JP7655670B2 - Resin composition - Google Patents

Description

This disclosure relates to a resin composition and a molded article made from the resin composition.

Alloy resin (PC/ABS resin) made of polycarbonate resin (PC resin) and styrene-acrylonitrile-butadiene resin (ABS resin) is widely used in vehicle parts, home appliances, and office equipment parts because of its excellent impact resistance, heat resistance, and moldability.

Patent Document 1 discloses a resin composition containing PC resin, ABS resin, and a styrene-maleic anhydride copolymer. Patent Document 2 discloses a resin composition containing a rubber-reinforced vinyl resin, a polyolefin resin, and a PC resin.

JP 2015-131867 A JP 2019-19238 A

There is a demand for further improvement in heat resistance of PC/ABS resins.
The present disclosure has been made in consideration of the above-mentioned circumstances, and has an object to provide a resin composition having excellent heat resistance and a molded article molded from the resin composition.
The present disclosure can be realized in the following forms.

[1] a polycarbonate resin;
ABS resin,
Styrene-N-phenylmaleimide-maleic anhydride-acrylonitrile copolymer;
A resin composition comprising:

The resin composition disclosed herein has excellent heat resistance.

Here, a preferred example of the present disclosure is given.
[2] The content of the polycarbonate resin is 5 parts by mass or more and 95 parts by mass or less,
The content of the ABS resin is 5 parts by mass or more and 95 parts by mass or less,
The content of the styrene-N-phenylmaleimide-maleic anhydride-acrylonitrile copolymer is 1 part by mass or more and 40 parts by mass or less.
[3] A resin composition comprising an acrylonitrile-acrylate-styrene copolymer.
[4] The resin composition, wherein the content of the acrylonitrile-acrylic acid ester-styrene copolymer is 1 part by mass or more and 10 parts by mass or less.
[5] A molded article obtained by molding the resin composition.

The present disclosure will be described in detail below. In this specification, when a numerical range is described using "to" it is intended to include the lower limit and the upper limit unless otherwise specified. For example, the description "10 to 20" is intended to include both the lower limit "10" and the upper limit "20". In other words, "10 to 20" has the same meaning as "10 or more and 20 or less".

1. Resin Composition The resin composition of the present disclosure contains a polycarbonate resin, an ABS resin, and a styrene-N-phenylmaleimide-maleic anhydride-acrylonitrile copolymer (hereinafter also referred to as a "PMI copolymer").

From the viewpoint of improving the heat resistance and moldability of the resin composition, the content of the polycarbonate resin is preferably 5 parts by mass or more, more preferably 20 parts by mass or more, and even more preferably 40 parts by mass or more. From the viewpoint of improving the heat resistance and moldability of the resin composition, the content of the polycarbonate resin is preferably 95 parts by mass or less, more preferably 85 parts by mass or less, and even more preferably 70 parts by mass or less. From these viewpoints, the content of the polycarbonate resin is preferably 5 parts by mass or more and 95 parts by mass or less, more preferably 20 parts by mass or more and 85 parts by mass or less, and even more preferably 40 parts by mass or more and 70 parts by mass or less.

From the viewpoint of improving the heat resistance and moldability of the resin composition, the content of ABS resin is preferably 5 parts by mass or more, more preferably 15 parts by mass or more, and even more preferably 25 parts by mass or more. From the viewpoint of improving the heat resistance and moldability of the resin composition, the content of ABS resin is preferably 95 parts by mass or less, more preferably 70 parts by mass or less, and even more preferably 40 parts by mass or less. From these viewpoints, the content of ABS resin is preferably 5 parts by mass or more and 95 parts by mass or less, more preferably 15 parts by mass or more and 70 parts by mass or less, and even more preferably 25 parts by mass or more and 40 parts by mass or less.

From the viewpoint of improving the heat resistance and moldability of the resin composition, the content of the PMI copolymer is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and even more preferably 3 parts by mass or more. From the viewpoint of improving the heat resistance and moldability of the resin composition, the content of the PMI copolymer is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 20 parts by mass or less. From these viewpoints, the content of the ABS resin is preferably 1 part by mass or more and 40 parts by mass or less, more preferably 2 parts by mass or more and 30 parts by mass or less, and even more preferably 3 parts by mass or more and 20 parts by mass or less.

The resin composition preferably contains an acrylonitrile-acrylic acid ester-styrene copolymer (hereinafter also referred to as AAS copolymer).

2. Polycarbonate resin The polycarbonate resin is not particularly limited. The polycarbonate resin is a polymer having a carbonate bond represented by the general formula -[-O-R-O-C(=O)-]-. R is generally a hydrocarbon, and depending on the type of divalent hydroxy compound used as the raw material, there are, for example, aromatic polycarbonates, aliphatic polycarbonates, and alicyclic polycarbonates. In addition, the polycarbonate may be a homopolymer consisting of one type of repeating unit, or a copolymer consisting of two or more types of repeating units. Polycarbonates using bisphenol A as the raw material for the divalent hydroxy compound are widely produced industrially and can be preferably used.

Divalent hydroxy compounds are compounds that have two hydroxyl groups in the molecule, such as 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), hydroquinone, resorcinol and other dihydroxybenzenes, 4 ,4'-biphenol, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl-3-methylphenyl)propane, 2,2-bis(3-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)methane, 1,1-bis(p-hydroxyphenyl)ethane, 2,2-bis(p-hydroxyphenyl)butane, 2,2-bis(p-hydroxyphenyl)pentane, 1,1-bis(p-hydroxyphenyl)cyclohexane, 1,1-bis(p-hydroxyphenyl)-4-isopropylcyclohexane, 1,1-bis(p-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(p -hydroxyphenyl)-1-phenylethane, 9,9-bis(p-hydroxyphenyl)fluorene, 9,9-bis(p-hydroxy-3-methylphenyl)fluorene, 4,4'-(p-phenylenediisopropylidene)bisphenol, 4,4'-(m-phenylenediisopropylidene)bisphenol, bis(p-hydroxyphenyl)oxide, bis(p-hydroxyphenyl)ketone, bis(p-hydroxyphenyl)ether, bis(p-hydroxyphenyl)ester, bis(p-hydroxyphenyl)sulfide, bis(p-hydroxy-3-methylphenyl)sulfide, bis(p-hydroxyphenyl)sulfone, bis(3,5-dibromo-4-hydroxyphenyl)sulfone, bis(p-hydroxyphenyl)sulfoxide, etc. These can be used alone or in combination of two or more.

A known method can be used to manufacture polycarbonate resin. For example, there is the transesterification method (also called the melting method or melt polymerization method) in which bisphenol A and diphenyl carbonate are melted at high temperature and transesterified under reduced pressure while removing the phenol produced, the phosgene method (also called the interfacial polymerization method) in which phosgene is reacted with an aqueous solution or suspension of bisphenol A in the presence of methylene chloride, and the pyridine method in which bisphenol A is reacted with pyridine and phosgene in the presence of methylene chloride to synthesize the resin.

The weight average molecular weight of the polycarbonate resin is preferably 10,000 to 200,000, and more preferably 10,000 to 100,000. The weight average molecular weight of the polycarbonate resin is a polystyrene-equivalent value measured by gel permeation chromatography (GPC).

3. ABS resin The ABS resin is not particularly limited. The ABS resin is a resin containing three components, acrylonitrile, butadiene, and styrene. The ABS resin may be a copolymer, a graft copolymer, or a polymer blend in which these are mixed. There is no particular limitation on the method for producing the ABS resin, and any method such as continuous bulk polymerization, emulsion polymerization, solution polymerization, and suspension polymerization may be used.

4. PMI Copolymer The PMI copolymer is not particularly limited. The PMI copolymer is a copolymer having styrene monomer units, N-phenylmaleimide monomer units, maleic anhydride monomer units, and acrylonitrile monomer units as constituent units. The weight average molecular weight and molecular weight distribution (ratio of weight average molecular weight/number average molecular weight) of the PMI copolymer are 100,000 to 180,000 and 2.0 to 3.5, respectively. If the weight average molecular weight is less than 100,000, the mechanical properties of the resulting resin composition are insufficient, and if the molecular weight distribution exceeds 3.5, the mechanical properties and heat resistance are insufficient. If the weight average molecular weight exceeds 180,000 or the molecular weight distribution is less than 2.0, the impact strength of the resin composition is reduced, and defects such as silver spots occur in the molded product.

The PMI copolymer preferably has a melt viscosity of 50 Pa·S to 600 Pa·S at a temperature of 280° C. and a shear rate of 1,000 s ^-1 . If the melt viscosity is less than 50 Pa·S, the heat resistance imparting effect is reduced. If the melt viscosity exceeds 600 Pa·S, the impact strength of the resin composition is reduced, and defects such as silver spots occur in molded products.

The Tg (glass transition temperature) of the PMI copolymer is preferably 140°C to 190°C, and more preferably 150°C to 190°C. If the Tg is less than 140°C, the heat resistance imparting effect is reduced. If the Tg exceeds 190°C, the impact strength of the resulting resin composition is reduced, and defects such as silver spots occur in the molded product.

The constituent units of the PMI copolymer, when the total of each monomer unit is taken as 100% by weight, are preferably styrene monomer units of 30% by weight or more and 70% by weight or less, N-phenylmaleimide monomer units of 25% by weight or more and 50% by weight or less, maleic anhydride monomer units of 0.1% by weight or more and 25% by weight or less, and acrylonitrile monomer units of 0.1% by weight or more and 40% by weight or less, from the viewpoint of improving the heat resistance and moldability of the resin composition. The constituent units of the PMI copolymer, are more preferably styrene monomer units of 40% by weight or more and 65% by weight or less, N-phenylmaleimide monomer units of 30% by weight or more and 50% by weight or less, maleic anhydride monomer units of 0.2% by weight or more and 10% by weight or less, and acrylonitrile monomer units of 0.5% by weight or more and 20% by weight or less, from the viewpoint of improving the heat resistance and moldability of the resin composition. From the viewpoint of improving the heat resistance and moldability of the resin composition, the constituent units of the PMI copolymer are more preferably 40% by weight or more and 50% by weight or less of styrene monomer units, 45% by weight or more and 55% by weight or less of N-phenylmaleimide monomer units, 0.5% by weight or more and 2% by weight or less of maleic anhydride monomer units, and 2% by weight or more and 10% by weight or less of acrylonitrile monomer units.

As a method for producing the PMI copolymer, styrene, N-phenylmaleimide, maleic anhydride used as necessary, and acrylonitrile copolymerizable with these monomers may be directly copolymerized by a known method, or maleic anhydride may be copolymerized with styrene and acrylonitrile copolymerizable with these monomers, and then reacted with ammonia and/or a primary amine to form an unsaturated dicarboxylic acid imide derivative. However, as a method for producing these copolymers, the latter method, that is, a method in which an unsaturated dicarboxylic acid anhydride monomer is copolymerized with an aromatic vinyl monomer and a vinyl monomer copolymerizable with these monomers and then imidized, is more preferable in terms of copolymerizability and economy. In addition, examples of primary amines used in the imidization reaction include methylamine, ethylamine, propylamine, butylamine, hexylamine, cyclohexylamine, decylamine, aniline, toluidine, naphthylamine, chlorophenylamine, dichlorophenylamine, bromophenylamine, dibromophenylamine, etc., and among these, aniline is particularly preferable.

The imidization reaction can be carried out in a solution state, a bulk state, or a suspension state using an autoclave. It is also possible to carry out the reaction in a molten state using a melt kneading device such as a screw extruder. Any solvent can be used in the solution reaction in the imidization, and examples of the solvent include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, ethers such as tetrahydrofuran and 1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethyl sulfoxide, and N-methyl-2-pyrrolidone. The reaction temperature for the imidization is preferably in the range of 50°C to 350°C, and particularly preferably in the range of 100°C to 300°C.

The imidization reaction does not necessarily require the presence of a catalyst, but if one is used, tertiary amines such as trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, and N,N-diethylaniline are suitable. The PMI copolymer may be obtained by any of the conventionally known methods such as continuous bulk polymerization, emulsion polymerization, solution polymerization, and suspension polymerization, or may be obtained by a combination of these polymerization methods, but a solution polymerization method is preferred.

5. AAS Copolymer The AAS copolymer is not particularly limited. The AAS copolymer is a copolymer having a vinyl cyanide monomer unit, an acrylic rubber monomer unit, and an aromatic vinyl monomer unit as constituent units. The AAS copolymer may have any other copolymerizable monomer as a constituent unit as necessary. The AAS copolymer is obtained, for example, by a method of graft polymerizing a monomer component in the presence of an acrylic rubber. Examples of the polymerization method include continuous bulk polymerization, emulsion polymerization, solution polymerization, and suspension polymerization. The AAS copolymer may be used alone or in combination of two or more types.

Examples of vinyl cyanide monomers include acrylonitrile and methacrylonitrile, and among these, acrylonitrile is preferred. The vinyl cyanide monomers may be used alone or in combination of two or more kinds.

As the acrylic rubber, for example, one having an α,β-unsaturated carboxylic acid ester as a structural unit is preferable. Examples of the α,β-unsaturated carboxylic acid ester include acrylic acid ester and methacrylic acid ester, and acrylic acid ester is preferable. Examples of the acrylic acid ester include ethyl acrylate, butyl acrylate, and octyl acrylate. The acrylic rubber may be used alone or in combination of two or more kinds.

Examples of aromatic vinyl monomers include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, and p-t-butylstyrene, and among these, styrene and α-methylstyrene are preferred. Aromatic vinyl monomers may be used alone or in combination of two or more types.

AAS copolymer, also referred to as ASA, is preferably a copolymer whose constituent units are acrylonitrile monomer units, acrylic acid ester monomer units, and styrene monomer units.

From the viewpoint of improving the heat resistance and moldability of the resin composition, the content of the AAS copolymer is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and even more preferably 3 parts by mass or more. From the viewpoint of improving the heat resistance and moldability of the resin composition, the content of the AAS copolymer is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and even more preferably 6 parts by mass or less. From these viewpoints, the content of the AAS copolymer is preferably 1 part by mass or more and 10 parts by mass or less, more preferably 2 parts by mass or more and 8 parts by mass or less, and even more preferably 3 parts by mass or more and 6 parts by mass or less.

The viscosity of the AAS copolymer is preferably such that the melt viscosity at a temperature of 240° C. and a shear rate of 1,000 s ⁻¹ is 200 Pa·S to 500 Pa·S.

When the total of each monomer unit is 100% by weight, the constituent units of the AAS copolymer are preferably 5% by weight or more and 35% by weight or less of acrylonitrile monomer units, 3% by weight or more and 35% by weight or less of acrylic acid ester monomer units, and 50% by weight or more and 85% by weight or less of styrene monomer units, from the viewpoint of improving the heat resistance and moldability of the resin composition. The constituent units of the AAS copolymer are more preferably 10% by weight or more and 30% by weight or less of acrylonitrile monomer units, 10% by weight or more and 30% by weight or less of acrylic acid ester monomer units, and 55% by weight or more and 70% by weight or less of styrene monomer units, from the viewpoint of improving the heat resistance and moldability of the resin composition. The constituent units of the AAS copolymer are even more preferably 15% by weight or more and 25% by weight or less of acrylonitrile monomer units, 15% by weight or more and 25% by weight or less of acrylic acid ester monomer units, and 60% by weight or more and 65% by weight or less of styrene monomer units, from the viewpoint of improving the heat resistance and moldability of the resin composition.

6. Molded Products The resin composition can be molded by known methods, such as injection molding, sheet extrusion molding, vacuum molding, blow molding, foam molding, and profile extrusion molding. Molded products can be used for automobile parts, home appliances, office equipment parts, and the like.

The following provides a more detailed explanation using examples.

1. Preparation of Resin Compositions Various resin compositions were prepared according to the blending ratios shown in Table 1-2. In Table 1-2, the details of the main raw materials are shown below.
Polycarbonate resin (1): Lupilon (registered trademark) S-1000 manufactured by Mitsubishi Engineering Plastics Corporation Weight average molecular weight Mw: 25,000 to 26,000 MVR measured according to ISO 1183: 7.1
Polycarbonate resin (2): Lupilon (registered trademark) S-2000 manufactured by Mitsubishi Engineering Plastics Corporation Weight average molecular weight Mw: 23,000 to 24,000 MVR measured according to ISO 1183: 9.0
Polycarbonate resin (3): Lupilon (registered trademark) H-3000 manufactured by Mitsubishi Engineering Plastics Corporation Weight average molecular weight Mw: 18,000 to 19,000 MVR measured according to ISO 1183: 28
ABS resin (1): Clalastic (registered trademark) SRE manufactured by Nippon A&L Co., Ltd., MVR measured according to ISO 1133: 7.0 (220 ° C, 10 kg), manufacturing method: emulsion polymerization method ABS resin (2): Clalastic (registered trademark) ET-70 manufactured by Nippon A&L Co., Ltd., MVR measured according to ISO 1133: 9.0 (220 ° C, 10 kg), manufacturing method: continuous bulk polymerization method PMI copolymer: Denka IP (registered trademark) IPX-74 manufactured by Denka Co., Ltd., MVR measured according to ISO 1133: 7.0 (240 ° C, 10 kg), glass transition temperature (Tg): 177 ° C (DSC method)
AAS copolymer: Unibright (registered trademark) UA-1500 manufactured by Nippon A&L Co., Ltd., MVR measured according to ISO 1133: 11.0
Specifically, the raw materials for the resin compositions of Examples 1 to 12 and Comparative Example 1 were determined as follows.

<Example 1-3>
In Example 1-3, polycarbonate resin, ABS resin, PMI copolymer, and AAS copolymer were used as raw materials. In Example 1-3, polycarbonate resins (1) to (3) were used as the polycarbonate resin in the blending ratio shown in Table 1. In Example 1-3, ABS resin (2) produced by continuous bulk polymerization was used as the ABS resin.

<Example 4-12>
In Example 4-12, polycarbonate resin, ABS resin, and PMI copolymer were used as raw materials. In Example 4-12, polycarbonate resins (1) to (3) were used as the polycarbonate resin in the blending ratio shown in Table 1. In Example 4-11, ABS resin (2) produced by continuous bulk polymerization was used as the ABS resin. In Example 12, ABS resin (1) produced by emulsion polymerization was used as the ABS resin.

<Comparative Example 1>
In Comparative Example 1, polycarbonate resin and ABS resin were used as raw materials. In Comparative Example 1, polycarbonate resins (2) and (3) were used as the polycarbonate resin in the blending ratio shown in Table 1. In Comparative Example 1, ABS resin (2) produced by continuous bulk polymerization was used as the ABS resin.

2. Evaluation method (1) Heat resistance evaluation Heat resistance evaluation was performed by measuring the deflection temperature under load according to ISO 75-1. Using the Flatwise A method (load 1.80 MPa), a test piece of 4 mm x 10 mm x 80 mm was heated at a starting temperature of 23.0°C and a heating rate of 120.0°C/h, and the temperature (heat distortion temperature) at which the deflection amount reached the standard deflection amount (0.34 mm) was measured.

(2) Moldability Evaluation The appearance of the molded articles (test pieces) molded from each of the resin compositions of Examples 1-12 and Comparative Example 1 was evaluated. For each of the resin compositions of Examples 1-12 and Comparative Example 1, 20 molded articles each having a length of 12 cm, a width of 10 cm, a thickness of 3 mm and a tip with a 30° inclined shape were produced by one-point gate injection using an injection molding machine (FANUC S-2000i100A) under molding conditions of a cylinder temperature of 260° C., a mold temperature of 60° C., and an injection speed of 80 mm/s. The number of samples with appearance defects such as surface peeling and flow marks around the gate and within a range of 5 cm directly below the gate in the molded article was counted, and the appearance was evaluated.
In Table 1-2, the A, B, and C in the column for molded appearance are as follows:

<Molding appearance (condition of molded product)>
A: The number of samples with poor appearance (surface peeling, flow marks, etc.) was 0. B: The number of samples with poor appearance (surface peeling, flow marks, etc.) was 1 to 2. C: The number of samples with poor appearance (surface peeling, flow marks, etc.) was 3 or more.

(3) Paintability Evaluation Paintability was evaluated for molded articles molded from each of the resin compositions of Examples 1-12 and Comparative Example 1. As in the above (2) moldability evaluation, molded articles (test pieces) were prepared by molding each of the resin compositions of Examples 1-12 and Comparative Example 1. Each molded article was left in a thermostatic chamber at room temperature of 23°C and a relative humidity of 50% for 24 hours to condition it. The front surface of each molded article was spray-painted with a color base paint of an acrylic base agent so that the coating thickness was 20 μm to 30 μm, and left at room temperature for 10 minutes. Next, spray-painted with a paint consisting of an acrylic polyol base agent, an isocyanate curing agent, and a thinner so that the coating thickness was 30 μm to 40 μm, and dried at 80°C for 30 minutes to obtain a coated test piece.
In Table 1-2, the paintability columns A, B, and C are as follows:

<Paintability (condition of painted test piece)>
A: No crazing occurs near the injection gate of the coated test piece, and there are no poppings at the tip (slope) corners. B: Thin crazing of 5 mm or less occurs near the injection gate of the coated test piece, and there are no poppings at the tip (slope) corners. C: Thin crazing of 5 mm or more occurs near the injection gate of the coated test piece, or popping occurs at the tip (slope) corners.

3. Evaluation results (1) Satisfaction of each requirement of Examples 1 to 12 The resin compositions of Examples 1 to 3 satisfy all of the following requirements (a) to (d). The resin compositions of Examples 4 to 12 satisfy all of the following requirements (a) to (c).
Requirement (a): Contains a polycarbonate resin.
Requirement (b): Contains ABS resin.
Requirement (c): Contains a PMI copolymer.
Requirement (d): Contains an AAS copolymer.
(2) Satisfaction of Each Requirement in Comparative Example 1 The resin composition of Comparative Example 1 does not satisfy the above requirements (c) and (d).

(3) Results and Discussion The resin compositions of Examples 1-12 had heat distortion temperatures (temperatures at which the amount of deflection reached the standard amount of deflection (0.34 mm)) of 103°C to 110°C. The resin composition of Comparative Example 1 had a heat distortion temperature of 98°C. It is believed that the resin compositions of Examples 1-12 had improved heat resistance by satisfying the above requirement (c) (containing a PMI copolymer).
The resin compositions of Examples 1-12 were evaluated for molded appearance as A or B. The resin composition of Comparative Example 1 was evaluated for molded appearance as C. It is believed that the resin compositions of Examples 1-12 had improved moldability by satisfying the above requirement (c) (containing a PMI copolymer).
The resin compositions of Examples 1-12 were rated for coatability as A or B. The resin composition of Comparative Example 1 was rated for coatability as C. It is believed that the resin compositions of Examples 1-12 had improved coatability by satisfying the above requirement (c) (containing a PMI copolymer).
The resin composition of Example 1-3 was evaluated as an A for molded appearance and paintability. The resin composition of Example 4-12 was evaluated as a B for molded appearance and paintability. It is considered that the resin composition of Example 1-3 satisfies the above requirement (d) (contains an AAS copolymer), and thus has further improved moldability and paintability.
The resin composition of Example 1-11 using the ABS resin produced by the continuous bulk polymerization method and the resin composition of Example 12 using the ABS resin produced by the emulsion polymerization method both had improved heat resistance, moldability, and paintability compared to the resin composition of Comparative Example 1.

4. Effects of the Examples According to the above examples, the resin composition was able to improve heat resistance, moldability, and paintability. According to the examples, even if a molded article is produced by an injection molding method that tends to generate residual strain and then painted, the occurrence of painting defects such as crazing and popping is suppressed, and a painted molded article having a good appearance can be provided.

This disclosure is not limited to the embodiments detailed above, and various modifications and variations are possible.

Claims (1)

Polycarbonate resin;
ABS resin,
Styrene-N-phenylmaleimide-maleic anhydride-acrylonitrile copolymer;
an acrylonitrile-acrylate-styrene copolymer;
Including,
The constituent units of the styrene-N-phenylmaleimide-maleic anhydride-acrylonitrile copolymer are, when the total of the monomer units is taken as 100% by weight, 30% by weight or more and 70% by weight or less of styrene monomer units, 25% by weight or more and 50% by weight or less of N-phenylmaleimide monomer units, 0.1% by weight or more and 25% by weight or less of maleic anhydride monomer units, and 0.1% by weight or more and 40% by weight or less of acrylonitrile monomer units,
The content of the polycarbonate resin is 40 parts by mass or more and 70 parts by mass or less,
The content of the ABS resin is 25 parts by mass or more and 40 parts by mass or less,
The content of the styrene-N-phenylmaleimide-maleic anhydride-acrylonitrile copolymer is 3 parts by mass or more and 20 parts by mass or less,
The content of the acrylonitrile-acrylic acid ester-styrene copolymer is 1 part by mass or more and 10 parts by mass or less .