylmaleimide are preferred from the viewpoint of economy, antibacterial effect, or heat resistance imparting properties. The second maleimide monomer unit may be used alone or in combination of two or more types. For the second maleimide monomer unit, for example, a raw material made of a maleimide monomer can be used. Alternatively, it can be obtained by imidizing a raw material consisting of unsaturated dicarboxylic anhydride monomer units with ammonia or a primary amine.

The second maleimide monomer unit according to this embodiment may have a tertiary amino group in the side chain. That is, as the second maleimide monomer, an N-tertiary amino group maleimide and a maleimide monomer in which the NH moiety is substituted with a substituent other than the tertiary amino group may be used in combination. Furthermore, in one embodiment of the present invention, all the second maleimide monomer units do not need to have a tertiary amino group in their side chains.

The maleimide copolymer (C) preferably contains 20 to 70% by mass, preferably 30 to 60% by mass of the second maleimide monomer unit in 100% by mass of the maleimide copolymer (C). It is more preferable to do so. Specifically, the content of the second maleimide monomer unit is, for example, 20, 25, 30, 35, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 55, 60, 65, or 70% by mass, and may be within a range between any two of the numerical values exemplified here. If the content of the second maleimide monomer unit is within this range, the compatibility with the ABS resin (B) described below will improve, and the antibacterial heat-resistant resin composition will have excellent impact strength. The content of the second maleimide monomer unit is a value measured by 13C-NMR. In addition, when a second maleimide monomer unit is used in combination, the content of the second maleimide monomer unit means the total amount of the second maleimide monomer unit used in combination.

<Second aromatic vinyl monomer unit>
As the aromatic vinyl monomer from which the second aromatic vinyl monomer unit is derived, for example, those exemplified in the above-mentioned first aromatic vinyl monomer unit can be used. Among these, styrene is preferred because it is industrially easily available, can be used at low cost, can be copolymerized with various monomers, and is lightweight and has excellent moldability. The second aromatic vinyl monomer unit may be used alone or in combination of two or more types.

The maleimide copolymer (C) preferably contains 30 to 80 mass% of the second aromatic vinyl monomer unit in 100 mass% of the maleimide copolymer (C), and preferably 40 to 70 mass%. % is more preferable. Specifically, the content of the second aromatic vinyl monomer unit is, for example, 30, 35, 40, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 60, 65, 70, 75, or 80% by mass, and may be within a range between any two of the numerical values exemplified here. If the content of the second aromatic vinyl monomer unit is within this range, the compatibility with the later-described ABS resin (B) will improve, and the antibacterial heat-resistant resin composition will have excellent impact strength. The content of the second aromatic vinyl monomer unit is a value measured by 13C-NMR. In addition, when the second aromatic vinyl monomer unit is used in combination, the content of the second aromatic vinyl monomer unit is equal to the content of the second aromatic vinyl monomer unit used in combination. means the total amount.

<Second unsaturated dicarboxylic anhydride monomer unit>
Examples of the unsaturated dicarboxylic anhydride monomer from which the second unsaturated dicarboxylic anhydride monomer unit is derived include those exemplified in the above-mentioned first unsaturated dicarboxylic anhydride monomer unit. You can use the one you made. Among these, maleic anhydride is preferred from the viewpoint of industrial availability. The second unsaturated dicarboxylic anhydride monomer unit may be used alone, or two or more types may be used in combination.

The maleimide copolymer (C) preferably contains 0 to 10% by mass of the second unsaturated dicarboxylic anhydride monomer unit in 100% by mass of the maleimide copolymer (C), It is more preferable to contain up to 5% by mass. Specifically, for example, it is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10% by mass, and is within the range between any two of the numerical values exemplified here. Good too. If the content of the second unsaturated dicarboxylic anhydride monomer unit is within this range, the maleimide copolymer (C) will have excellent thermal stability. The content of the second unsaturated dicarboxylic anhydride monomer unit is a value measured by a titration method. In addition, when the second unsaturated dicarboxylic anhydride monomer unit is used together, the content of the second unsaturated dicarboxylic anhydride monomer unit is the same as the content of the second unsaturated dicarboxylic anhydride monomer unit used together. It means the total amount of acid anhydride monomer units.

In one embodiment of the present invention, the maleimide copolymer (C) contains 20 to 70% by mass of the second maleimide monomer unit in 100% by mass of the maleimide copolymer (C), and the second aromatic monomer unit. It is preferable to contain 30 to 80% by mass of vinyl monomer units and 0 to 10% by mass of second unsaturated dicarboxylic anhydride monomer units. More preferably, 30 to 60% by mass of the second maleimide monomer unit and 40 to 70% by mass of the second aromatic vinyl monomer unit are contained in 100% by mass of the maleimide copolymer (C). , contains 0 to 5% by mass of a second unsaturated dicarboxylic anhydride monomer unit. If the structural unit is within the above range, the maleimide copolymer (C) will have excellent fluidity, heat resistance, and thermal stability.

<Other monomers>
The maleimide copolymer (C) according to the present embodiment includes a second maleimide monomer unit, a third aromatic vinyl monomer, and a second unsaturated dicarboxylic anhydride monomer unit. Other monomer units may be copolymerized within a range that does not impede the effects of the present invention. Examples of monomers providing other monomer units include vinyl cyanide monomers such as acrylonitrile, methacrylonitrile, ethacrylonitrile, fumaronitrile, methyl acrylate, ethyl acrylate, Examples include acrylic ester monomers such as butyl acrylic ester, methacrylic ester monomers such as methyl methacrylic ester and ethyl methacrylic ester, acrylic amide, and methacrylic amide. Other monomer units may be used alone or in combination of two or more types.
Other monomer units can be copolymerized within a range that does not impede the effects of the present invention, but from the viewpoint of imparting heat resistance to the resin composition, the monomer units contained in the maleimide copolymer (C) are It is preferably 20% by mass or less, more preferably 10% by mass or less, when the total of 100% by mass is taken as 100% by mass.

<Intermediate glass transition temperature (Tmg) of maleimide copolymer (C)>
From the viewpoint of efficiently improving the heat resistance of the antibacterial heat-resistant resin composition, the intermediate glass transition temperature (Tmg) of the maleimide copolymer (C) is preferably 150°C to 190°C, more preferably The temperature is 170°C to 190°C. The glass transition temperature is a value measured by DSC, and is a value measured under the measurement conditions described below.
Device name: Robot DSC6200 manufactured by Seiko Instruments Co., Ltd.
Heating rate: 10℃/min

<Content of maleimide copolymer (C)>
The content of the maleimide copolymer (C) in one aspect of the present invention is preferably 20.0 parts by mass or less, more preferably 15.0 parts by mass or less based on 100 parts by mass of the antibacterial heat-resistant resin composition. It is. Specifically, the content of the maleimide copolymer (C) is, for example, 1.0, 2.0, 3.0, 4.0, 5.0, 10.0, 15.0, or 20. It is preferably 0 part by mass, and may be within a range between any two of the numerical values exemplified here. If the content of the maleimide copolymer (C) is within this range, the resin composition will have excellent heat resistance. In addition, when a maleimide copolymer (C) is used together, the content of the maleimide copolymer (C) means the total amount of the maleimide copolymer (C) used together.

<Production method of maleimide copolymer (A) and maleimide copolymer (C)>
As a method for producing the maleimide copolymer (A) and the maleimide copolymer (C), known methods can be employed. For example, there is a method of copolymerizing a monomer mixture consisting of an aromatic vinyl monomer, a maleimide monomer, an unsaturated dicarboxylic anhydride monomer, and other copolymerizable monomers. After copolymerizing a monomer mixture consisting of an aromatic vinyl monomer, an unsaturated dicarboxylic anhydride monomer, and other copolymerizable monomers, the unsaturated dicarboxylic anhydride monomer There is a method in which a part of the body unit is reacted with ammonia or a primary amine to imidize it and convert it into a maleimide monomer unit (hereinafter referred to as "post-imidization method").

Examples of the polymerization mode of the maleimide copolymer (A) and the maleimide copolymer (C) include solution polymerization and bulk polymerization. Solution polymerization is preferred from the viewpoint that a maleimide copolymer having a more uniform copolymerization composition can be obtained by polymerizing while performing partial addition or the like. It is preferable that the solvent for solution polymerization is non-polymerizable from the viewpoint that by-products are less likely to be produced and there are fewer adverse effects. For example, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and acetophenone, ethers such as tetrahydrofuran and 1,4-dioxane, aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene, N,N-dimethylformamide, and dimethyl These include sulfoxide, N-methyl-2-pyrrolidone, etc., and methyl ethyl ketone and methyl isobutyl ketone are preferred from the viewpoint of ease of solvent removal during devolatilization and recovery of the maleimide copolymer (A). The polymerization process may be a continuous polymerization type, a batch type (batch type), or a semi-batch type. The polymerization method is not particularly limited, but radical polymerization is preferred from the viewpoint that it can be manufactured with good productivity through a simple process.

In solution polymerization or bulk polymerization, a polymerization initiator and a chain transfer agent can be used, and the polymerization temperature is preferably in the range of 80 to 150°C. Examples of the polymerization initiator include azo compounds such as azobisisobutyronitrile, azobiscyclohexanecarbonitrile, azobismethylproponitrile, and azobismethylbutyronitrile, benzoyl peroxide, t-butylperoxybenzoate, 1 , 1-di(t-butylperoxy)cyclohexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexanoate, di-t-butyl peroxide, dicumyl peroxide, ethyl- These are peroxides such as 3,3-di-(t-butylperoxy)butyrate, and one or more of these may be used in combination. From the viewpoint of polymerization reaction rate and polymerization rate control, it is preferable to use an azo compound or an organic peroxide having a 10-hour half-life of 70 to 120°C. The amount of the polymerization initiator used is not particularly limited, but it is preferably used in an amount of 0.1 to 1.5% by mass, more preferably 0.1 to 1.5% by mass based on 100% by mass of all monomer units. It is 1.0% by mass. It is preferable that the amount of the polymerization initiator used is 0.1% by mass or more because a sufficient polymerization rate can be obtained. When the amount of the polymerization initiator used is 1.5% by mass or less, the polymerization rate can be suppressed, so reaction control becomes easy and it becomes easy to obtain the target molecular weight. Examples of chain transfer agents include n-octylmercaptan, n-dodecylmercaptan, t-dodecylmercaptan, α-methylstyrene dimer, ethyl thioglycolate, limonene, and terpinolene. The amount of chain transfer agent used is not particularly limited as long as the target molecular weight can be obtained, but is 0.1 to 0.8% by mass based on 100% by mass of all monomer units. It is preferably 0.15 to 0.5% by mass, and more preferably 0.15 to 0.5% by mass. If the amount of chain transfer agent used is 0.1% by mass to 0.8% by mass, the target molecular weight can be easily obtained.

The maleimide monomer units can be introduced into the maleimide copolymer (A) and the maleimide copolymer (C) by a method of copolymerizing maleimide monomers or by a post-imidization method. The post-imidization method is preferable because it reduces the amount of residual maleimide monomer in the maleimide copolymer (A) and maleimide copolymer (C). The post-imidization method is a process in which a monomer mixture consisting of an aromatic vinyl monomer, an unsaturated dicarboxylic anhydride monomer, and other copolymerizable monomers is copolymerized, and then unsaturated This is a method in which a part of the dicarboxylic anhydride monomer unit is reacted with ammonia or a primary amine to imidize it, thereby converting it into a maleimide monomer unit. Primary amines include, for example, dimethylaminopropylamine, methylamine, ethylamine, n-propylamine, iso-propylamine, n-butylamine, n-pentylamine, n-hexylamine, n-octylamine, and cyclohexylamine. , alkylamines such as decylamine, chloro- or bromo-substituted alkylamines, aromatic amines such as aniline, toluidine, and naphthylamine, and among these, dimethylaminopropylamine and aniline are preferred. These primary amines may be used alone or in combination of two or more. During post-imidization, a catalyst can be used to improve the dehydration ring closure reaction in the reaction of the primary amine with the unsaturated dicarboxylic anhydride monomer unit. The catalyst is, for example, a tertiary amine such as trimethylamine, triethylamine, tripropylamine, tributylamine, N,N-dimethylaniline, N,N-diethylaniline. The temperature of the post-imidization is preferably 100 to 250°C, more preferably 120 to 200°C. If the temperature of the imidization reaction is 100° C. or higher, the reaction rate will improve, which is preferable from the viewpoint of productivity. It is preferable that the temperature of the imidization reaction is 250° C. or lower, since deterioration of physical properties due to thermal deterioration of the maleimide copolymer (A) and the maleimide copolymer (C) can be suppressed.

Volatilization of the solvent used in solution polymerization and unreacted monomers from the solution after solution polymerization of maleimide copolymer (A) and maleimide copolymer (C) or from the solution after post-imidization. A known method can be used as a method for removing the component (devolatilization method). For example, a vacuum devolatilization tank equipped with a heater or a devolatilization extruder equipped with a vent can be used. The devolatilized molten maleimide copolymer (A) and maleimide copolymer (C) are transferred to a granulation process, where they are extruded into strands from a porous die and subjected to a cold cut method, an air hot cut method, It can be processed into pellets using an underwater hot cut method.

<ABS resin (B)>
The ABS resin (B) according to one embodiment of the present invention has ABS (vinyl cyanide-conjugated diene-aromatic vinyl graft copolymer) resin as an essential component, and optionally ASA resin, AES resin, SAN resin. This is a resin that is used in combination with at least one resin selected from (vinyl cyanide-aromatic vinyl copolymer). ABS resin is a graft copolymer obtained by graft copolymerizing at least a styrene monomer and an acrylonitrile monomer onto a rubbery polymer. For example, a butadiene rubber such as polybutadiene or styrene-butadiene copolymer is used as the rubbery polymer. At the time of graft copolymerization, two or more of these rubbery polymers may be used in combination. When using an acrylic rubber such as butyl acrylate or ethyl acrylate, an ASA resin may be used, and when using an ethylene rubber such as an ethylene-α-olefin copolymer, an AES resin may be used in combination.
The content of the ABS resin in the ABS resin (B) is preferably 10 to 100% by mass, more preferably 15 to 60% by mass based on 100% by mass of the ABS resin (B). Specifically, for example, it is 10, 15, 20, 25, 30, 35, 40, 45, 50, 60, 70, or 100% by mass, and within the range between any two of the numerical values exemplified here. There may be. Note that the ABS resin (B) may be substantially only an ABS resin.

<Conjugated diene monomer unit>
The conjugated diene monomer unit contained in the ABS resin (B) according to one embodiment of the present invention is a copolymerized rubber-like polymer. Examples of rubbery polymers include butadiene rubbers such as polybutadiene and styrene-butadiene copolymers, acrylic rubbers such as butyl acrylate and ethyl acrylate, and ethylene rubbers such as ethylene-α-olefin copolymers. Can be mentioned. These rubbery polymers may be used alone or in combination of two or more.

<Third aromatic vinyl monomer unit>
Examples of the aromatic vinyl monomer from which the third aromatic vinyl monomer unit contained in the ABS resin (B) according to an embodiment of the present invention are derived include the above-mentioned first Those exemplified in the explanation of the aromatic vinyl monomer unit can be used. Among these, styrene is preferred because it is industrially easily available, can be used at low cost, can be copolymerized with various monomers, and is lightweight and has excellent moldability. The third aromatic vinyl monomer unit may be used alone or in combination of two or more types.

<Vinyl cyanide monomer unit>
Examples of vinyl cyanide monomers from which vinyl cyanide monomer units contained in the ABS resin (B) according to an embodiment of the present invention include acrylonitrile, methacrylonitrile, and ethacrylonitrile. Examples include nitrile, fumaronitrile, and the like. Among these, acrylonitrile is preferred from the viewpoint of industrial availability. The vinyl cyanide monomer unit may be used alone, or two or more types may be used in combination.

<Production method of ABS resin (B)>
As a method for producing the ABS resin (B), a known method can be adopted. For example, production methods using emulsion polymerization and continuous bulk polymerization may be mentioned. A method using emulsion polymerization is preferred because it allows easy adjustment of the content of the rubbery polymer in the final antibacterial heat-resistant resin composition.

A method for producing ABS resin (B) by emulsion polymerization includes a method of emulsion graft polymerization of a third aromatic vinyl monomer and a vinyl cyanide monomer to a rubbery polymer latex (hereinafter referred to as (referred to as "emulsion graft polymerization method"). A graft copolymer latex can be obtained by emulsion graft polymerization.

In the emulsion graft polymerization method, water, an emulsifier, a polymerization initiator, and a chain transfer agent are used, and the polymerization temperature is preferably in the range of 30 to 90°C. Examples of emulsifiers include anionic surfactants, nonionic surfactants, and amphoteric surfactants. Examples of the polymerization initiator include organic peroxides such as cumene hydroperoxide, diisopropylenezene peroxide, t-butyl peroxyacetate, t-hexyl peroxybenzoate, and t-butyl peroxybenzoate, potassium persulfate, and ammonium persulfate. etc., azo compounds such as azobisbutyronitrile, reducing agents such as iron ions, secondary reducing agents such as sodium formaldehyde sulfoxylate, and chelating agents such as disodium ethylenediaminetetraacetate. Examples of chain transfer agents include n-octylmercaptan, n-dodecylmercaptan, t-dodecylmercaptan, α-methylstyrene dimer, ethyl thioglycolate, limonene, and terpinolene.

The latex of the graft copolymer can be coagulated by a known method, and the graft copolymer can be recovered. For example, a powdery graft copolymer can be obtained by adding a coagulant to the latex of the graft copolymer, coagulating the latex, washing and dehydrating it with a dehydrator, and passing through a drying process.

From the viewpoint of impact resistance, the content of the rubbery polymer in the graft copolymer obtained by the emulsion graft polymerization method is preferably 40 to 70% by mass, more preferably 45 to 65% by mass. . The content of the rubbery polymer can be adjusted, for example, by the ratio of the third aromatic vinyl monomer and the vinyl cyanide monomer to the rubbery polymer during emulsion graft polymerization.

The structural units other than the rubbery polymer of the graft copolymer obtained by the emulsion graft polymerization method are 65 to 85% by mass of the third aromatic vinyl monomer unit from the viewpoint of impact resistance and chemical resistance. , the vinyl cyanide monomer unit is preferably 15 to 35% by mass.

<Components other than graft copolymer>
When the above method for producing ABS resin (B) is carried out, components other than the graft copolymer are also produced at the same time. Components other than the graft copolymer include, for example, SAN resin. The SAN resin is a copolymer having a third aromatic vinyl monomer unit and a vinyl cyanide monomer unit, and includes, for example, a styrene-acrylonitrile copolymer.
The SAN resin may be contained in the ABS resin (B) as produced during the implementation of the method for producing the ABS resin (B), but the SAN resin may be separately produced by the method described below. In this case, the SAN resin may contain other monomer units in addition to the third aromatic vinyl monomer unit and vinyl cyanide monomer unit.

<Other monomer units>
Other monomer units of the SAN resin include, for example, (meth)acrylic ester monomer units such as methyl methacrylate, acrylic ester monomer units such as butyl acrylate and ethyl acrylate, and methacrylate monomer units. (Meth)acrylic acid monomer units such as acids, acrylic acid monomer units such as acrylic acid, and N-substituted maleimide monomer units such as N-phenylmaleimide can be used.

The constituent units of the SAN resin are preferably 60 to 90% by mass of the third aromatic vinyl monomer unit and 10 to 40% by mass of the vinyl cyanide monomer unit, and more preferably, the third aromatic vinyl monomer unit is 10 to 40% by mass. The content is 65 to 80% by mass of group vinyl monomer units, and 20 to 35% by mass of vinyl cyanide monomer units. When the structural unit is within the above range, the resulting antibacterial heat-resistant resin composition has an excellent balance between impact strength and fluidity. The third aromatic vinyl monomer unit and vinyl cyanide monomer unit are values measured by 13C-NMR.

As a method for producing SAN resin, a known method can be adopted. For example, it can be produced by bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, etc. As for the method of operating the reactor, any of a continuous type, a batch type (batch type), and a semi-batch type can be applied. From the standpoint of quality and productivity, bulk polymerization or solution polymerization is preferred, and continuous polymerization is preferred. Examples of solvents for bulk polymerization or solution polymerization include alkylbenzenes such as benzene, toluene, ethylbenzene, and xylene, ketones such as acetone and methyl ethyl ketone, and aliphatic hydrocarbons such as hexane and cyclohexane.

In bulk polymerization or solution polymerization of SAN resin, a polymerization initiator and a chain transfer agent can be used, and the polymerization temperature is preferably in the range of 120 to 170°C. Examples of the polymerization initiator include 1,1-di(t-butylperoxy)cyclohexane, 2,2-di(t-butylperoxy)butane, and 2,2-di(4,4-di-t-butyl). peroxyketals such as peroxycyclohexyl)propane and 1,1-di(t-amylperoxy)cyclohexane, hydroperoxides such as cumene hydroperoxide and t-butyl hydroperoxide, and t-butyl peroxyacetate. , alkyl peroxides such as t-amyl peroxyisononanoate, dialkyl peroxides such as t-butylcumyl peroxide, di-t-butyl peroxide, dicumyl peroxide, di-t-hexyl peroxide, Peroxy esters such as t-butylperoxyacetate, t-butylperoxybenzoate, t-butylperoxyisopropyl monocarbonate, t-butylperoxyisopropyl carbonate, polyethertetrakis (t-butylperoxycarbonate), etc. Peroxycarbonates, N,N'-azobis(cyclohexane-1-carbonitrile), N,N'-azobis(2-methylbutyronitrile), N,N'-azobis(2,4-dimethylvaleronitrile) , N,N'-azobis[2-(hydroxymethyl)propionitrile], etc., and these may be used alone or in combination of two or more. Examples of chain transfer agents include n-octylmercaptan, n-dodecylmercaptan, t-dodecylmercaptan, α-methylstyrene dimer, ethyl thioglycolate, limonene, and terpinolene.

As a devolatilization method for removing volatile components such as unreacted monomers and the solvent used in the solution polymerization from the solution after the completion of polymerization of the SAN resin, a known method can be adopted. For example, a vacuum devolatilization tank with a preheater or a devolatilization extruder with a vent can be used. The devolatilized molten SAN resin is transferred to a granulation process, extruded into a strand from a porous die, and can be processed into pellets by a cold cut method, an air hot cut method, or an underwater hot cut method.

The weight average molecular weight of the SAN resin is preferably from 50,000 to 250,000, more preferably from 70,000 to 200,000, from the viewpoint of impact resistance and moldability of the antibacterial heat-resistant resin composition. Specifically, for example, it is 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 200,000, and any of the numerical values exemplified here. It may be within a range between the two. The weight average molecular weight of the SAN resin is a polystyrene equivalent value measured in THF solvent using gel permeation chromatography (GPC), and is a value measured in the same manner as the maleimide copolymer (A). be. The weight average molecular weight can be adjusted by the type and amount of chain transfer agent during polymerization, solvent concentration, polymerization temperature, and type and amount of polymerization initiator.

As the ABS resin (B), for example, there is a method of using two types: a powdered graft copolymer obtained by an emulsion polymerization method and a pelletized SAN resin obtained by a continuous bulk polymerization method. It will be done. In addition, a powdery graft copolymer obtained by emulsion polymerization method and a pelletized SAN resin obtained by continuous bulk polymerization are melt-blended in an extruder etc. to obtain pelletized ABS resin (B). One method is to use a

The content of the graft copolymer in the ABS resin (B) is preferably 10 to 100% by mass, more preferably 15 to 60% by mass based on 100% by mass of the ABS resin (B). Specifically, for example, it is 10, 15, 20, 25, 30, 35, 40, 45, 50, 60, 70, or 100% by mass, and within the range between any two of the numerical values exemplified here. There may be. Note that the ABS resin (B) may be substantially only a graft copolymer.
Further, from the viewpoint of impact strength, the content of the rubber component in the ABS resin (B) is preferably 10 to 35% by mass, more preferably 12 to 30% by mass based on 100% by mass of the ABS resin (B). Mass%. Specifically, for example, it is 10, 15, 20, 25, 30, or 35% by mass, and may be within a range between any two of the numerical values exemplified here. Note that the rubber component refers to a soft polymer component that can impart impact strength to the material, and examples thereof include a conjugated diene component contained in polybutadiene, an acrylate component contained in acrylic rubber, and an ethylene propylene component contained in ethylene propylene rubber.

<Content of ABS resin (B)>
The content of the ABS resin (B) in one embodiment of the present invention is 50.0 to 98.0 parts by mass, preferably 75.0 to 98.0 parts by mass in 100 parts by mass of the antibacterial heat-resistant resin composition. It is. Specifically, the content of the ABS resin (B) is, for example, 50.0, 55.0, 60.0, 65.0, 70.0, 75.0, 80.0, 85.0, 90 .0, 95.0, 96.0, 97.0, or 98.0 parts by mass, and may be within a range between any two of the numerical values exemplified here. If the content of ABS resin (B) is within this range, it will have good impact resistance. In addition, when copolymer (B) is used together, the content of copolymer (B) means the total amount of copolymer (B) used together.

<Method for producing antibacterial heat-resistant resin composition>
As a method for producing an antibacterial heat-resistant resin composition in one embodiment of the present invention, for example, a maleimide copolymer (A), an ABS resin (B), and, if necessary, a maleimide copolymer (C) are used. , melt kneading using an extruder.

A known method can be used for melt-kneading using an extruder. As the extruder, a known device can be used, such as a twin-screw extruder, a single-screw extruder, a multi-screw extruder, a continuous kneader with a twin-screw rotor, and the like. From the viewpoint that the screw configuration can be arbitrarily set and the kneading properties can be adjusted, it is preferable to use a twin-screw extruder, and intermeshing co-rotating twin-screw extruders are generally widely used. Used and preferred. The cylinder temperature of the kneading section of the extruder in the embodiment of the present invention is higher than 260°C, preferably 270 to 330°C. If the cylinder temperature in the kneading section is 260° C. or lower, the dispersibility of the maleimide copolymer and the inorganic antibacterial agent will deteriorate, and the melt viscosity will be too high, making extrusion difficult.

A molded article can be obtained by molding the resin composition according to this embodiment by a known method. Examples of the molding method include injection molding, sheet extrusion molding, vacuum molding, blow molding, foam molding, and profile extrusion molding. Moreover, the obtained molded body is suitably used as an interior member or an exterior member of an automobile.

<Content of maleimide monomer unit having a tertiary amino group in the side chain in the antibacterial heat-resistant resin composition>
The antibacterial heat-resistant resin composition in one aspect of the present invention has a content of maleimide monomer units having a tertiary amino group in the side chain of 0.80 parts by mass or more in 100 parts by mass of the antibacterial heat-resistant resin composition. The amount is preferably 1.25 parts by mass or more, and more preferably 1.50 parts by mass or more. Specifically, for example, it is preferably 0.80, 1.00, 1.25, 1.50, 1.75, 2.00, 5.00, 15.00, or 20.00 parts by mass. , it may be within the range between any two of the numerical values exemplified here. If the content of the maleimide monomer unit having a tertiary amino group in the side chain in the antibacterial heat-resistant resin composition is within this range, it will have excellent antibacterial properties. In addition, when a maleimide monomer unit having a tertiary amino group in the side chain is used in combination, the content of the maleimide monomer unit having a tertiary amino group in the side chain is 3. It means the total amount of maleimide monomer units having grade amino groups. The content of the maleimide monomer unit having a tertiary amino group in the side chain in the antibacterial heat-resistant resin composition is a value measured by 13C-NMR.

The content of the maleimide monomer unit having a tertiary amino group in the side chain in the antibacterial heat-resistant resin composition is determined by the content in each of the maleimide copolymer (A) and the maleimide copolymer (C). The content of the maleimide monomer unit having a tertiary amino group in the side chain of the maleimide copolymer (A) and maleimide copolymer (C) in the antibacterial heat-resistant resin composition can be adjusted It can be controlled by adjusting the content of.

<Content of maleimide monomer unit having a tertiary amino group in the side chain in the maleimide monomer unit>
The antibacterial heat-resistant resin composition in one aspect of the present invention has a content of maleimide monomer units having a tertiary amino group in the side chain of 20 to 20 parts by mass in 100 parts by mass of the total maleimide monomer units. The amount is preferably 80 parts by weight, and more preferably 30 to 60 parts by weight. Specifically, for example, it is preferably 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, or 80 parts by mass, and any two of the numerical values exemplified here. It may be within the range between two. If the content of the maleimide monomer unit having a tertiary amino group in the side chain in the total amount of 100 parts by mass of the maleimide monomer unit is within this range, it has excellent antibacterial properties. In addition, when a maleimide monomer unit having a tertiary amino group in the side chain is used in combination, the content of the maleimide monomer unit having a tertiary amino group in the side chain is 3. It means the total amount of maleimide monomer units having grade amino groups. The content of the maleimide monomer unit having a tertiary amino group in the side chain in the maleimide monomer unit can be determined by measuring the content of the maleimide monomer unit in the antibacterial heat-resistant resin composition by 13C-NMR. It can be calculated from the measured value and the content of the maleimide monomer unit having a tertiary amino group in the side chain in the antibacterial heat-resistant resin composition.

The content of the maleimide monomer unit having a tertiary amino group in the side chain in 100 parts by mass of the total amount of the maleimide monomer unit is the content of the maleimide copolymer (A) and the maleimide copolymer ( It can be controlled by adjusting the content of the maleimide monomer unit having a tertiary amino group in the side chain contained in each of C).

<Vicat softening temperature of antibacterial heat-resistant resin composition>
The Vicat softening temperature of the antibacterial heat-resistant resin composition in one aspect of the present invention based on JIS K7206:1999 is preferably 105°C or higher, more preferably 106°C or higher. Specifically, for example, it is preferably 105, 106, 107, 108, 109, 110, 115, 120, or 125°C, and even within the range between any two of the numerical values exemplified here. good. If the Vicat softening temperature is within this range, the antibacterial heat-resistant resin composition will have sufficient heat resistance.
The Vicat softening point can be measured, for example, based on JIS K7206:1999 using the 50 method (load 50 N, temperature increase rate 50° C./hour) using a test piece measuring 20 mm×20 mm and 4 mm thick. As the measuring device, for example, an HDT&VSPT test device manufactured by Toyo Seiki Seisakusho Co., Ltd. can be used.

<Charpy impact strength of test piece obtained from antibacterial heat-resistant resin composition>
In the antibacterial heat-resistant resin composition according to one aspect of the present invention, the Charpy impact strength measured using a notched test piece by the method described in JIS K7111-1 is 8.0 kJ/m ² or more. is preferable, and more preferably 15 kJ/m ² or more. Specifically, for example, 8.0, 9.0, 10.0, 14.0, 15.0, 16.0, 17.0, 18.0, 19.0, 20.0, or 25.0. It is preferably 0 kJ/m ² , and may be within a range between any two of the numerical values exemplified here. If the Charpy impact strength is within this range, the molded article obtained from the antibacterial heat-resistant resin composition will have sufficient impact strength.
Charpy impact strength can be measured, for example, in accordance with JIS K-7111, using a notched test piece, using an edgewise impact direction, and at a relative humidity of 50% and an ambient temperature of 23°C. As the measuring device, for example, a digital impact tester manufactured by Toyo Seiki Seisakusho Co., Ltd. can be used.

At the time of melt-kneading, an antioxidant can be used in combination, and the antioxidant may be a hindered phenol antioxidant or a phosphorus antioxidant, either alone or in combination. By adding an antioxidant, it is possible to prevent yellowing of the antibacterial heat-resistant resin composition during molding and during actual use.

A hindered phenolic antioxidant is an antioxidant that has a phenolic hydroxyl group in its basic skeleton. Examples of hindered phenolic antioxidants include octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, ethylenebis(oxyethylene)bis[3-(5-tert-butyl- 4-hydroxy-m-tolyl)propionate], 3,9-bis[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]- 2,4,8,10-tetraoxaspiro[5.5]undecane, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 4,6-bis(octyl) thiomethyl)-o-cresol, 4,6-bis[(dodecylthio)methyl]-o-cresol, 2,4-dimethyl-6-(1-methylpentadecyl)phenol, tetrakis[methylene-3-(3, 5-di-t-butyl-4-hydroxyphenyl)propionate] methane, 4,4'-thiobis(6-t-butyl-3-methylphenol), 1,1,3-tris(2-methyl-4- hydroxy-5-t-butylphenyl)butane, 4,4'-butylidenebis(3-methyl-6-t-butylphenol), bis-[3,3-bis-(4'-hydroxy-3'-tert-butyl) phenyl)-butanoic acid]-glycol ester, 2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenylacrylate, 2-[1-(2-hydroxy -3,5-di-t-pentylphenyl)ethyl]-4,6-di-t-pentylphenyl acrylate and the like. Preferably, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, ethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl) pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]. More preferred is octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate. The hindered phenolic antioxidant may be used alone or in combination of two or more types.

Phosphorous antioxidants are phosphite esters that are trivalent phosphorus compounds. The phosphorus antioxidant is, for example, 6-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-t-butylbenz[d,f [1,3,2]dioxaphosphepine, 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9- Diphosphaspiro[5.5]undecane, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, 2,2'-methylenebis(4,6-di-tert-butyl-1-phenyloxy)(2-ethylhexyl) oxy)phosphorus, tris(2,4-di-tert-butylphenyl)phosphite, bis[2,4-bis(1,1-dimethylethyl)-6-methylphenyl]ethyl ester phosphorous acid, bis(2 , 4-di-tert-butylphenyl) pentaerythritol diphosphite, cyclic neopentanetetrylbis (octadecyl phosphite), bis(nonylphenyl) pentaerythritol diphosphite, 4,4'-biphenylene diphosphinic acid tetrakis ( 2,4-di-tert-butylphenyl), 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, tetrakis(2,4-di-tert-butyl-5-methylphenyl)- Examples include 4,4'-biphenylene diphosphonite. Preferably, 6-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-t-butylbenz[d,f][1,3, 2] Dioxaphosphepine, 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5] Undecane, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, 2,2'-methylenebis(4,6-di-tert-butyl-1-phenyloxy)(2-ethylhexyloxy)phosphorus, tris( 2,4-di-tert-butylphenyl) phosphite and bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite. More preferably, 6-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-t-butylbenz[d,f][1,3 , 2] Dioxaphosphepine, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl)phosphite, bis(2,4-di-tert -butylphenyl)pentaerythritol diphosphite, more preferably 6-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-t -Butylbenz[d,f][1,3,2]dioxaphosphepine, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)penta It is erythritol diphosphite. The phosphorus antioxidants may be used alone or in combination of two or more.

When producing the antibacterial heat-resistant resin composition, other resin components, impact modifiers, fluidity modifiers, hardness modifiers, antioxidants, inorganic fillers, Matting agents, flame retardants, flame retardant aids, anti-drip agents, sliding properties agents, heat dissipating materials, electromagnetic wave absorbers, plasticizers, lubricants, mold release agents, ultraviolet absorbers, light stabilizers, anti-mold agents, Antistatic agents, carbon black, titanium oxide, pigments, dyes, etc. may be added.

Hereinafter, detailed contents will be explained using examples, but the present invention is not limited to the following examples.

<Production example of maleimide copolymer (A-1)>
A maleimide copolymer (A-1) was produced in the following manner.
In an autoclave with a capacity of approximately 120 liters equipped with a stirrer, 66 parts by mass of styrene, 12.3 parts by mass of maleic anhydride, 0.2 parts by mass of 2,4-diphenyl-4-methyl-1-pentene, and 31 parts by mass of methyl ethyl ketone. After purging the system with nitrogen gas, the temperature was raised to 92°C, and 5.3 parts by mass of maleic anhydride and 0.19 parts by mass of t-butylperoxy-2-ethylhexanoate were added. A solution prepared by dissolving the above in 110 parts by mass of methyl ethyl ketone was added continuously over 7 hours. After the addition, the temperature was raised to 120°C and the reaction was carried out for 30 minutes to complete the polymerization. Thereafter, 16.5 parts by mass of dimethylaminopropylamine and 0.6 parts by mass of triethylamine were added to the polymerization solution, and the mixture was reacted at 140° C. for 7 hours. After the completion of the reaction, the imidization reaction solution was put into a vent type screw extruder, and volatile components were removed to obtain a maleimide copolymer (A-1) in the form of pellets. The composition of the maleimide copolymer (A-1) is 68% by mass of styrene units, 30% by mass of N-3-dimethylaminopropylmaleimide units, and 2% by mass of maleic anhydride units, and has an intermediate glass transition temperature (Tmg). was 120°C. The analysis results are shown in Table 1.

<Production example of maleimide copolymer (A-2)>
A maleimide copolymer (A-2) was produced in the following manner.
In an autoclave with a capacity of about 120 liters equipped with a stirrer, 51.9 parts by mass of styrene, 17.2 parts by mass of maleic anhydride, 0.2 parts by mass of 2,4-diphenyl-4-methyl-1-pentene, and methyl ethyl ketone. After charging 31 parts by mass and purging the system with nitrogen gas, the temperature was raised to 92°C, and 7.4 parts by mass of maleic anhydride and 0.19 parts of t-butylperoxy-2-ethylhexanoate were added. A solution in which parts by mass were dissolved in 110 parts by mass of methyl ethyl ketone was continuously added over 7 hours. After the addition, the temperature was raised to 120°C and the reaction was carried out for 30 minutes to complete the polymerization. Thereafter, 23.6 parts by mass of dimethylaminopropylamine and 0.6 parts by mass of triethylamine were added to the polymerization solution and reacted at 140° C. for 7 hours. After the completion of the reaction, the imidization reaction solution was put into a vent type screw extruder, and volatile components were removed to obtain a maleimide copolymer (A-2) in the form of pellets. The composition of the maleimide copolymer (A-2) is 54% by mass of styrene units, 44% by mass of N-3-dimethylaminopropylmaleimide units, and 2% by mass of maleic anhydride units, and has an intermediate glass transition temperature (Tmg). The temperature was 133°C. The analysis results are shown in Table 1.

<Production example of maleimide copolymer (A-3)>
A maleimide copolymer (A-3) was produced in the following manner.
In an autoclave with a capacity of about 120 liters equipped with a stirrer, 81 parts by mass of styrene, 7.0 parts by mass of maleic anhydride, 0.2 parts by mass of 2,4-diphenyl-4-methyl-1-pentene, and 31 parts by mass of methyl ethyl ketone. After purging the system with nitrogen gas, the temperature was raised to 92°C, and 3.0 parts by mass of maleic anhydride and 0.19 parts by mass of t-butylperoxy-2-ethylhexanoate were added. A solution prepared by dissolving the above in 110 parts by mass of methyl ethyl ketone was added continuously over 7 hours. After the addition, the temperature was raised to 120°C and the reaction was carried out for 30 minutes to complete the polymerization. Thereafter, 9.1 parts by mass of dimethylaminopropylamine and 0.6 parts by mass of triethylamine were added to the polymerization solution, and the mixture was reacted at 140° C. for 7 hours. After the completion of the reaction, the imidization reaction solution was put into a vent type screw extruder, and volatile components were removed to obtain a maleimide copolymer (A-3) in the form of pellets. The composition of the maleimide copolymer (A-3) is 82% by mass of styrene units, 16% by mass of N-3-dimethylaminopropylmaleimide units, and 2% by mass of maleic anhydride units, and has an intermediate glass transition temperature (Tmg). The temperature was 113°C. The analysis results are shown in Table 1.

<Production example of maleimide copolymer (C-1)>
A maleimide copolymer (C-1) was produced in the following manner.
In an autoclave with a capacity of about 120 liters equipped with a stirrer, 50 parts by mass of styrene, 18.5 parts by mass of maleic anhydride, 0.0.2 parts by mass of 2,4-diphenyl-4-methyl-1-pentene, and methyl ethyl ketone. After charging 31 parts by mass and purging the system with nitrogen gas, the temperature was raised to 92°C, and 7.9 parts by mass of maleic anhydride and 0.19 parts of t-butylperoxy-2-ethylhexanoate were added. A solution in which parts by mass were dissolved in 110 parts by mass of methyl ethyl ketone was continuously added over 7 hours. After the addition, the temperature was raised to 140°C and the reaction was carried out for 30 minutes to complete the polymerization. Thereafter, 23.6 parts by mass of aniline and 0.6 parts by mass of triethylamine were added to the polymerization solution and reacted at 140° C. for 7 hours. After the completion of the reaction, the imidization reaction solution was put into a vent type screw extruder, and volatile components were removed to obtain a maleimide copolymer (C-1) in the form of pellets. The composition of the maleimide copolymer (C-1) is 52% by mass of styrene units, 46% by mass of N-phenylmaleimide units, and 2% by mass of maleic anhydride units, and the intermediate glass transition temperature (Tmg) is 185°C. there were. The analysis results are shown in Table 1.

<ABS resin (B)>
<Graft copolymer (B-1)>
A graft copolymer (B-1) was produced in the following manner.
The graft copolymer (B-1) was produced by emulsion graft polymerization. In a reaction vessel equipped with a stirrer, 126 parts by mass of polybutadiene latex with an average particle diameter of 0.3 μm, 17 parts by mass of styrene-butadiene latex with an average particle diameter of 0.5 μm and a styrene content of 24% by mass, and sodium stearate. 1 part by mass, 0.2 parts by mass of sodium formaldehyde sulfoxylate, 0.01 part by mass of tetrasodium ethylenediamine tetraacetic acid, 0.005 parts by mass of ferrous sulfate, and 150 parts of pure water. Heated to 50°C. To this, 45 parts by mass of a monomer mixture of 75% by mass of styrene and 25% by mass of acrylonitrile, 1.0 parts by mass of t-dodecylmercaptan, and 0.15 parts by mass of cumene hydroperoxide were added continuously in portions over 6 hours. After the addition was completed in portions, the temperature was raised to 65° C., and polymerization was completed over a further 2 hours to obtain a latex of graft copolymer (B-1). The obtained latex was coagulated using magnesium sulfate and sulfuric acid as coagulants so that the pH of the slurry at the time of coagulation was 6.8, washed, dehydrated, and dried to form a powdery graft copolymer (B -1) was obtained.
The Tg of the obtained graft copolymer (B-1) was -85°C.
In addition, in 100% by mass of the graft copolymer (B-1), the content of aromatic vinyl monomer units is 31.9% by mass, and the content of vinyl cyanide monomer units is 10.6% by mass. %, and the content of conjugated diene monomer units was 57.5% by mass.
・SAN resin (B-2) (copolymer of styrene and acrylonitrile): AS-EXS, manufactured by Denka Corporation ・SAN resin (B-3) (copolymer of styrene and acrylonitrile): GR-AT-6S, Manufactured by Denka Co., Ltd.

<Example/Comparative example>
The maleimide copolymer (A), the ABS resin (B), and if necessary the maleimide copolymer (C) are melt-kneaded using an extruder in the proportions shown in Table 2 or Table 3, and antibacterial A heat-resistant resin composition was manufactured. A twin screw extruder (TEM-35B manufactured by Toshiba Machine Co., Ltd.) was used as the extruder, and extrusion was performed at a screw rotation speed of 250 rpm and a feed rate of 30 kg/hr. The evaluation results are shown in Tables 2 and 3.

(Melt mass flow rate)
The melt mass flow rate of the resin composition was measured at 220° C. and a load of 10 kg based on JIS K7210.

(Vicat softening temperature)
The Vicat softening point of the resin composition was measured based on JIS K7206 using the 50 method (load 50 N, temperature increase rate 50° C./hour) using a test piece measuring 10 mm×10 mm and 4 mm thick. The measuring device used was an HDT & VSPT testing device manufactured by Toyo Seiki Seisakusho.

(Charpy impact strength)
The Charpy impact strength of the resin composition was measured based on JIS K7111-1 using a notched test piece and using an edgewise impact direction. The measuring device used was a digital impact tester manufactured by Toyo Seiki Seisakusho.

(Antibacterial property against Staphylococcus aureus)
Using the pellets obtained in the production of the antibacterial heat-resistant resin composition, a plate-shaped molded product with a thickness of 127 x 127 x 2 mm was formed using an injection molding machine (J140AD-180H, manufactured by Japan Steel Works, Ltd.) at a molding temperature of 260°C. Molded. A test was conducted using the molded product according to JIS Z 2801:2012 Antibacterial Processed Products - Antibacterial Test Method/Antibacterial Effect (Film Adhesion Method). The test conditions are as follows.
Bacterial species: E. coli (E. coli) NBRC3972, S. aureus (Staphylococcus aureus) NBRC12732
Bacterial liquid conditions: 1/500NB, 0.4mL
Working conditions: 35℃, 24 hours

Regarding the obtained results, the following judgments were made with reference to the method for measuring antibacterial activity values described in the antibacterial performance standards for antibacterial products of the Antibacterial Product Technology Council.
Antibacterial activity value 3.0 or more: ◎ (very excellent)
Antibacterial activity value is 2.0 or more and less than 3.0: ○ (excellent)
Antibacterial activity value is 1.0 or more and less than 2.0: △ (good)
Antibacterial activity value less than 1.0: × (poor)

(Heat-resistant)
Regarding the measurement results of the Vicat softening temperature of the resin composition, heat resistance was evaluated based on the following criteria.
Vicat softening temperature is 110℃ or higher: ◎ (very excellent)
Vicat softening temperature is 105℃ or higher and lower than 110℃: ○ (excellent)
Vicat softening temperature less than 105℃: △ (good)

(Impact resistance)
Regarding the Charpy impact strength measurement results, heat resistance was evaluated based on the following criteria.
Charpy impact strength of 12.0 kJ/ ^m2 or more: ◎ (very excellent)
Charpy impact strength is 8.0 kJ/ ^m2 or more and less than 12.0 kJ/ ^m2 : ○ (excellent)
Charpy impact strength less than 8.0 kJ/ ^m2 : × (good)

Examples 1 to 16 using the antibacterial heat-resistant resin composition of the present invention had an excellent balance of impact resistance, heat resistance, and antibacterial properties.
On the other hand, in Comparative Examples 1 to 6 using antibacterial heat-resistant resin compositions and resin compositions that do not meet the provisions of the present invention, the performance was inferior in at least one of impact resistance, heat resistance, and antibacterial properties. Ta.

According to the present invention, an antibacterial heat-resistant resin composition having excellent impact resistance and heat resistance and antibacterial properties is provided, and the composition is an interior material for automobiles that requires an excellent balance of impact resistance, heat resistance, and antibacterial properties. It is suitable for use in applications such as.

Claims (11)

An antibacterial heat-resistant resin composition containing a maleimide copolymer (A) containing a first aromatic vinyl monomer unit and a first maleimide monomer unit, and an ABS resin (B). And,
The content of the ABS resin (B) in 100 parts by mass of the antibacterial heat-resistant resin composition is 50.0 to 98.0 parts by mass,
At least some of the first maleimide monomer units are maleimide monomer units having a tertiary amino group in the side chain,
The content of the maleimide monomer unit having a tertiary amino group in the side chain in 100 parts by mass of the antibacterial heat-resistant resin composition is 0.80 parts by mass or more.
Antibacterial heat-resistant resin composition. The antibacterial resin composition according to claim 1, wherein the content of the maleimide copolymer (A) is 2.0 to 50.0 parts by mass in 100 parts by mass of the antibacterial heat-resistant resin composition. The antibacterial heat-resistant resin composition according to claim 1 or 2, wherein the antibacterial heat-resistant resin composition has a Vicat softening temperature of 105° C. or higher based on JIS K7206:1999. According to any one of claims 1 to 3, the Charpy impact strength is 8.0 kJ/m ² or more, as measured by the method described in JIS K7111-1 using a notched test piece. antibacterial heat-resistant resin composition. Any one of claims 1 to 4, wherein the content of the maleimide monomer unit having a tertiary amino group in the side chain in 100 parts by mass of the antibacterial heat-resistant resin composition is 1.25 parts by mass or more. The antibacterial heat-resistant resin composition according to item (1). The content of maleimide monomer units having a tertiary amino group in the side chain is 20 to 80 parts by mass in the total amount of 100 parts by mass of maleimide monomer units contained in the antibacterial heat-resistant resin composition. The antibacterial heat-resistant resin composition according to any one of claims 1 to 5, which is The antibacterial heat-resistant resin composition further contains a maleimide copolymer (C) having a glass transition temperature of 150° C. to 190° C. and containing a second maleimide monomer unit, and the antibacterial heat-resistant resin composition The antibacterial heat-resistant resin composition according to any one of claims 1 to 6, wherein the content of the maleimide copolymer (C) in 100 parts by mass of the resin composition is 20.0 parts by mass or less. thing. A method for producing an antibacterial heat-resistant resin composition according to any one of claims 1 to 6, comprising melting the maleimide copolymer (A) and the ABS resin (B) in an extruder. A manufacturing method including a step of kneading, wherein the extruder is a twin screw extruder. 8. The method for producing an antibacterial heat-resistant resin composition according to claim 7, wherein the maleimide copolymer (A), the ABS resin (B), and the maleimide copolymer (C) are processed in an extruder. A manufacturing method comprising the step of melt-kneading the extruder, wherein the extruder is a twin-screw extruder. A molded article formed from the antibacterial heat-resistant resin composition according to any one of claims 1 to 7. The molded article according to claim 10, which is used as an interior or exterior member of an automobile.