阅读说明：本技术 热塑性树脂组合物及其成型品 (Thermoplastic resin composition and molded article thereof ) 是由 柿本佑生 于 2019-03-08 设计创作，主要内容包括：一种热塑性树脂组合物,其含有芳香族聚碳酸酯树脂(A)、接枝共聚物(B)和(甲基)丙烯酸酯系共聚物(C),该接枝共聚物(B)是在橡胶状聚合物(X)上接枝聚合一种以上的乙烯基系单体(Y)而成的,该(甲基)丙烯酸酯系共聚物(C)是将含有(甲基)丙烯酸酯系单体的乙烯基系单体混合物(m1)聚合而成的。该热塑性树脂组合物优选在芳香族聚碳酸酯树脂(A)、接枝共聚物(B)和(甲基)丙烯酸酯系共聚物(C)合计100质量份中含有芳香族聚碳酸酯树脂(A)25～80质量份、接枝共聚物(B)10～30质量份、(甲基)丙烯酸酯系共聚物(C)10～45质量份。一种热塑性树脂成型品,其是将该热塑性树脂组合物成型而成的。(A thermoplastic resin composition comprising an aromatic polycarbonate resin (A), a graft copolymer (B) obtained by graft-polymerizing at least one vinyl monomer (Y) onto a rubbery polymer (X), and a (meth) acrylate copolymer (C) obtained by polymerizing a vinyl monomer mixture (m1) containing a (meth) acrylate monomer. The thermoplastic resin composition preferably contains 25 to 80 parts by mass of the aromatic polycarbonate resin (A), 10 to 30 parts by mass of the graft copolymer (B) and 10 to 45 parts by mass of the (meth) acrylate copolymer (C) per 100 parts by mass of the total of the aromatic polycarbonate resin (A), the graft copolymer (B) and the (meth) acrylate copolymer (C). A thermoplastic resin molded article is obtained by molding the thermoplastic resin composition.)

1. A thermoplastic resin composition comprising an aromatic polycarbonate resin (A), a graft copolymer (B) obtained by graft-polymerizing one or more vinyl monomers (Y) onto a rubbery polymer (X), and a (meth) acrylate copolymer (C) obtained by polymerizing a vinyl monomer mixture (m1) containing a (meth) acrylate monomer.

2. The thermoplastic resin composition according to claim 1, wherein said vinyl monomer mixture (m1) contains an N-substituted maleimide monomer and/or an aromatic vinyl monomer.

3. The thermoplastic resin composition according to claim 1 or 2, wherein the aromatic polycarbonate resin (A) is contained in an amount of 25 to 80 parts by mass, the graft copolymer (B) is contained in an amount of 10 to 30 parts by mass, and the (meth) acrylate copolymer (C) is contained in an amount of 10 to 45 parts by mass, based on 100 parts by mass of the total of the aromatic polycarbonate resin (A), the graft copolymer (B), and the (meth) acrylate copolymer (C).

4. The thermoplastic resin composition according to any one of claims 1 to 3, wherein the content of the (meth) acrylate monomer is 52 to 92% by mass in 100% by mass in total of the vinyl monomer mixture (m 1).

5. The thermoplastic resin composition according to any one of claims 1 to 4, wherein the rubber-like polymer (X) is a silicone/acrylic composite rubber, and the vinyl monomer (Y) contains an aromatic vinyl monomer and a vinyl cyanide monomer.

6. The thermoplastic resin composition according to claim 1 to 5, further comprising a NO-alkyl type hindered amine light stabilizer (D).

7. The thermoplastic resin composition according to claim 6, wherein the number of carbon atoms of the alkoxy group bonded to the nitrogen atom of the NO-alkyl hindered amine light stabilizer (D) is5 to 15, and the molecular weight of the NO-alkyl hindered amine light stabilizer (D) is in the range of 500 to 1000.

8. The thermoplastic resin composition according to claim 6 or 7, wherein the NO-alkyl hindered amine light stabilizer (D) is contained in an amount of 0.1 to 0.8 parts by mass based on 100 parts by mass of the total of the aromatic polycarbonate resin (A), the graft copolymer (B) and the (meth) acrylate copolymer (C).

9. The thermoplastic resin composition according to claim 5,

the organic silicon/acrylic composite rubber is formed by compounding organic polysiloxane (a) and alkyl ester (methyl) acrylate polymer (b),

the ratio of the polyorganosiloxane (a) is 4 to 14% by mass and the ratio of the alkyl (meth) acrylate polymer (b) is 96 to 86% by mass, based on 100% by mass of the total of the polyorganosiloxane (a) and the alkyl (meth) acrylate polymer (b).

10. The thermoplastic resin composition according to any one of claims 1 to 9, wherein the graft copolymer (B) is obtained by graft polymerizing 30 to 80 parts by mass of the vinyl monomer (Y) to 20 to 70 parts by mass of the rubbery polymer (X), and the total amount of the rubbery polymer (X) and the vinyl monomer (Y) is 100 parts by mass.

11. The thermoplastic resin composition according to any one of claims 1 to 10, wherein the content of the N-substituted maleimide monomer is from 7 to 39 mass% and the content of the N-substituted maleimide monomer is 13 mass% or less, based on 100 mass% of the total of the vinyl monomer mixture (m 1).

12. A thermoplastic resin molded article obtained by molding the thermoplastic resin composition according to any one of claims 1 to 11.

Technical Field

The present invention relates to a thermoplastic resin composition having excellent color developability, impact resistance, and the like, and a molded article thereof.

In the present specification, "(meth) acrylic acid" means either or both of "acrylic acid" and "methacrylic acid". The same applies to "(meth) acrylate".

Background

Aromatic polycarbonate resins are excellent in transparency, impact resistance, heat resistance and the like, and molded articles obtained therefrom are also excellent in dimensional stability and the like, and therefore, they are widely used as raw materials for producing housings of electric and electronic devices, automobile parts, precision molded articles such as optical disk-related parts and the like. In particular, a housing of a home appliance, an electronic device, an image display device, or the like can be provided with a high commercial value by utilizing its beautiful appearance.

Aromatic polycarbonate resins have disadvantages of poor flowability and molding processability, and therefore, a method of alloying with other resins is often employed. For example, a resin having improved flowability and moldability obtained by alloying an aromatic polycarbonate resin with an ABS resin (hereinafter referred to as "PC/ABS resin") has excellent mechanical and thermal properties and is widely used in various fields such as OA equipment field, electronic and electric equipment field, and automobile field.

However, since the PC/ABS resin is obtained by alloying an ABS resin with an aromatic polycarbonate resin, there is a disadvantage that the color developability (coloring property) inherent in the aromatic polycarbonate resin is lowered, and it is difficult to satisfy the color developability (coloring property) which has been recently attracting attention in the market as a non-coated one.

As a method for improving the color developability (coloring property) of a PC/ABS resin, the following methods have been proposed: the (meth) acrylate-based resin is provided with excellent appearance and color development characteristic to the (meth) acrylate-based resin by mixing a (meth) acrylate-based resin typified by polymethyl methacrylate (PMMA). However, there is a problem that the blend of the (meth) acrylate resin significantly lowers impact resistance, heat resistance, and the like.

Patent document 1 proposes a method of compounding polymethyl methacrylate (PMMA) into a PC/ABS resin, and further describes that impact resistance is improved by compounding an elastomer. In patent document 1, when PMMA having excellent color developability (coloring property) is compounded into a PC/ABS resin having excellent impact resistance and heat resistance, the color developability (coloring property) can be imparted, but the impact resistance is greatly reduced, and therefore the reduction in impact resistance is improved by compounding an elastomer. However, when an elastomer is compounded, the color development characteristic of PMMA may be reduced.

In the PC/ABS resin, impact resistance and color developability (colorability) are in a relationship of two-note bar, and it is difficult to achieve both of them at present.

A polymer alloy obtained by blending a (meth) acrylate resin such as PMMA with a PC/ABS resin has excellent weather resistance and color development, but when the polymer alloy is excessively exposed to light containing ultraviolet rays, the surface of a molded article is easily discolored to yellow, and the resin is decomposed by the ultraviolet rays, which causes a problem that the strength of the molded article is significantly reduced. In addition, there is a problem that hydrolysis under high temperature and humidity causes extreme decrease in molecular weight. Further, since polymethyl methacrylate (PMMA) is compounded for the purpose of achieving weather resistance and color development, there is also a concern about a significant decrease in impact resistance.

As a technique for solving the yellow discoloration caused by ultraviolet rays, a technique of blending a benzotriazole-based ultraviolet absorber and a hindered amine-based light stabilizer has been studied. In particular, the hindered amine light stabilizer is considered to have a very high effect of suppressing yellow discoloration of the appearance which occurs when ultraviolet light is irradiated. However, the hindered amine-based light stabilizer has a problem that it reacts with a polycarbonate resin to promote hydrolysis in pelletization and molding.

In patent document 2, the weather resistance is improved by adding a hindered amine light stabilizer, but no study has been made on the hydrolysis resistance.

It is considered that it is very difficult to express physical properties such as weather resistance, hydrolysis resistance and impact resistance without adversely affecting the properties.

Patent document 1: japanese patent laid-open No. 2012 and 131908

Patent document 2: japanese patent No. 6298935

Disclosure of Invention

The present invention aims to provide a thermoplastic resin composition and a molded article thereof, which have both impact resistance and color developability (colorability) that have been considered difficult to achieve in PC/ABS resins, and which are excellent in color developability, impact resistance, heat resistance and rigidity.

It is another object of the present invention to provide a thermoplastic resin composition which has both of physical properties such as weather resistance, hydrolysis resistance and impact resistance, which have been considered difficult to achieve at the same time, and which is excellent in durability and weather resistance such as color development property, impact resistance and hydrolysis resistance, and a molded article thereof.

The present inventors have found that a thermoplastic resin composition having excellent color developability, impact resistance, heat resistance, and rigidity can be provided by blending a (meth) acrylate copolymer (C) obtained by polymerizing a vinyl monomer mixture (m1) containing a (meth) acrylate monomer with an aromatic polycarbonate resin (a) and a graft copolymer (B).

The present inventors have also found that a thermoplastic resin composition having excellent color development, impact resistance, durability and weather resistance can be provided by blending a (meth) acrylate copolymer (C) obtained by polymerizing a vinyl monomer mixture (m1) containing a (meth) acrylate monomer with an aromatic polycarbonate resin (a) and a graft copolymer (B), and adding a hindered amine light stabilizer (D), particularly an NO-alkyl type hindered amine light stabilizer (D), among the hindered amine light stabilizers.

The gist of the present invention is as follows.

[1] A thermoplastic resin composition comprising an aromatic polycarbonate resin (A), a graft copolymer (B) obtained by graft-polymerizing one or more vinyl monomers (Y) onto a rubbery polymer (X), and a (meth) acrylate copolymer (C) obtained by polymerizing a vinyl monomer mixture (m1) containing a (meth) acrylate monomer.

[2] The thermoplastic resin composition according to [1], wherein the vinyl monomer mixture (m1) contains an N-substituted maleimide monomer and/or an aromatic vinyl monomer.

[3] The thermoplastic resin composition according to [1] or [2], wherein the aromatic polycarbonate resin (A) is contained in an amount of 25 to 80 parts by mass, the graft copolymer (B) is contained in an amount of 10 to 30 parts by mass, and the (meth) acrylate copolymer (C) is contained in an amount of 10 to 45 parts by mass, based on 100 parts by mass of the total of the aromatic polycarbonate resin (A), the graft copolymer (B), and the (meth) acrylate copolymer (C).

[4] The thermoplastic resin composition as described in any one of [1] to [3], wherein the content of the (meth) acrylate monomer is 52 to 92% by mass in 100% by mass of the total of the vinyl monomer mixture (m 1).

[5] The thermoplastic resin composition according to any one of [1] to [4], wherein the rubber-like polymer (X) is a silicone/acrylic composite rubber, and the vinyl monomer (Y) contains an aromatic vinyl monomer and a vinyl cyanide monomer.

[6] The thermoplastic resin composition according to any one of [1] to [5], further comprising a NO-alkyl type hindered amine light stabilizer (D).

[7] The thermoplastic resin composition as recited in claim 6, wherein the number of carbon atoms of the alkoxy group bonded to the nitrogen atom of the NO-alkyl hindered amine light stabilizer (D) is5 to 15, and the molecular weight of the NO-alkyl hindered amine light stabilizer (D) is in the range of 500 to 1000.

[8] The thermoplastic resin composition according to [6] or [7], wherein the NO-alkyl hindered amine light stabilizer (D) is contained in an amount of 0.1 to 0.8 part by mass based on 100 parts by mass of the total of the aromatic polycarbonate resin (A), the graft copolymer (B) and the (meth) acrylate copolymer (C).

[9] A thermoplastic resin molded article obtained by molding the thermoplastic resin composition according to any one of [1] to [8 ].

ADVANTAGEOUS EFFECTS OF INVENTION

According to the thermoplastic resin composition of the present invention containing the aromatic polycarbonate resin (a), the graft copolymer (B) and the (meth) acrylate copolymer (C), a thermoplastic resin composition excellent in color developability, impact resistance, heat resistance and rigidity, and a molded article thereof can be provided. The thermoplastic resin molded article of the present invention can provide excellent design properties without coating in various products due to its excellent color developability, impact resistance, heat resistance and rigidity.

The thermoplastic resin composition of the present invention further containing an NO-alkyl hindered amine light stabilizer (D) can provide a thermoplastic resin composition excellent in color developability, impact resistance, durability and weather resistance, and a molded article thereof. The thermoplastic resin molded article of the present invention can be provided with excellent design properties and high durability without coating in various products due to its excellent durability and weather resistance such as color development, impact resistance, hydrolysis resistance and the like.

Detailed Description

The embodiments of the present invention will be described in detail below.

[ thermoplastic resin composition ]

The thermoplastic resin composition of the present invention contains the aromatic polycarbonate resin (a), the graft copolymer (B) and the (meth) acrylate copolymer (C) described below as essential components, and may further contain an NO-alkyl hindered amine light stabilizer (D).

< aromatic polycarbonate resin (A) >

The aromatic polycarbonate resin (a) is a polymer having a basic structure of a carbonate bond represented by the general formula- (-O-R-O-C (═ O) -) -and is a polycarbonate resin in which a carbon atom directly bonded to the carbonate bond is an aromatic carbon atom. In the formula, R is usually an aromatic hydrocarbon group, and may be an aromatic hydrocarbon group into which a hetero atom or a hetero bond is introduced in order to impart various characteristics. As the aromatic polycarbonate resin (a), there can be mentioned, as a representative example, an aromatic polycarbonate resin produced from a dihydroxyaryl compound such as 2, 2-bis (4-hydroxyphenyl) propane (bisphenol a).

As the above dihydroxy diaryl compound, in addition to bisphenol A, examples thereof include bis (hydroxyaryl) alkanes such as bis (4-hydroxyphenyl) methane, 1-bis (4-hydroxyphenyl) ethane, 2-bis (4-hydroxyphenyl) butane, 2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) diphenylmethane, 2-bis (4-hydroxy-3-methylphenyl) propane, 1-bis (4-hydroxy-3-tert-butylphenyl) propane, 2-bis (4-hydroxy-3-bromophenyl) propane, 2-bis (4-hydroxy-3, 5-dibromophenyl) propane, 2-bis (4-hydroxy-3, 5-dichlorophenyl) propane and the like; bis (hydroxyaryl) cycloalkanes such as 1, 1-bis (4-hydroxyphenyl) cyclopentane, 1-bis (4-hydroxyphenyl) cyclohexane; dihydroxydiaryl ethers such as 4,4 ' -dihydroxydiphenyl ether and 4,4 ' -dihydroxy-3, 3 ' -dimethyldiphenyl ether; dihydroxy diaryl sulfides such as 4,4 ' -dihydroxy diphenyl sulfide and 4,4 ' -dihydroxy-3, 3 ' -dimethyl diphenyl sulfide; dihydroxydiarylsulfoxides such as 4, 4' -dihydroxydiphenylsulfoxide; dihydroxy diaryl sulfones such as 4,4 ' -dihydroxy diphenyl sulfone and 4,4 ' -dihydroxy-3, 3 ' -dimethyl diphenyl sulfone.

These dihydroxy diaryl compounds may be used alone or in combination of two or more, and piperazine, dipiperidinohydroquinone, resorcinol, 4' -dihydroxybiphenyl, and the like may be used in combination.

The dihydroxy diaryl compound described above may be used in combination with a 3-membered or higher phenol compound shown below. Examples of the 3-or more-membered phenol compound include phloroglucinol, 4, 6-dimethyl-2, 4, 6-tris (4-hydroxyphenyl) heptene, 2,4, 6-trimethyl-2, 4, 6-tris (4-hydroxyphenyl) heptane, 1,3, 5-tris (4-hydroxyphenyl) benzene, 1,1, 1-tris (4-hydroxyphenyl) ethane, and 2, 2-bis (4, 4-bis (4-hydroxyphenyl) cyclohexyl) propane.

The viscosity average molecular weight (Mv) of the aromatic polycarbonate resin (A) is not particularly limited, and it is preferable to use 15000 to 40000. When the viscosity average molecular weight (Mv) is less than 15000, impact resistance and heat resistance tend to be poor, and when the viscosity average molecular weight (Mv) is more than 40000, flowability tends to be poor and moldability tends to be poor. The viscosity average molecular weight (Mv) of the aromatic polycarbonate resin (A) is more preferably 16000 to 35000, and still more preferably 18000 to 30000.

Therefore, when the aromatic polycarbonate resin (A) is produced, it is preferable to produce an aromatic polycarbonate resin having such a viscosity average molecular weight by using the above dihydroxy diaryl compound and the like and, if necessary, a molecular weight modifier, a catalyst and the like.

Here, viscosity average molecular weight [ Mv ]]The intrinsic viscosity at 20 ℃ was determined using methylene chloride as a solvent and an Ubbelohde viscometer [ η ]](dl/g units) from Schnell's viscosity formula, i.e. η ═ 1.23 × 10^-4Mv^0.83The calculated value.

Intrinsic viscosity [ η]Is to measure the concentration [ C ] in each solution]Specific viscosity in (g/dl) [ η_sp]The value is calculated by the following equation.

[ number 1]

Specific examples of the aromatic polycarbonate resin (A) include "IUPILON series", "NOVAREX series", and "タフロン series", which are commercially available from Mitsubishi engineering plastics corporation.

The aromatic polycarbonate resin (a) may be used alone, or two or more kinds of aromatic polycarbonate resins having different monomer compositions, physical properties, and the like may be used in combination. For example, two or more aromatic polycarbonate resins having different viscosity average molecular weights may be mixed and used while adjusting the viscosity average molecular weight to the above-mentioned preferable viscosity average molecular weight.

In the thermoplastic resin composition of the present invention, the content of the aromatic polycarbonate resin (a) is preferably 25 to 80 parts by mass based on 100 parts by mass of the total of the aromatic polycarbonate resin (a), the graft copolymer (B) and the (meth) acrylate copolymer (C) from the viewpoints of impact resistance, heat resistance and color developability. The content of the aromatic polycarbonate resin (A) is more preferably 35 to 80 parts by mass, and still more preferably 40 to 75 parts by mass. When the content of the aromatic polycarbonate resin (A) is not less than the lower limit, the impact resistance and heat resistance are good, and when the content is not more than the upper limit, the color developability and rigidity are good.

< graft copolymer (B) >

The graft copolymer (B) is obtained by graft-polymerizing at least one of vinyl monomers (Y) such as a vinyl cyanide monomer, an aromatic vinyl monomer, a (meth) acrylate monomer, and a maleimide monomer to the rubbery polymer (X).

Examples of the rubber-like polymer (X) forming the graft copolymer (B) include butadiene-based rubbers such as polybutadiene, styrene/butadiene copolymers, and acrylate/butadiene copolymers, conjugated diene-based rubbers such as styrene/isoprene copolymers, acrylic-based rubbers such as polybutyl acrylate, silicone/acrylic-based rubbers, and olefin-based rubbers such as ethylene/propylene copolymers. These rubbery polymers may be used alone or in combination of two or more. Among these, polybutadiene-based rubber, acrylic rubber, olefin-based rubber, and silicone/acrylic composite rubber are preferable from the viewpoint of impact resistance. From the viewpoint of color developability, a silicone/acrylic composite rubber is more preferable.

The silicone/acrylic composite rubber is preferably a silicone/acrylic composite rubber in which a polyorganosiloxane (a) and an alkyl ester of (meth) acrylic acid polymer (b) are compounded.

The silicone/acrylic composite rubber will be described below. The silicone/acrylic composite rubber can be produced by the method described in, for example, japanese patent application laid-open No. 2016-125006.

< polyorganosiloxane (a) >

The polyorganosiloxane (a) constituting the rubber-like polymer (X) as the silicone/acrylic composite rubber is not particularly limited, but a polyorganosiloxane containing a vinyl polymerizable functional group (a polyorganosiloxane containing a vinyl polymerizable functional group) is preferable, and a polyorganosiloxane having a siloxane unit containing a vinyl polymerizable functional group and a dimethylsiloxane unit is more preferable.

The proportion of the vinyl-polymerizable functional group-containing siloxane unit in the polyorganosiloxane (a) is preferably 0.3 to 3 mol%. When the proportion of the vinyl-polymerizable functional group-containing siloxane unit is within the above range, the polyorganosiloxane (a) and the alkyl (meth) acrylate polymer (b) are sufficiently combined, and the polyorganosiloxane (a) hardly bleeds out on the surface of the obtained molded article. Therefore, the surface appearance of the molded article is further improved, and the impact resistance of the molded article is further improved.

The polyorganosiloxane (a) preferably has 3 or more siloxane bonds in a proportion of 0 to 1 mol% based on the total silicon atoms in the polyorganosiloxane, for the purpose of further improving the surface appearance of the molded article.

Preferred examples of the polyorganosiloxane (a) include the following polyorganosiloxanes: the silicone composition is composed of 0.3-3 mol% of siloxane units containing vinyl polymerizable functional groups and 99.7-97 mol% of dimethyl siloxane units (wherein the total of the siloxane units containing vinyl polymerizable functional groups and the dimethyl siloxane units is 100 mol%), and silicon atoms with more than 3 siloxane bonds are less than 1 mol% relative to all silicon atoms in the polyorganosiloxane.

The average particle diameter of the polyorganosiloxane (a) is not particularly limited, but is preferably 400nm or less, more preferably 150nm or less, for the reason that the surface appearance of the molded article becomes further good. The lower limit of the average particle diameter of the polyorganosiloxane (a) is preferably 20nm or more.

The average particle diameter of the polyorganosiloxane (a) is a value (mass average particle diameter) calculated from a particle diameter distribution obtained by measuring a mass-based particle diameter distribution using a particle diameter distribution measuring instrument.

Alkyl ester of (meth) acrylic acid Polymer (b)

The (meth) acrylate polymer (b) constituting the rubber-like polymer (X) as the silicone/acrylic composite rubber is obtained by polymerizing a monomer component containing at least one alkyl (meth) acrylate monomer. The monomer component may contain a monomer (other monomer) other than the alkyl (meth) acrylate monomer.

The alkyl (meth) acrylate monomer is not particularly limited, and examples thereof include alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate; and alkyl methacrylates such as hexyl methacrylate, 2-ethylhexyl methacrylate and n-lauryl methacrylate. These alkyl (meth) acrylate monomers may be used alone or in combination of two or more. Among these, n-butyl acrylate is preferable in terms of further improving the impact resistance of the obtained molded article.

The proportion of the alkyl (meth) acrylate monomer in 100% by mass of the monomer component is preferably 80 to 100% by mass, and more preferably 90 to 100% by mass.

The other monomer is not particularly limited as long as it can be copolymerized with the alkyl (meth) acrylate monomer, and examples thereof include aromatic vinyl monomers (e.g., styrene, α -methylstyrene, p-methylstyrene, etc.), cyanide vinyl monomers (e.g., acrylonitrile, methacrylonitrile, etc.), and the like. One of the other monomers may be used alone, or two or more of them may be used in combination.

In order to introduce a crosslinked structure into the alkyl ester of (meth) acrylic acid polymer (b) obtained from the alkyl ester of (meth) acrylic acid monomer, it is preferable to add a crosslinking agent to carry out polymerization. The polymeric crosslinking agent contained in the composite rubber also functions as a graft cross-point for graft-bonding the vinyl monomer (Y) at the time of production of the graft copolymer (B).

Examples of the crosslinking agent include allyl (meth) acrylate, butanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1, 3-butanediol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, triallyl cyanurate, and triallyl isocyanurate. These crosslinking agents may be used singly or in combination of two or more.

The amount of the crosslinking agent used is not particularly limited, but is preferably 0.1 to 5.0 parts by mass based on 100 parts by mass of the total of the crosslinking agent and the alkyl (meth) acrylate monomer.

The method for producing the alkyl ester of (meth) acrylic acid polymer (b) is not particularly limited, and it can be carried out by a known method.

< composition of Silicone/acrylic composite rubber >

The proportions of the polyorganosiloxane (a) and the alkyl (meth) acrylate polymer (b) in the rubber-like polymer (X) as the silicone/acrylic composite rubber are not particularly limited, and it is preferable that the proportions of the polyorganosiloxane (a) and the alkyl (meth) acrylate polymer (b) are 4 to 14% by mass and 96 to 86% by mass, respectively, when the total of the polyorganosiloxane (a) and the alkyl (meth) acrylate polymer (b) is 100% by mass, for the reason that the molded article obtained is more excellent in impact resistance and surface appearance.

< volume average particle diameter >

The volume average particle diameter of the rubber-like polymer (X) as the silicone/acrylic composite rubber is not particularly limited, but is preferably 100 to 200nm, and particularly preferably 120 to 180 nm. When the volume average particle diameter is 100nm or more, the resulting molded article has good impact resistance and surface smoothness. When the volume average particle diameter is 200nm or less, the surface smoothness of the resulting molded article is good.

The volume average particle diameter of the rubber-like polymer (X) is a value calculated from the obtained particle diameter distribution by measuring the volume-based particle diameter distribution using a particle diameter distribution measuring instrument.

The proportion of particles having a particle diameter of 300 to 500nm in the total particles of the rubbery polymer (X) is preferably 5 to 25% by volume. That is, the rubbery polymer (X) preferably has a particle size distribution in which particles having a particle size of 300 to 500nm account for 5 to 25 vol% of the total particles. When the proportion of particles having a particle diameter of 300 to 500nm is 5% by volume or more, the resulting molded article has excellent impact resistance. When the proportion of particles having a particle diameter of 300 to 500nm is 25% by volume or less, the surface smoothness of the resulting molded article is good. The proportion of particles having a particle diameter of 300 to 500nm is preferably 5 to 15 vol%, because the balance between the impact resistance and the surface appearance of the molded article obtained is more favorable.

The rubbery polymer (X) may be used alone or in combination of two or more.

The vinyl monomer (Y) forming the graft copolymer (B) is not particularly limited, and examples thereof include aromatic vinyl monomers, (meth) acrylic acid alkyl ester monomers, vinyl cyanide monomers, and maleimide monomers.

Examples of the aromatic vinyl monomer include styrene, α -methylstyrene, and p-methylstyrene.

Examples of the alkyl ester (meth) acrylate monomer include methyl methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, and tert-butyl acrylate.

Examples of the vinyl cyanide monomer include acrylonitrile and methacrylonitrile.

These monomers may be used alone or in combination of two or more. For the reason that the impact resistance of the molded article obtained is further improved, it is preferable to use an aromatic vinyl monomer such as styrene in combination with a vinyl cyanide monomer such as acrylonitrile.

The monomer composition ratio of the vinyl monomer (Y) graft-polymerized with the rubber-like polymer (X) is not particularly limited, and when an aromatic vinyl monomer and a vinyl cyanide monomer are used in combination, it is preferable to use 60 to 95 mass% of the aromatic vinyl monomer and 5 to 40 mass% of the vinyl cyanide monomer in 100 mass% of the total of the aromatic vinyl monomer and the vinyl cyanide monomer, from the viewpoint of the impact resistance, heat resistance and rigidity effects of the combination of the aromatic vinyl monomer and the vinyl cyanide monomer.

The graft copolymer (B) is preferably a graft copolymer (B) obtained by graft-polymerizing 30 to 80 parts by mass of one or more vinyl monomers (Y) to 20 to 70 parts by mass of the rubbery polymer (X) (wherein the total amount of the rubbery polymer (X) and the vinyl monomer (Y) is 100 parts by mass) from the viewpoint of achieving both impact resistance, fluidity, rigidity, and the like. The proportion is preferably 32 to 78 parts by mass of the vinyl monomer (Y) to 22 to 68 parts by mass of the rubbery polymer (X), and more preferably 34 to 76 parts by mass of the vinyl monomer (Y) to 24 to 66 parts by mass of the rubbery polymer (X) (wherein the total of the rubbery polymer (X) and the vinyl monomer (Y) is 100 parts by mass).

The graft copolymer (B) can be produced by graft-polymerizing the vinyl monomer (Y) in the presence of the rubbery polymer (X) by a conventional method.

The method for producing the graft copolymer (B) is not particularly limited, and a generally known method such as bulk polymerization, solution polymerization, bulk suspension polymerization, or emulsion polymerization is used.

In order to ensure the balance between the impact resistance of the resulting molded article and the appearance characteristics of the resulting molded article, the graft ratio of the graft copolymer (B) is preferably in the range of 20 to 80%, which is determined by the method in examples to be described later. When the graft ratio of the graft copolymer (B) is not less than the lower limit, the appearance characteristics of the resulting molded article are good. When the graft ratio of the graft copolymer (B) is within the above range, the impact resistance is good.

The acetone-soluble component of the graft copolymer (B) preferably has a reduced viscosity of 0.1 to 1.5dL/g, particularly preferably 0.15 to 1.45 dL/g. When the reduced viscosity of the acetone-soluble component of the graft copolymer (B) is not less than the lower limit, the impact resistance is improved, and when it is not more than the upper limit, good appearance and moldability of the molded article can be secured. The reduced viscosity of the acetone-soluble component of the graft copolymer (B) was determined by the method described in the section of examples to be described later.

In the thermoplastic resin composition of the present invention, the content of the graft copolymer (B) is preferably 10 to 30 parts by mass based on 100 parts by mass of the total of the aromatic polycarbonate resin (a), the graft copolymer (B) and the (meth) acrylate copolymer (C) from the viewpoint of impact resistance and heat resistance. The content of the graft copolymer (B) is more preferably 10 to 25 parts by mass, and still more preferably 15 to 25 parts by mass. When the content of the graft copolymer (B) is not less than the lower limit, the impact resistance is good, and when it is not more than the upper limit, the heat resistance and rigidity are good.

[ meth (acrylate) copolymer (C) >

The (meth) acrylate copolymer (C) is obtained by polymerizing a vinyl monomer mixture (m1) containing a (meth) acrylate monomer by a known method. The vinyl monomer mixture (m1) contains a (meth) acrylate monomer as an essential component and, if necessary, other vinyl monomers. Examples of the other vinyl monomer include an N-substituted maleimide monomer, an aromatic vinyl monomer, and other monomers.

The content of the (meth) acrylate monomer in the vinyl monomer mixture (m1) is not particularly limited, but is preferably 52 to 99 mass%, more preferably 60 to 95 mass%, and still more preferably 65 to 92 mass% of the total 100 mass% of the vinyl monomer mixture (m1), for reasons of excellent color developability of the resulting (meth) acrylate copolymer (C), thermoplastic resin composition, and molded article thereof. When the content of the (meth) acrylate monomer is within the above range, the resulting (meth) acrylate copolymer (C), thermoplastic resin composition, and molded article thereof are excellent in color developability and impact resistance.

The (meth) acrylate monomer constituting the vinyl monomer mixture (m1) is not particularly limited, and examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclodecyl (meth) acrylate, phenyl (meth) acrylate, and 2,4, 6-tribromophenyl (meth) acrylate. Of these, methyl methacrylate is most preferable. When two or more of these (meth) acrylate monomers are used in combination as needed, the amount of methyl methacrylate is preferably 25% by mass or more, and more preferably 50% by mass or more, based on the total amount of the (meth) acrylate monomers.

The N-substituted maleimide monomer as another vinyl monomer used in the vinyl monomer mixture (m1) is not particularly limited, and examples thereof include N-substituted aryl maleimides such as N-phenylmaleimide and N-o-chlorophenylmaleimide, N-substituted alkyl maleimides such as N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide and N-t-butylmaleimide, and N-substituted cycloalkyl maleimides such as N-cyclohexylmaleimide. Among these, N-phenylmaleimide is preferable from the viewpoint of heat resistance and rigidity. Two or more of these N-substituted maleimide monomers may be used in combination as required. When used in combination, the N-phenylmaleimide is contained in an amount of preferably 25 mass% or more, more preferably 50 mass% or more, based on the total amount of the N-substituted maleimide-based monomer.

The content of the N-substituted maleimide monomer in the vinyl monomer mixture (m1) is not particularly limited, but is 13 mass% or less, preferably 2 mass% or more and 13 mass% or less, and more preferably 3 mass% or more and 13 mass% or less, based on 100 mass% of the total of the vinyl monomer mixture (m1), for the reason that the resulting (meth) acrylate copolymer (C), thermoplastic resin composition, and molded article thereof are excellent in heat resistance and color developability. When the content of the N-substituted maleimide is 13% by mass or less, the resulting (meth) acrylate copolymer (C), thermoplastic resin composition and molded article thereof have good color developability, flowability and impact resistance. When the content of the N-substituted maleimide is within the above range, the resulting (meth) acrylate copolymer (C), thermoplastic resin composition and molded article thereof are excellent in heat resistance and color developability.

The aromatic vinyl monomer used as another vinyl monomer in the vinyl monomer mixture (m1) is not particularly limited, and examples thereof include styrene, α -methylstyrene, and vinyltoluene. Among these, styrene and α -methylstyrene are preferred. When two or more of these aromatic vinyl monomers are used in combination as necessary, the styrene and/or α -methylstyrene content is preferably 25 mass% or more, and more preferably 50 mass% or more, based on the total amount of the aromatic vinyl monomers.

The content of the aromatic vinyl monomer in the vinyl monomer mixture (m1) is not particularly limited, but is preferably 7 to 39 mass%, more preferably 8 to 30 mass%, and still more preferably 9 to 25 mass% of the total 100 mass% of the vinyl monomer mixture (m1), from the viewpoint of excellent color developability of the resulting (meth) acrylate copolymer (C), thermoplastic resin composition, and molded article thereof. When the content of the aromatic vinyl monomer is 7% by mass or more, the fluidity of the resulting (meth) acrylate copolymer (C), thermoplastic resin composition and molded article thereof is good, and when it is 39% by mass or less, the color developability and impact resistance are good.

The vinyl monomer mixture (m1) may contain, in addition to the (meth) acrylate monomer and the above-mentioned vinyl monomers, another vinyl monomer copolymerizable with these monomers, if necessary. Examples of the other copolymerizable vinyl monomer include conjugated dienes such as butadiene and isoprene, cyanide vinyl monomers such as acrylonitrile, and unsaturated carboxylic acids such as acrylic acid, maleic acid, and maleic anhydride. These other monomers may be used alone or in combination of two or more.

These other monomers may be added in accordance with the characteristics of the (meth) acrylate-based copolymer (C), and the content of the other vinyl monomer in 100% by mass of the vinyl monomer mixture (m1) is preferably 35% by mass or less, and particularly preferably 30% by mass or less, from the viewpoint of easily maintaining the basic characteristics of the (meth) acrylate-based copolymer (C) such as heat resistance, color developability, and high mechanical properties.

The mass average molecular weight (Mw) of the (meth) acrylate-based copolymer (C) is not particularly limited, and is preferably in the range of 10000 to 300000, and particularly preferably in the range of 50000 to 200000. When the mass average molecular weight of the (meth) acrylate copolymer (C) is within the above range, the resulting (meth) acrylate copolymer (C) and the thermoplastic resin composition are excellent in flowability, scratch resistance and impact resistance.

The mass average molecular weight of the (meth) acrylate copolymer (C) is measured by dissolving it in Tetrahydrofuran (THF) using (GPC), and the obtained molecular weight is expressed in terms of standard Polystyrene (PS).

From the viewpoint of heat resistance, the glass transition temperature (Tg) of the (meth) acrylate copolymer (C) is preferably 100 to 140 ℃, and particularly preferably 105 to 135 ℃.

In the thermoplastic resin composition of the present invention, the content of the (meth) acrylate copolymer (C) is preferably 10 to 45 parts by mass based on 100 parts by mass of the total of the aromatic polycarbonate resin (a), the graft copolymer (B) and the (meth) acrylate copolymer (C) from the viewpoints of impact resistance, heat resistance and rigidity. The content of the (meth) acrylate copolymer (C) is more preferably 10 to 40 parts by mass, and still more preferably 10 to 35 parts by mass. When the content of the (meth) acrylate-based copolymer (C) is not less than the lower limit, the impact resistance, heat resistance and rigidity are good, and when the content is not more than the upper limit, the impact resistance is good.

< NO-alkyl hindered amine light stabilizer (D) >

The NO-alkyl type hindered amine light stabilizer is a substance in which a hydrogen atom bonded to a nitrogen atom of a 2,2,6, 6-tetramethylpiperidine skeleton is substituted with an alkoxy group.

The NO-alkyl hindered amine light stabilizer (D) may be a monocyclic light stabilizer having 12, 2,6, 6-tetramethylpiperidine ring, or a bicyclic light stabilizer in which 2,2,6, 6-tetramethylpiperidine rings are ester-bonded to a dicarboxylic acid such as sebacic acid or a carbonic acid, and is preferably a bicyclic light stabilizer from the viewpoint of the effect of improving hydrolysis resistance, weather resistance, and impact resistance.

The number of carbon atoms of the alkoxy group bonded to the nitrogen atom of the 2,2,6, 6-tetramethylpiperidine skeleton is preferably 5 to 15, more preferably 6 to 14, and even more preferably 7 to 13, from the viewpoint of the effect of improving hydrolysis resistance, weather resistance, and impact resistance.

The molecular weight of the NO-alkyl type hindered amine light stabilizer (D) is preferably in the range of 500 to 1000 from the viewpoint of impact resistance. The molecular weight of the NO-alkyl hindered amine light stabilizer (D) is more preferably 550 to 950, and still more preferably 600 to 900.

As the NO-alkyl type hindered amine light stabilizer (D), the corresponding commercially available products can be used. Examples of commercially available products of the NO-alkyl hindered amine light stabilizer (D) include "ADEKASTABLA-81" manufactured by ADEKA corporation and "Tinuvin PA 123" manufactured by BASF corporation, which are represented by the following structural formulae.

[ solution 1]

The NO-alkyl type hindered amine light stabilizer (D) may be used singly or in combination of two or more.

When the thermoplastic resin composition of the present invention contains the NO-alkyl hindered amine light stabilizer (D), the content of the NO-alkyl hindered amine light stabilizer (D) in the thermoplastic resin composition of the present invention is preferably 0.1 to 0.8 parts by mass, more preferably 0.2 to 0.7 parts by mass, based on 100 parts by mass of the total of the aromatic polycarbonate resin (a), the graft copolymer (B), and the (meth) acrylate copolymer (C). When the content of the NO-alkyl hindered amine light stabilizer (D) is not less than the above lower limit, excellent hydrolysis resistance and weather resistance tend to be obtained and impact resistance tends to be improved. When the content of the NO-alkyl hindered amine light stabilizer (D) is not more than the upper limit, the durability tends to be good.

< other thermoplastic resins >

The thermoplastic resin composition of the present invention may contain, if necessary, other thermoplastic resins other than the aromatic polycarbonate resin (a), the graft copolymer (B), and the (meth) acrylate copolymer (C). The other thermoplastic resin is not particularly limited, and examples thereof include AS resins, polybutylene terephthalate (PBT resin), polyethylene terephthalate (PET resin), polyvinyl chloride, polystyrene, polyacetal resins, modified polyphenylene ether (modified PPE resin), ethylene-vinyl acetate copolymers, polyarylates, liquid crystal polyester resins, polyethylene resins, polypropylene resins, fluorine resins, and polyamide resins (nylon). These other thermoplastic resins may be used alone or in combination of two or more.

When the thermoplastic resin composition of the present invention contains such another thermoplastic resin, the content of the other thermoplastic resin in 100 mass% of the total thermoplastic resin components in the thermoplastic resin composition is preferably 40 mass% or less, and particularly preferably 30 mass% or less, from the viewpoint of more effectively obtaining the effects of impact resistance, heat resistance, rigidity, and color developability.

< additives >

The thermoplastic resin composition of the present invention may contain other additives which are conventionally used in the production (mixing) of thermoplastic resin compositions and the molding thereof, for example, a lubricant, a pigment, a dye, a filler (carbon black, silica, titanium oxide, etc.), a heat-resistant agent (heat stabilizer), an antioxidant deterioration agent, a weather-resistant agent (ultraviolet absorber, light stabilizer) other than the NO-alkyl hindered amine light stabilizer (D), a release agent, a plasticizer, an antistatic agent, a flame retardant aid, a curing agent, a curing accelerator, a conductivity-imparting agent, a stress relaxation agent, a crystallization accelerator, a hydrolysis inhibitor, a lubricant, an impact-imparting agent, a sliding property-improving agent, a solubilizer, a nucleating agent, a reinforcing agent, a flow control agent, a thickener, a lubricant, a slip property-improving agent, a solubilizer, a nucleating agent, Anti-settling agents, anti-dripping agents, defoaming agents, coupling agents, light diffusing fine particles, rust inhibitors, antibacterial agents, antifungal agents, antifouling agents, conductive polymers, and the like.

< method for producing thermoplastic resin composition >

The thermoplastic resin composition of the present invention can be produced by a known method using a known apparatus. For example, a melt mixing method is a common method, and examples of an apparatus used in this method include an extruder, a banbury mixer, a roll mill, and a kneader. The mixing may be performed by either a batch method or a continuous method. The order of mixing the components is not particularly limited, as long as all the components can be uniformly mixed.

[ molded article ]

The molded article of the present invention is obtained by molding the thermoplastic resin composition of the present invention. Examples of the molding method include injection molding, injection compression molding, extrusion, blow molding, vacuum molding, pressure molding, calendering, and inflation molding. Among these, injection molding and injection compression molding are preferable because they are excellent in mass productivity and can provide a molded article with high dimensional accuracy.

[ use ]

The thermoplastic resin composition of the present invention comprising the aromatic polycarbonate resin (a), the graft copolymer (B) and the (meth) acrylate copolymer (C) is excellent in flowability of a molded article thereof, and is also excellent in color developability (coloring property), heat resistance, impact resistance and rigidity, and therefore, is suitable for use in a wide range of fields such as automotive interior and exterior parts, office equipment, home appliances and building materials.

The thermoplastic resin composition of the present invention containing an NO-alkyl hindered amine light stabilizer (D) and a molded article thereof are excellent in flowability and color developability (colorability), impact resistance, durability and weather resistance, and therefore, are suitable for use in a wide range of fields such as automotive interior and exterior parts, office equipment, home appliances and building materials.