JP7310078B2 - Resin composition and molded product - Google Patents

Description

The present invention relates to resin compositions and molded articles. In particular, the present invention relates to a resin composition using a polycarbonate resin that is excellent in transparency, scratch resistance, light resistance, etc., and that can provide a molded article that is extremely excellent in surface hardness.

Polycarbonate resins are excellent in mechanical strength, electrical properties, transparency, etc., and are widely used as engineering plastics in various fields such as electric and electronic equipment fields and automobile fields. In recent years, in these fields, molded products have become thinner, smaller, and lighter, and further improvements in the performance of molding materials have been demanded, and several proposals have been made.

For example, Patent Document 1 discloses a graft copolymer (B ) contains 0.1 to 12 parts by mass of a polycarbonate resin composition. The document also describes that the polycarbonate resin composition is excellent in scratch resistance with nails.

Japanese Unexamined Patent Application Publication No. 2017-110180

Conventionally, it has been known that polycarbonate resins containing structural units derived from bisphenol C tend to have high pencil hardness. Here, there is a case where a molded article molded from a polycarbonate resin containing a structural unit derived from bisphenol C is used as a product without being subjected to a treatment such as coating (hereinafter sometimes referred to as "paintless"). However, as a result of investigation by the present inventor, it was found that such a molded article has a slight problem in resistance to scratching by fingernails, although it has a high pencil hardness. Although the resin composition described in Patent Document 1 is a resin composition having excellent resistance to scratching by nails, jet blackness and the like are pursued in the examples of the same document. In other words, development of new materials is required for applications that require transparency. In addition, it is required to maintain high transparency even after the abrasion test.
In addition, depending on the application, light resistance is required, but even if the appropriate additives are blended with the polycarbonate resin, even if it is excellent in scratch resistance, and in particular, it can maintain high transparency after the abrasion test, it can be done without painting. It was a situation that the light resistance was inferior to use for
An object of the present invention is to solve the above problems. An object of the present invention is to provide an excellent resin composition and a molded article using the resin composition.

式（１）中、Ｒ¹はメチル基を表し、Ｒ²は水素原子またはメチル基を表し、Ｘ¹は下記のいずれかの式を表し、

Ｒ³およびＲ⁴は、それぞれ独立に、水素原子またはメチル基を表し、ＺはＣと結合して炭素数６～１２の、置換基を有していてもよい脂環式炭化水素を形成する基を表す；
式（Ｘ）

式（Ｘ）中、Ｒ⁵、Ｒ⁶およびＲ⁷は、それぞれ独立に、水素原子または炭素数１～２０の炭化水素基を表し、Ｒ⁸は置換基を有していてもよい炭素数６～２０の芳香族炭化水素基、または、置換基を有していてもよい炭素数６～１７の芳香族炭化水素基で置換された炭素数１～３の脂肪族炭化水素基を表す。
＜２＞前記（Ｂ）エステル化合物が、１価カルボン酸と１価アルコールとから形成されている、＜１＞に記載の樹脂組成物。
＜３＞前記式（Ｘ）におけるＲ⁵、Ｒ⁶およびＲ⁷は、それぞれ独立に、水素原子またはメチル基である、＜１＞または＜２＞に記載の樹脂組成物。
＜４＞前記式（Ｘ）におけるＲ⁸は、置換基を有していてもよいフェニル基、置換基を有していてもよいナフチル基または置換基を有していてもよいベンジル基である、＜１＞～＜３＞のいずれか１つに記載の樹脂組成物。
＜５＞前記（Ｃ）アクリル樹脂は、式（Ｘ）で表される構造単位（ｃ１）と、式（Ｘ１）で表される構造単位（ｃ２）を有する共重合体であり、前記（ｃ１）／（ｃ２）の質量比が５～８０／９５～２０となる割合で含有する、＜１＞～＜４＞のいずれか１つに記載の樹脂組成物；
式（Ｘ１）

式（Ｘ１）中、Ｒ⁵、Ｒ⁶およびＲ⁷は、それぞれ独立に、水素原子または炭素数１～２０の炭化水素基を表し、Ｒ⁹は、水素原子または置換基を有していてもよい炭素数１～２０の脂肪族炭化水素基を示す（ただし、置換基が芳香族炭化水素基を含むものを除く）。
＜６＞前記（Ｃ）アクリル樹脂の重量平均分子量が５，０００～３０，０００である、＜１＞～＜５＞のいずれか１つに記載の樹脂組成物。
＜７＞前記（Ｃ）アクリル樹脂の含有量が、（Ａ）ポリカーボネート樹脂１００質量部に対し１～４５質量部である、＜１＞～＜６＞のいずれか１つに記載の樹脂組成物。
＜８＞（Ｂ）エステル化合物の（Ｃ）アクリル樹脂に対する比率（（Ｂ）／（Ｃ）×１００）（質量％）が、３～２００である、＜１＞～＜７＞のいずれか１つに記載の樹脂組成物。
＜９＞（Ａ）ポリカーボネート樹脂は、さらに、下記式（２）で表される構造単位を含む、＜１＞～＜８＞のいずれか１つに記載の樹脂組成物；
式（２）

式（２）中、Ｘ²は下記のいずれかの式を表し、

Ｒ³およびＲ⁴は、それぞれ独立に、水素原子またはメチル基を表し、ＺはＣと結合して炭素数６～１２の、置換基を有していてもよい脂環式炭化水素を形成する基を表す。
＜１０＞前記樹脂組成物から形成される厚み２ｍｍの試験片は、サラシを使用した往復摩耗試験前後のヘイズの差であるΔヘイズが４．００％以下である、＜１＞～＜９＞のいずれか１つに記載の樹脂組成物。
＜１１＞＜１＞～＜１０＞のいずれか１つに記載の樹脂組成物から形成される成形品。 Based on the above-mentioned problems, the present inventors conducted studies and found that the above-mentioned problems can be solved by blending an ester compound with a predetermined polycarbonate resin and setting the haze and dynamic friction coefficient within a predetermined range. Found it. Specifically, the above problems have been solved by the following means <1>, preferably by <2> to <11>.
<1> (A) A thermoplastic resin composition containing 0.5 to 10.0 parts by mass of an ester compound and (C) 1 to 100 parts by mass of an acrylic resin per 100 parts by mass of a polycarbonate resin. wherein the (A) polycarbonate resin contains 5 mol% or more and less than 50 mol% of structural units represented by the following formula (1) among all structural units, and the (B) ester compound is an alcohol and a carboxylic acid The (C) acrylic resin contains a structural unit represented by the following formula (X), and a test piece having a thickness of 2 mm formed from the resin composition has a haze measured in accordance with ISO 14782 is 5.0% or less, and the dynamic friction coefficient according to ISO 19252 at a load of 30 N is 0.38 or less;
formula (1)

In formula (1), R ¹ represents a methyl group, R ² represents a hydrogen atom or a methyl group, X ¹ represents any of the following formulas,

R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group, and Z is combined with C to form an alicyclic hydrocarbon having 6 to 12 carbon atoms, which may have a substituent. representing a group;
Formula (X)

In formula (X), R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ⁸ is an optionally substituted C 6 represents an aromatic hydrocarbon group of up to 20 or an aliphatic hydrocarbon group of 1 to 3 carbon atoms substituted with an optionally substituted aromatic hydrocarbon group of 6 to 17 carbon atoms.
<2> The resin composition according to <1>, wherein the (B) ester compound is formed from a monohydric carboxylic acid and a monohydric alcohol.
<3> The resin composition according to <1> or <2>, wherein R ⁵ , R ⁶ and R ⁷ in formula (X) are each independently a hydrogen atom or a methyl group.
<4> R ⁸ in the above formula (X) is a phenyl group optionally having substituent(s), a naphthyl group optionally having substituent(s) or a benzyl group optionally having substituent(s) , The resin composition according to any one of <1> to <3>.
<5> The (C) acrylic resin is a copolymer having a structural unit (c1) represented by the formula (X) and a structural unit (c2) represented by the formula (X1), and the (c1 )/(c2) at a mass ratio of 5 to 80/95 to 20, the resin composition according to any one of <1> to <4>;
Formula (X1)

In formula (X1), R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ⁹ is a hydrogen atom or may have a substituent. A good aliphatic hydrocarbon group having 1 to 20 carbon atoms (excluding those containing an aromatic hydrocarbon group as a substituent).
<6> The resin composition according to any one of <1> to <5>, wherein the (C) acrylic resin has a weight average molecular weight of 5,000 to 30,000.
<7> The resin composition according to any one of <1> to <6>, wherein the content of the (C) acrylic resin is 1 to 45 parts by mass with respect to 100 parts by mass of the (A) polycarbonate resin. .
<8> Any one of <1> to <7>, wherein the ratio ((B)/(C) × 100) (mass%) of the (B) ester compound to the (C) acrylic resin is 3 to 200 The resin composition according to 1.
<9> (A) The resin composition according to any one of <1> to <8>, wherein the polycarbonate resin further comprises a structural unit represented by the following formula (2);
Formula (2)

In formula (2), X ² represents any of the following formulas,

R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group, and Z is combined with C to form an alicyclic hydrocarbon having 6 to 12 carbon atoms and optionally having a substituent. represents a group.
<10> A test piece having a thickness of 2 mm formed from the resin composition has a haze difference of 4.00% or less before and after a reciprocating abrasion test using a bleached cloth, <1> to <9>. The resin composition according to any one of.
<11> A molded article formed from the resin composition according to any one of <1> to <10>.

According to the present invention, a resin composition having extremely excellent surface hardness, excellent scratch resistance, particularly high transparency retention rate after an abrasion test, and excellent light resistance, and the resin composition are used. It became possible to provide molded products with

The contents of the present invention will be described in detail below. In this specification, the term "~" is used to mean that the numerical values before and after it are included as the lower limit and the upper limit.

式（１）中、Ｒ¹はメチル基を表し、Ｒ²は水素原子またはメチル基を表し、Ｘ¹は下記のいずれかの式を表し、

Ｒ³およびＲ⁴は、それぞれ独立に、水素原子またはメチル基を表し、ＺはＣと結合して炭素数６～１２の、置換基を有していてもよい脂環式炭化水素を形成する基を表す。
式（Ｘ）

式（Ｘ）中、Ｒ⁵、Ｒ⁶およびＲ⁷は、それぞれ独立に、水素原子または炭素数１～２０の炭化水素基を表し、Ｒ⁸は置換基を有していてもよい炭素数６～２０の芳香族炭化水素基、または、置換基を有していてもよい炭素数６～１７の芳香族炭化水素基で置換された炭素数１～３の脂肪族炭化水素基を表す。
このような構成とすることにより、表面硬度に優れ、耐擦傷性に優れ、特に、摩耗試験後も高い透明性を高く維持でき、さらには、耐光性にも優れた樹脂組成物を提供可能になる。さらに押出性も向上させることが可能になる。
以下、本発明の詳細について説明する。 The resin composition of the present invention comprises (A) 100 parts by mass of a polycarbonate resin, (B) 0.5 to 10.0 parts by mass of an ester compound, and (C) 1 to 100 parts by mass of an acrylic resin. In the plastic resin composition, the (A) polycarbonate resin contains 5 mol% or more and less than 50 mol% of structural units represented by the following formula (1) in all structural units, and the (B) ester compound is composed of an alcohol and a carboxylic acid, the (C) acrylic resin contains a structural unit represented by the following formula (X), and a test piece having a thickness of 2 mm formed from the resin composition is in accordance with ISO 14782 The measured haze is 5.0% or less, and the dynamic friction coefficient according to ISO 19252 at a load of 30 N is 0.38 or less.
formula (1)

In formula (1), R ¹ represents a methyl group, R ² represents a hydrogen atom or a methyl group, X ¹ represents any of the following formulas,

R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group, and Z is combined with C to form an alicyclic hydrocarbon having 6 to 12 carbon atoms, which may have a substituent. represents a group.
Formula (X)

In formula (X), R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ⁸ is an optionally substituted C 6 represents an aromatic hydrocarbon group of up to 20 or an aliphatic hydrocarbon group of 1 to 3 carbon atoms substituted with an optionally substituted aromatic hydrocarbon group of 6 to 17 carbon atoms.
With such a configuration, it is possible to provide a resin composition that has excellent surface hardness, excellent scratch resistance, can maintain high transparency even after an abrasion test, and is also excellent in light resistance. Become. Furthermore, it becomes possible to improve extrudability.
The details of the present invention will be described below.

式（１）中、Ｒ¹はメチル基を表し、Ｒ²は水素原子またはメチル基を表し、Ｘ¹は下記のいずれかの式を表し、

Ｒ³およびＲ⁴は、それぞれ独立に、水素原子またはメチル基を表し、ＺはＣと結合して炭素数６～１２の、置換基を有していてもよい脂環式炭化水素を形成する基を表す。 <(A) polycarbonate resin>
The polycarbonate resin used in the resin composition of the present invention contains the structural unit represented by formula (1) in a proportion of 5 mol % or more and less than 50 mol % in all structural units.
formula (1)

In formula (1), R ¹ represents a methyl group, R ² represents a hydrogen atom or a methyl group, X ¹ represents any of the following formulas,

R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group, and Z is combined with C to form an alicyclic hydrocarbon having 6 to 12 carbon atoms, which may have a substituent. represents a group.

Two R ² in formula (1) may be the same or different, and are preferably the same. R ² is preferably a hydrogen atom.

である場合、Ｒ³およびＲ⁴は、少なくとも一方がメチル基であることが好ましく、両方がメチル基であることがより好ましい。
またＸ¹が、

の場合、Ｚは、上記式（１）中の２個のフェニル基と結合する炭素Ｃと結合して、炭素数６～１２の２価の脂環式炭化水素基を形成するが、２価の脂環式炭化水素基としては、例えば、シキロヘキシリデン基、シクロヘプチリデン基、シクロドデシリデン基、アダマンチリデン基、シクロドデシリデン基等のシクロアルキリデン基が挙げられる。置換されたものとしては、これらのメチル置換基、エチル置換基を有するもの等が挙げられる。これらの中でも、シクロヘキシリデン基、シキロヘキシリデン基のメチル置換体（好ましくは３，３，５－トリメチル置換体）、シクロドデシリデン基が好ましい。
式（１）中、Ｘ¹は下記構造が好ましい。

In formula (1), X ¹ is

When , at least one of R ³ and R ⁴ is preferably a methyl group, more preferably both are methyl groups.
Also, if X ¹ is

In the case of, Z is combined with the carbon C that bonds to the two phenyl groups in the above formula (1) to form a divalent alicyclic hydrocarbon group having 6 to 12 carbon atoms, but the divalent Examples of the alicyclic hydrocarbon group include cycloalkylidene groups such as a cyclohexylidene group, a cycloheptylidene group, a cyclododecylidene group, an adamantylidene group, and a cyclododecylidene group. Substituted groups include those having methyl substituents, ethyl substituents, and the like. Among these, a cyclohexylidene group, a methyl-substituted cyclohexylidene group (preferably a 3,3,5-trimethyl-substituted group), and a cyclododecylidene group are preferred.
In formula (1), X ¹ preferably has the following structure.

Specific examples of preferred structural units of formula (1) include the following i) to iv).
i) a structural unit composed of 2,2-bis(3-methyl-4-hydroxyphenyl)propane, ie, R ¹ is a methyl group, R ² is a hydrogen atom, and X ¹ is --C(CH ₃ ) ₂ -- A structural unit that is
ii) a structural unit composed of 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, ie R ¹ is a methyl group, R ² is a methyl group and X ¹ is --C(CH ₃ ) ₂ - structural unit,
iii) a structural unit composed of 2,2-bis(3-methyl-4-hydroxyphenyl)cyclohexane, ie a structural unit in which R ¹ is a methyl group, R ² is a hydrogen atom and X ¹ is a cyclohexylidene group ,
iv) a structural unit composed of 2,2-bis(3-methyl-4-hydroxyphenyl)cyclododecane, ie R ¹ is a methyl group, R ² is a hydrogen atom and X ¹ is a cyclododecylidene group It is a structural unit.
Among these, the above i), ii) and iii) are preferred, the above i) and iii) are more preferred, and the above i) is even more preferred.

In the polycarbonate resin (A) in the present invention, the structural unit represented by formula (1) is 5 mol% or more, preferably 10 mol% or more, more preferably 15 mol% or more, more preferably 15 mol% or more, more preferably 20 mol % or more, more preferably 25 mol % or more. Further, the upper limit is less than 50 mol%, preferably 48 mol% or less, more preferably 47 mol% or less, 45 mol% or less, 43 mol% or less, 40 mol% or less good. By making it 5 mol % or more, the surface hardness of the molded product tends to be improved. By making it less than 50 mol %, the light resistance tends to be improved.

In the present invention, (A) the polycarbonate resin may contain only one type of structural unit represented by formula (1), or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

式（２）中、Ｘ²は下記のいずれかの式を表し、

Ｒ³およびＲ⁴は、それぞれ独立に、水素原子またはメチル基を表し、ＺはＣと結合して炭素数６～１２の、置換基を有していてもよい脂環式炭化水素を形成する基を表す。
ＺがＣと結合して形成される脂環式炭化水素としては、シクロヘキシリデン基、シクロヘプチリデン基、シクロドデシリデン基、アダマンチリデン基、シクロドデシリデン基等のシクロアルキリデン基が挙げられる。ＺがＣと結合して形成される置換基を有する脂環式炭化水素としては、上述した脂環式炭化水素基のメチル置換体、エチル置換体などが挙げられる。これらの中でも、シクロヘキシリデン基、シクロヘキシリデン基のメチル置換体（好ましくは３，３，５－トリメチル置換体）、シクロドデシリデン基が好ましい。 In the present invention, (A) the polycarbonate resin may have structural units other than the structural unit represented by the formula (1). As another structural unit, a structural unit represented by the following formula (2) is preferable.
formula (2)

In formula (2), X ² represents any of the following formulas,

R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group, and Z is combined with C to form an alicyclic hydrocarbon having 6 to 12 carbon atoms, which may have a substituent. represents a group.
The alicyclic hydrocarbon formed by combining Z with C includes a cycloalkylidene group such as a cyclohexylidene group, a cycloheptylidene group, a cyclododecylidene group, an adamantylidene group, and a cyclododecylidene group. is mentioned. Examples of the alicyclic hydrocarbon having a substituent formed by combining Z with C include methyl-substituted and ethyl-substituted alicyclic hydrocarbon groups described above. Among these, a cyclohexylidene group, a methyl-substituted cyclohexylidene group (preferably a 3,3,5-trimethyl-substituted group), and a cyclododecylidene group are preferred.

Ｒ³およびＲ⁴は、少なくとも一方がメチル基であることが好ましく、両方がメチル基であることがより好ましい。 The preferred range of X ² in formula (2) is synonymous with the preferred range of X ¹ in formula (1). That is, in formula (2), X ² preferably has the following structure.

At least one of R ³ and R ⁴ is preferably a methyl group, more preferably both are methyl groups.

A preferred specific example of the structural unit represented by the above formula (2) is 2,2-bis(4-hydroxyphenyl)propane, that is, a structural unit composed of bisphenol-A (carbonate structural unit).
In the present invention, the structural unit represented by formula (2) is preferably 50 mol% or more, more preferably 52 mol% or more, still more preferably 53 mol% or more, and still more preferably 55 mol% of all structural units. Above, more preferably 57 mol % or more, still more preferably 60 mol % or more. Also, the upper limit is 95 mol % or less, preferably 90 mol % or less, more preferably 85 mol % or less, and even more preferably 80 mol % or less, of all structural units.
In the present invention, (A) the polycarbonate resin preferably contains a structural unit represented by formula (2), and may contain only one type or two or more types. When two or more types are included, the total amount is preferably within the above range.

In the present invention, (A) the polycarbonate resin, as a dihydroxy compound constituting a structural unit other than the structural unit represented by the formula (1) and the structural unit represented by the formula (2), for example, the following aromatic dihydroxy compounds such as;
Bis(4-hydroxyphenyl)methane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)pentane, 2,2-bis(4-hydroxyphenyl)-4-methyl Pentane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3- (1-methylethyl)phenyl)propane, 2,2-bis(4-hydroxy-3-tert-butylphenyl)propane, 2,2-bis(4-hydroxy-3-(1-methylpropyl)phenyl)propane , 2,2-bis(4-hydroxy-3-cyclohexylphenyl)propane, 2,2-bis(4-hydroxy-3-phenylphenyl)propane, 1,1-bis(4-hydroxyphenyl)decane, 1, 1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,1-bis(4-hydroxyphenyl)phenylmethane, 1,1-bis(4- hydroxy-3-methylphenyl)cyclohexane, 1,1-bis(4-hydroxy-3,5-dimethylphenyl)cyclohexane, 1,1-bis(4-hydroxy-3-(1-methylethyl)phenyl)cyclohexane, 1,1-bis(4-hydroxy-3-tert-butylphenyl)cyclohexane, 1,1-bis(4-hydroxy-3-(1-methylpropyl)phenyl)cyclohexane, 1,1-bis(4-hydroxy -3-cyclohexylphenyl)cyclohexane, 1,1-bis(4-hydroxy-3-phenylphenyl)cyclohexane, 1,1-bis(4-hydroxy-3-methylphenyl)-1-phenylethane, 1,1- Bis(4-hydroxy-3,5-dimethylphenyl)-1-phenylethane, 1,1-bis(4-hydroxy-3-(1-methylethyl)phenyl)-1-phenylethane, 1,1-bis (4-hydroxy-3-tert-butylphenyl)-1-phenylethane, 1,1-bis(4-hydroxy-3-(1-methylpropyl)phenyl)-1-phenylethane, 1,1-bis( 4-hydroxy-3-cyclohexylphenyl)-1-phenylethane, 1,1-bis(4-hydroxy-3-phenylphenyl)-1-phenylethane, 1,1-bis(4-hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclooctane, 4,4′-(1,3-phenylenediisopropylidene)bisphenol, 4,4′-(1,4-phenylenediisopropylidene)bisphenol, 9, 9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxyphenyl ether, 4,4'- dihydroxybiphenyl, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4-hydroxy-6-methyl-3-tert-butylphenyl)butane.

Further, as an embodiment of other structural units, structural units represented by formula (1) described in paragraph 0008 of WO2017/099226 are also exemplified, and further, paragraphs 0043 to 0052 of WO2017/099226. The description can also be considered, and the contents thereof are incorporated herein.

式（３）中、Ｒ¹⁵～Ｒ¹⁸は、それぞれ独立に、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、炭素数１～９のアルキル基、炭素数６～１２のアリール基、炭素数１～５のアルコキシ基、炭素数２～５のアルケニル基または炭素数７～１７のアラルキル基を表す；ｎ１、ｎ２およびｎ３は、それぞれ独立に、０～４の整数を表す。
式（３）で表される構造単位の詳細は、特開２０１１－０４６７６９号公報の記載を参酌でき、これらの内容は本明細書に組み込まれる。 Furthermore, as another embodiment of another structural unit, a structural unit represented by the following formula (3) is also exemplified.

In formula (3), R ¹⁵ to R ¹⁸ each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 9 carbon atoms, an aryl group having 6 to 12 carbon atoms, represents an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an aralkyl group having 7 to 17 carbon atoms;
Details of the structural unit represented by formula (3) can be referred to in JP-A-2011-046769, and the contents thereof are incorporated herein.

In the present invention, the content of structural units other than the structural units represented by the above formula (1) and the structural units represented by the formula (2) in the polycarbonate resin (A) is 30 mol% of the total structural units. is preferably 20 mol % or less, more preferably 10 mol % or less, may be 5 mol % or less, or may be 1 mol % or less.

Embodiments of the (A) polycarbonate resin in the present invention are described below.
Among all structural units, the structural unit represented by formula (1) is 5 mol% or more and less than 50 mol% (preferably 10 to 48 mol%), and a structure other than the structural unit represented by formula (1) Polycarbonate resins containing units (preferably 50 to 95 mol %, more preferably 52 to 90 mol % of structural units represented by formula (2)) are exemplified by the following blend forms.
- A polycarbonate resin (A1) in which 5 mol% or more and less than 50 mol% of all structural units are structural units represented by formula (1), and more than 50 mol% of all structural units are represented by formula (2) A mixture of a polycarbonate resin (A2) consisting of a structural unit comprising:
Copolycarbonate resin (A3) in which the total of the structural units represented by formula (1) and the structural units represented by formula (2) accounts for more than 95 mol% of all structural units, provided that the polycarbonate resin (A3) The structural unit of formula (1) accounts for 5 mol% or more and less than 50 mol%:
- A mixture of the polycarbonate resin (A1), the polycarbonate resin (A2), and the copolymerized polycarbonate resin (A3):
- A mixture of the polycarbonate resin (A1) and the copolymerized polycarbonate resin (A3);
- A mixture of the copolymerized polycarbonate resin (A3) and the polycarbonate resin (A2);
- In any of the above embodiments, a mixture containing two or more of at least one of the polycarbonate resin (A1), the polycarbonate resin (A2) and the copolymerized polycarbonate resin (A3);
In any embodiment, the structural unit represented by the formula (1) in the polycarbonate resin (A) may be contained at a ratio of 5 mol% or more and less than 50 mol%, and further, the structural unit represented by the formula (1) It is preferable that the structural unit represented by and the structural unit represented by formula (2) are contained in all the structural units in a proportion satisfying the above-described preferable range.

In the present invention, among the blend forms exemplified above, a form containing (A1) a polycarbonate resin and (A2) a polycarbonate resin is particularly preferred. When (A1) polycarbonate resin and (A2) polycarbonate resin are included, the mixing ratio of the two is preferably 5:95 to 48:52, more preferably 10:90 to 47:53, by mass. It is preferably 15:85 to 45:55, even more preferably 20:80 to 43:57, and even more preferably 25:75 to 40:60.
The resin composition of the present invention may contain only one kind of (A1) polycarbonate resin and (A2) polycarbonate resin, or may contain two or more kinds thereof. When two or more types are included, the total amount is preferably within the above range. With such a configuration, the pencil hardness of the molded article obtained from the resin composition can be HB or higher, further F or higher. Although the upper limit of the pencil hardness is not particularly defined, it may be 4H or less, or even 3H or less.

In the present invention, the lower limit of the viscosity-average molecular weight (Mv) of the polycarbonate resin (A) is preferably 9,000 or more, more preferably 10,000 or more, and more preferably 12,000 or more. More preferred. Also, the upper limit of Mv is preferably 32,000 or less, more preferably 30,000 or less, and even more preferably 28,000 or less.
By setting the viscosity-average molecular weight to the above lower limit or more, moldability is improved and a molded product having high mechanical strength can be obtained. Further, by setting the content to the above upper limit or less, the fluidity of the molded product is improved, and thin molded products can be efficiently produced.
The viscosity-average molecular weight (Mv) is measured according to the method described in the examples below (the same applies to Mv hereinafter). When two or more types of (A) polycarbonate resins are included, the sum of the values obtained by multiplying the viscosity-average molecular weight of each polycarbonate resin by the mass fraction is used. Hereinafter, the viscosity average molecular weight will be similarly considered.

The (A) polycarbonate resin has a pencil hardness measured according to ISO 15184 of 3B to 2H, preferably B to 2H, and more preferably HB to 2H. The pencil hardness is measured according to the method described in the examples below (the same applies to the pencil hardness below). When two or more types of (A) polycarbonate resins are included, the pencil hardness of the mixture is preferably within the above range.

The method for producing the (A) polycarbonate resin is not particularly limited, and any known method can be adopted. Examples thereof include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid-phase transesterification method of a prepolymer. Among these, the interfacial polymerization method and the melt transesterification method are preferred.

The resin composition of the present invention preferably contains (A) a polycarbonate resin and (C) an acrylic resin in a total amount of 80% by mass or more of the composition, more preferably 85% by mass or more. It is more preferably contained at a rate of 90% by mass or more, and even more preferably at a rate of 93% by mass or more. Although the upper limit of the total content of (A) the polycarbonate resin and (C) the acrylic resin is not particularly defined, it can be, for example, 99.4% by mass or less.

<(B) Ester compound>
The resin composition of the present invention contains (B) an ester compound. The (B) ester compound used in the present invention is composed of an alcohol and a carboxylic acid, and can be appropriately selected from known ester compounds regardless of the type thereof.

An example of an embodiment of the ester compound in the present invention is, for example, a fatty acid ester, more specifically an ester compound formed from a saturated straight-chain carboxylic acid and a saturated straight-chain alcohol. Preferred embodiments of the ester compound of the present invention will be specifically described below, and among them, the monoester compound is particularly preferred.

A first embodiment of (B) an ester compound in the present invention is a monoester compound having one ester group formed from a monovalent carboxylic acid and a monohydric alcohol. By reducing the number of ester groups in this way, the transparency of the resulting molded article can be further improved.

The monoester compound used in the present invention preferably has a hydroxyl value of 100 mgKOH/g or less and/or a carbon number of 42 or more.
By lowering the hydroxyl value, the monoester compound and the polycarbonate resin are less likely to decompose during extrusion, and the generation of gas during molding can be effectively suppressed. The hydroxyl value is more preferably 80 mgKOH/g or less, still more preferably 50 mgKOH/g or less, still more preferably 35 mgKOH/g or less.
The hydroxyl value is measured according to the method described in Examples below.

In addition, in the present invention, by using a monoester compound having a carbon number of a predetermined value or more, it is possible to effectively suppress the generation of gas during extrusion and molding.
The number of carbon atoms in the monoester compound is preferably 42 or more, more preferably 44 or more. Although the upper limit of the number of carbon atoms in the monoester compound is not particularly defined, it is preferably 100 or less, more preferably 90 or less. (The number of carbon atoms in a monoester compound is the total number of carbon atoms contained in one molecule. Therefore, when the monoester compound is formed from a monovalent carboxylic acid and a monohydric alcohol, The total number of carbon atoms contained in the alcohol is the number of carbon atoms in the monoester compound.
Moreover, when 2 or more types of monoester compounds are included, let carbon number be the total value of the value which multiplied the mass fraction to the carbon number of each monoester compound.

The molecular weight of the monoester compound used in the present invention is preferably 2000 or less, more preferably 1500 or less, even more preferably 1200 or less. With such a configuration, it is possible to obtain a molded article having a good balance between high transparency and high scratch resistance. Details such as the structure will be described in detail.

The monoester compound used in the present invention may have a straight chain structure or a branched structure, but preferably has a straight chain structure and both ends are alkyl groups having 15 or more carbon atoms (preferably carbon 15 to 30 alkyl groups). With such a configuration, it becomes easier to obtain a molded article having a good balance between high transparency and high scratch resistance.

Next, carboxylic acid will be explained.
In the present invention, the carboxylic acid may be any of a saturated fatty acid, an unsaturated fatty acid, and an aromatic carboxylic acid as long as it is a monovalent carboxylic acid, and may have a branched structure. The carboxylic acid in the present invention is preferably a saturated fatty acid, particularly preferably a linear saturated fatty acid.
Moreover, the carboxylic acid may or may not have a substituent, but it is preferable not to have it. The transparency of the resulting molded article tends to be more improved when it does not have a substituent.
Furthermore, the carboxylic acid is preferably composed only of oxygen atoms, carbon atoms and hydrogen atoms. The carboxylic acid preferably has 2 to 45 carbon atoms, more preferably 10 to 40 carbon atoms, still more preferably 15 to 36 carbon atoms, and particularly preferably 20 to 30 carbon atoms.
Specific examples of carboxylic acids (the number in parentheses is the number of carbon atoms) include lauric acid (saturated C12), myristic acid (saturated C14), palmitic acid (saturated C16), stearic acid (saturated C18), oleic acid (unsaturated C18), linoleic acid (unsaturated C18), arachidic acid (saturated C20), eicosenoic acid (unsaturated C20), behenic acid (saturated C22), erucic acid (unsaturated C22), lignocericic acid (saturated C24), serotin Acid (saturated C26), montanic acid (saturated C28), melissic acid (saturated C30) are exemplified.

Next, alcohol will be explained.
In the present invention, the alcohol is preferably a monohydric alcohol, and may be a saturated alcohol, an unsaturated alcohol, or an aromatic alcohol, and may have a branched structure. The alcohol in the present invention is preferably a saturated alcohol, particularly preferably a linear saturated alcohol.
Also, the alcohol may or may not have a substituent, but preferably not. The transparency of the resulting molded article tends to be more improved when it does not have a substituent.
Furthermore, the alcohol is preferably composed only of oxygen atoms, carbon atoms and hydrogen atoms.
The alcohol preferably has 2 to 45 carbon atoms, more preferably 5 to 36 carbon atoms.
Specific examples of alcohols (the number in parentheses is the number of carbon atoms) include octanol (saturated C8), dodecanol (saturated C12), stearyl alcohol (saturated C18), oleyl alcohol (unsaturated C18), behenyl alcohol (saturated C22), Silyl alcohols (unsaturated C22), and montanyl alcohols (saturated C28) are exemplified.

In the monoester compound, the difference between the number of carbon atoms in the carboxylic acid and the number of carbon atoms in the alcohol is preferably 6 or less, more preferably 4 or less, may be 3 or less, or may be 2 or less. , there is no difference in the number of carbon atoms, that is, the number of carbon atoms may be the same.

Specific examples of monoester compounds (number of carbon atoms in parentheses) used in the present invention include behenyl behenate (C44), montanyl montanate (C56), stearyl montanate (C46), montanyl stearate (C46), Behenyl montanate (C50) and montanyl behenate (C50) are exemplified, and montanyl montanate (C56) and behenyl behenate (C44) are particularly preferred.

The monoester compound used in the present invention is often a mixture of a plurality of compounds with different carbon numbers, but in the present invention, the main component (preferably 50 mass% or more, more preferably 70 mass% or more) contains It refers to an ester compound that

A second embodiment of the (B) ester compound in the present invention is a diester compound.
The diester compound used in the present invention is a diester compound obtained from a polycarboxylic acid and a monohydric alcohol (preferably a monohydric alcohol having 16 or more carbon atoms, more preferably a monohydric alcohol having 16 to 50 carbon atoms), a polyhydric A diester compound obtained from an alcohol and a monovalent carboxylic acid (preferably a monovalent carboxylic acid having 16 or more carbon atoms, more preferably a monovalent carboxylic acid having 16 to 50 carbon atoms) or a mixture of both is preferred.
When the resin composition of the present invention contains such a diester compound, the decomposition of the polycarbonate resin is suppressed, the generation of gas during molding can be effectively suppressed, and the compatibility with the polycarbonate resin is excellent. Therefore, it is possible to obtain a resin composition that can form a molded article that has excellent extrudability, high transparency, and excellent resistance to fingernail scratches at the initial stage and after wiping with ethanol-soaked cotton. .

The diester compound is preferably a diester compound composed of a divalent carboxylic acid and a monohydric alcohol, a diester compound composed of a monovalent carboxylic acid and a dihydric alcohol, or a mixture thereof. The monohydric carboxylic acid and the monohydric alcohol may each contain an aliphatic structure, an alicyclic structure and/or an aromatic structure, and each contain an aliphatic structure and/or an alicyclic structure. is preferred. The monohydric carboxylic acid and the monohydric alcohol preferably comprise a linear or branched aliphatic structure or alicyclic structure and a carboxyl group or a hydroxyl group, respectively.
The monohydric alcohol and monocarboxylic acid each have 16 or more carbon atoms, and may also have 18 or more carbon atoms or 20 or more carbon atoms. The upper limit of the number of carbon atoms in each of the monohydric alcohol and monocarboxylic acid is preferably 50 or less, more preferably 40 or less, still more preferably 32 or less, even more preferably 30 or less, and may be 28 or less.
The dihydric carboxylic acid and the dihydric alcohol may each contain an aliphatic structure, an alicyclic structure and/or an aromatic structure, and each contain an aliphatic structure and/or an alicyclic structure. is preferred.
The dihydric carboxylic acid and the dihydric alcohol preferably comprise a linear or branched aliphatic structure or alicyclic structure and a carboxyl group or a hydroxyl group, respectively. The number of carbon atoms in each of the dihydric carboxylic acid and the dihydric alcohol is preferably 3 or more, more preferably 4 or more, even more preferably 5 or more, and even more preferably 6 or more. preferable. The number of carbon atoms in each of the dihydric carboxylic acid and the dihydric alcohol is preferably 10 or less, more preferably 8 or less.

In particular, the diester compound used in the present invention is a diester compound obtained from a divalent carboxylic acid having 3 to 10 carbon atoms and a monohydric alcohol having 16 to 40 carbon atoms, or a dihydric alcohol having 3 to 10 carbon atoms and a carbon number. It is preferably a diester compound obtained from a monovalent carboxylic acid having 16 to 40 carbon atoms, or a mixture thereof, and a diester obtained from a divalent carboxylic acid having 3 to 10 carbon atoms and a monohydric alcohol having 16 to 30 carbon atoms. compound, or a diester compound obtained from a dihydric alcohol having 3 to 10 carbon atoms and a monovalent carboxylic acid having 16 to 30 carbon atoms, or a mixture thereof, and a dihydric carboxylic acid having 3 to 10 carbon atoms. More preferably, it is a diester compound obtained from an acid and a monohydric alcohol having 16 to 30 carbon atoms or a mixture thereof.
Furthermore, in the diester compound composed of a divalent carboxylic acid and a monohydric alcohol used in the present invention, the number of carbon atoms in the monohydric alcohol is greater than the number of carbon atoms in the divalent carboxylic acid by 10 or more, preferably 10 to 20. is more preferable. Alternatively, in the diester compound composed of a monovalent carboxylic acid and a dihydric alcohol used in the present invention, the number of carbon atoms in the dihydric alcohol is greater than the number of carbon atoms in the monovalent carboxylic acid by 10 or more, preferably 10 to 20. is more preferable. By adopting such a structure, gas is less likely to be generated during extrusion or molding, and the appearance and physical properties of the molded product tend to be further improved.

Specific examples of monovalent carboxylic acids (number of carbon atoms in parentheses) include behenic acid (22), lignocericic acid (24), cerotic acid (26), montanic acid (28), and melissic acid (30). be done.

Specific examples of monohydric alcohols (number of carbon atoms in parentheses) include stearyl alcohol (18), behenyl alcohol (22) and montanyl alcohol (28).

Specific examples of divalent carboxylic acids (number of carbon atoms in parentheses) include oxalic acid (2), malonic acid (3), succinic acid (4), glutaric acid (5), adipic acid (6), pimelic acid ( 7), suberic acid (8), azelaic acid (9), sebacic acid (10), phthalic acid (8), isophthalic acid (8), terephthalic acid (8), 1,4-cyclohexanedicarboxylic acid (8), 1,3-cyclohexanedicarboxylic acid (8), 1,2-cyclohexanedicarboxylic acid (8) and the like.

Specific examples of dihydric alcohols (number of carbon atoms in parentheses) include ethylene glycol (2), propylene glycol (3), tetramethylene glycol (4), diethylene glycol (4), and 1,4-benzenedimethanol (8). , 1,4-cyclohexanedimethanol (8) and the like.

The hydroxyl value of the diester compound is preferably 100 mgKOH/g or less, more preferably 70 mgKOH/g or less, still more preferably 50 mgKOH/g or less, and even more preferably 10 mgKOH/g or less. . Although the lower limit of the hydroxyl value of the diester compound is not particularly defined, it is, for example, 1 mgKOH/g or more. By setting the hydroxyl value of the diester compound to 100 mgKOH/g or less, the promotion of decomposition of the polycarbonate resin is effectively suppressed, gas is less likely to be generated during extrusion and molding, and the appearance and physical properties of the molded product are improved. tend to and are preferred.
According to this aspect, the molded article obtained from the composition of the present invention is also excellent in resistance to nail scratches after wiping with cotton impregnated with ethanol.

The diester compound used in the present invention is often a mixture of a plurality of compounds with different carbon numbers, but in the present invention, the main component (preferably 50% by mass or more, more preferably 70% by mass or more) contains It refers to an ester compound.
The molecular weight is preferably 2,000 or less, more preferably 1,800 or less, even more preferably 1,400 or less, even more preferably 1,000 or less, and even more preferably 900 or less. The lower limit is preferably 200 or more, more preferably 500 or more. When the molecular weight of the diester compound is within the above range, a molded article having an excellent balance between high transparency and high scratch resistance can be obtained. In addition, when an ester compound is a mixture, let it be a number average molecular weight.
The diester compound used in the present invention is often a mixture of a plurality of compounds with different carbon numbers, but in the present invention, the main component (preferably 50% by mass or more, more preferably 70% by mass or more) contains It refers to an ester compound.

A third embodiment of the ester compound in the present invention is a triester compound.
The triester compound used in the present invention is an ester compound obtained from a polyhydric carboxylic acid and a monohydric alcohol having 20 or more carbon atoms (preferably 20 to 50 carbon atoms), a polyhydric alcohol and 20 or more carbon atoms (preferably carbon It is preferably an ester compound obtained from a monovalent carboxylic acid of numbers 20 to 50), or a mixture of both.
When the resin composition of the present invention contains such a triester compound, the decomposition of the polycarbonate resin is suppressed, the generation of gas during molding can be effectively suppressed, and the compatibility with the polycarbonate resin is excellent. . Therefore, it is possible to obtain a resin composition capable of forming a molded article having excellent extrudability, high transparency, and excellent resistance to fingernail scratches at the initial stage and after wiping off the solvent.

The triester compound is preferably a triester compound composed of a trivalent carboxylic acid and a monohydric alcohol, a triester compound composed of a monovalent carboxylic acid and a trihydric alcohol, or a mixture thereof.
The monohydric alcohol and monohydric carboxylic acid may each contain at least one of an aliphatic structure, an alicyclic structure and an aromatic structure, and each contain an aliphatic structure and/or an alicyclic structure. is preferred. Each of the monohydric alcohol and monocarboxylic acid preferably comprises a linear or branched aliphatic structure or alicyclic structure and a carboxyl group or a hydroxyl group.
The monohydric alcohol and the monovalent carboxylic acid each have 20 or more carbon atoms, preferably 21 or more carbon atoms, and the upper limit of the carbon number is preferably 50 or less, more preferably 40 or less, and 32 or less. More preferably, 30 or less is even more preferable.
The trihydric carboxylic acid and the trihydric alcohol may each contain at least one of an aliphatic structure, an alicyclic structure and an aromatic structure, and each may contain an aliphatic structure and/or an alicyclic structure. preferably included.
The trihydric carboxylic acid and the trihydric alcohol preferably comprise a linear or branched aliphatic structure or alicyclic structure and a carboxyl group or a hydroxyl group, respectively. It is preferable that each of the trihydric carboxylic acid and the trihydric alcohol has 3 or more carbon atoms. The number of carbon atoms in each of the trihydric carboxylic acid and the trihydric alcohol is preferably 10 or less, more preferably 8 or less.

In particular, the triester compound used in the present invention is a triester compound obtained from a trivalent carboxylic acid having 3 to 10 carbon atoms and a monohydric alcohol having 20 to 40 carbon atoms, a trihydric alcohol having 3 to 10 carbon atoms and carbon It is preferably a triester compound obtained from a monovalent carboxylic acid having 20 to 40 carbon atoms, or a mixture of two or more thereof, a trivalent carboxylic acid having 3 to 10 carbon atoms and a trivalent carboxylic acid having 20 to 30 carbon atoms. A triester compound obtained from a monohydric alcohol, a triester compound obtained from a trihydric alcohol having 3 to 10 carbon atoms and a monovalent carboxylic acid having 20 to 30 carbon atoms, or a mixture of two or more thereof. More preferably, it is a triester compound obtained from a trihydric alcohol having 3 to 10 carbon atoms and a monovalent carboxylic acid having 20 to 30 carbon atoms, or a mixture of two or more thereof.
Furthermore, in the triester compound composed of a trihydric alcohol and a monocarboxylic acid used in the present invention, the number of carbon atoms in the monovalent carboxylic acid is preferably 10 or more larger than the number of carbon atoms in the trihydric alcohol, preferably 10 to 20. Larger is more preferred. By adopting such a structure, gas is less likely to be generated during extrusion or molding, and the appearance and physical properties of the molded product tend to be further improved.

Specific examples of monovalent carboxylic acids having 20 or more carbon atoms (number of carbon atoms in parentheses) include behenic acid (22), lignocericic acid (24), cerotic acid (26), montanic acid (28), melissic acid ( 30) and the like.

Specific examples of monohydric alcohols having 20 or more carbon atoms (number of carbon atoms in parentheses) include behenyl alcohol (22) and montanyl alcohol (28).

Specific examples of trivalent carboxylic acids (number of carbon atoms in parentheses) include tricarballylic acid (6), 1,2,3-benzenetricarboxylic acid (9), 1,3,5-benzenetricarboxylic acid (9), 1,2,4-benzenetricarboxylic acid (9), 5-methyl-1,2,4-benzenetricarboxylic acid (10), 1,2,3-cyclohexanetricarboxylic acid (9), 1,3,5-cyclohexane tricarboxylic acid (9), 1,2,4-cyclohexanetricarboxylic acid (9), and the like.

Specific examples of trihydric alcohols (number of carbon atoms in parentheses) include glycerin (3), trimethylolpropane (6), trimethylolethane (5), triethylolethane (8), and 1,2,4-butanetriol. (4), hydroxyquinol (6), phloroglucinol (6), pyroganol (6), 1,2,4-cyclohexanetriol (6) and the like.

The hydroxyl value of the triester compound is preferably 100 mgKOH/g or less, more preferably 70 mgKOH/g or less, even more preferably 50 mgKOH/g or less, and even more preferably 10 mgKOH/g or less. preferable. Although the lower limit of the hydroxyl value of the triester compound is not particularly defined, it is, for example, 1 mgKOH/g or more. By setting the hydroxyl value of the triester compound to 100 mgKOH/g or less, the promotion of decomposition of the polycarbonate resin is effectively suppressed, gas is less likely to be generated during extrusion or molding, and the appearance and physical properties of the molded product are improved. There is a tendency to improve, which is desirable.
According to this aspect, the molded article obtained from the composition of the present invention is also excellent in resistance to nail scratches after wiping with cotton impregnated with ethanol.

The molecular weight of the triester compound used in the present invention is preferably 2000 or less, more preferably 1800 or less, even more preferably 1400 or less. The lower limit is preferably 1000 or more. When the molecular weight of the triester compound is within the above range, a molded article having an excellent balance between high transparency and high scratch resistance can be obtained.

The triester compound used in the present invention is often a mixture of a plurality of compounds with different carbon numbers. It refers to an ester compound that

A fourth embodiment of (B) the ester compound in the present invention is a tetraester compound.
The tetraester compound used in the present invention is an ester compound obtained from a polyhydric carboxylic acid and a monohydric alcohol having 20 or more carbon atoms (preferably 20 to 50 carbon atoms), a polyhydric alcohol and 20 or more carbon atoms (preferably carbon It is preferably an ester compound obtained from a monovalent carboxylic acid of numbers 20 to 50), or a mixture of both.
When the resin composition of the present invention contains such a tetraester compound, the decomposition of the polycarbonate resin is suppressed, the generation of gas during molding can be effectively suppressed, and the compatibility with the polycarbonate resin is excellent. . Therefore, it is possible to obtain a resin composition that can form a molded article that has excellent extrudability, high transparency, and excellent resistance to fingernail scratches at the initial stage and after wiping with ethanol-soaked cotton. .

The tetraester compound is preferably a tetraester compound composed of a tetravalent carboxylic acid and a monohydric alcohol, a tetraester compound derived from a monovalent carboxylic acid and a tetrahydric alcohol, or a mixture thereof.
The monohydric alcohol and monohydric carboxylic acid may each contain at least one of an aliphatic structure, an alicyclic structure and an aromatic structure, and each contain an aliphatic structure and/or an alicyclic structure. is preferred. Each of the monohydric alcohol and monocarboxylic acid preferably comprises a linear or branched aliphatic structure or alicyclic structure and a carboxyl group or a hydroxyl group.
The monohydric alcohol and the monovalent carboxylic acid each have 20 or more carbon atoms, preferably 21 or more carbon atoms, and the upper limit of the carbon number is preferably 50 or less, more preferably 40 or less, and 32 or less. More preferably, 30 or less is even more preferable.
The tetrahydric carboxylic acid and the tetrahydric alcohol each may contain at least one of an aliphatic structure, an alicyclic structure, and an aromatic structure, and each may have an aliphatic structure and/or an alicyclic It preferably contains a structure.
The tetrahydric carboxylic acid and the tetrahydric alcohol preferably comprise a linear or branched aliphatic structure or alicyclic structure and a carboxyl group or a hydroxyl group, respectively. The number of carbon atoms in the tetrahydric carboxylic acid and the tetrahydric alcohol is preferably 3 or more, more preferably 4 or more, and still more preferably 5 or more. The tetrahydric carboxylic acid and the tetrahydric alcohol each preferably have 10 or less carbon atoms, more preferably 8 or less.

In particular, the tetraester compound used in the present invention is a tetraester compound obtained from a tetravalent carboxylic acid having 3 to 10 carbon atoms and a monohydric alcohol having 20 to 40 carbon atoms, or a tetrahydric alcohol having 3 to 10 carbon atoms. It is preferably a tetraester compound obtained from a monovalent carboxylic acid having 20 to 40 carbon atoms, or a mixture thereof, from a tetravalent carboxylic acid having 3 to 10 carbon atoms and a monohydric alcohol having 20 to 30 carbon atoms. The obtained tetraester compound, or a tetraester compound obtained from a tetrahydric alcohol having 3 to 10 carbon atoms and a monovalent carboxylic acid having 20 to 30 carbon atoms, or a mixture thereof is more preferable, and has 3 to 10 carbon atoms. and a monovalent carboxylic acid having 20 to 30 carbon atoms or a mixture thereof.
Furthermore, in the tetraester compound consisting of a tetrahydric alcohol and a monovalent carboxylic acid used in the present invention, the number of carbon atoms in the monovalent carboxylic acid is greater than the number of carbon atoms in the tetrahydric alcohol by 10 or more, preferably 10 to 20. Larger is more preferred. By adopting such a structure, gas is less likely to be generated during extrusion or molding, and the appearance and physical properties of the molded product tend to be further improved.
The tetravalent carboxylic acid may or may not have a substituent, but it is preferable not to have it. The transparency of the resulting molded article tends to be more improved when it does not have a substituent. The carboxylic acid is preferably composed only of oxygen atoms, carbon atoms and hydrogen atoms.

Specific examples of monovalent carboxylic acids having 20 or more carbon atoms (number of carbon atoms in parentheses) include behenic acid (22), lignocericic acid (24), cerotic acid (26), montanic acid (28), melissic acid ( 30) and the like.

Specific examples of monohydric alcohols having 20 or more carbon atoms (number of carbon atoms in parentheses) include behenyl alcohol (22) and montanyl alcohol (28).

Specific examples of tetravalent carboxylic acids (number of carbon atoms in parentheses) include 1,2,4,5-cyclohexanetetracarboxylic acid (10), 1,2,3,5-cyclohexanetetracarboxylic acid (10), 1 , 2,4,5-benzenetetracarboxylic acid (10) and 1,2,3,5-benzenetetracarboxylic acid (10).

Specific examples of tetrahydric alcohols (number of carbon atoms in parentheses) include erythritol (4), pentaerythritol (5), 1,2,4,5-cyclohexanetetraol (6), 1,2,3,5- cyclohexanetetraol (6), 1,2,4,5-benzenetetraol (6), 1,2,3,5-benzenetetraol (6) and the like.

上記式中、波線は結合手を表す。 The tetraester compound used in the present invention preferably contains a partial structure represented by the following formula (B1).
Formula (B1)

In the above formula, the wavy line represents a bond.

Among them, the tetraester compound used in the present invention is preferably a compound represented by the following formula (B10).
Formula (B10)

In the above formula, RB ¹ to RB ⁴ each independently represent an aliphatic hydrocarbon group having 1 or more carbon atoms, and at least one of RB ¹ to RB ⁴ represents an aliphatic hydrocarbon group having 20 or more carbon atoms. The aliphatic hydrocarbon groups represented by RB ¹ to RB ⁴ are preferably saturated aliphatic hydrocarbon groups, more preferably linear saturated aliphatic hydrocarbon groups. The number of carbon atoms in the aliphatic hydrocarbon group represented by RB ¹ to RB ⁴ is preferably 2 or more, more preferably 5 or more, still more preferably 10 or more, and particularly preferably 20 or more. preferable. The upper limit is preferably 45 or less, more preferably 40 or less, and even more preferably 36 or less. The aliphatic hydrocarbon groups represented by RB ¹ to RB ⁴ preferably each independently have 20 or more carbon atoms.

The tetraester compound used in the present invention is often a mixture of a plurality of compounds with different carbon numbers. It refers to an ester compound that

The hydroxyl value of the tetraester compound is preferably 100 mgKOH/g or less, more preferably 70 mgKOH/g or less, even more preferably 50 mgKOH/g or less, and even more preferably 10 mgKOH/g or less. preferable. Although the lower limit of the hydroxyl value of the tetraester compound is not particularly defined, it is, for example, 1 mgKOH/g or more. By setting the hydroxyl value of the tetraester compound to 100 mgKOH/g or less, the promotion of decomposition of the polycarbonate resin is effectively suppressed, gas is less likely to be generated during extrusion or molding, and the appearance and physical properties of the molded product are improved. There is a tendency to improve, which is desirable.
According to this aspect, the molded article obtained from the composition of the present invention is also excellent in resistance to nail scratches after wiping with cotton impregnated with ethanol.

The molecular weight of the tetraester compound used in the present invention is preferably 2200 or less, more preferably 2000 or less, even more preferably 1800 or less. The lower limit is preferably 1400 or more. If the molecular weight of the tetraester compound is within the above range, it is possible to obtain a molded product with excellent balance between high transparency and high scratch resistance.

In the tetraester compound used in the present invention, the carboxylic acid constituting the ester structure may or may not have a substituent, but it is preferable not to have it. The transparency of the resulting molded article tends to be more improved when it does not have a substituent. The carboxylic acid is preferably composed only of oxygen atoms, carbon atoms and hydrogen atoms.

The resin composition of the present invention contains 0.5 to 10.0 parts by mass of (B) an ester compound per 100 parts by mass of (A) a polycarbonate resin.
The lower limit of the amount of the (B) ester compound is preferably 0.6 parts by mass or more, more preferably 0.8 parts by mass or more, relative to 100 parts by mass of the polycarbonate resin (A). It is particularly preferably 1.0 parts by mass or more, 1.5 parts by mass or more, or 1.8 parts by mass or more, more preferably 2.0 parts by mass or more, and more than 2.0 parts by mass. , and 2.2 parts by mass or more, the nail scratch resistance can be further improved.
The upper limit of the amount of the (B) ester compound is preferably 9.0 parts by mass or less, more preferably 8.0 parts by mass or less, relative to 100 parts by mass of the polycarbonate resin (A). More preferably 7.0 parts by mass or less, even more preferably 6.0 parts by mass or less, even more preferably 5.0 parts by mass or less, 4.0 parts by mass or less, 3.5 It may be 3.2 parts by mass or less. By setting it within the preferable range, hydrolysis resistance is improved, and mold contamination can be more effectively suppressed. In the present invention, even if the blending amount of (B) the ester compound is small, it is possible to obtain a configuration that is excellent in resistance to scratching by nails.
The resin composition of the present invention may contain only one type of (B) ester compound, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

<(C) acrylic resin>
The polycarbonate resin composition of the present invention contains (C) an acrylic resin.

式（Ｘ）中、Ｒ⁵、Ｒ⁶およびＲ⁷は、それぞれ独立に、水素原子または炭素数１～２０の炭化水素基を表し、Ｒ⁸は置換基を有していてもよい炭素数６～２０の芳香族炭化水素基、または、置換基を有していてもよい炭素数６～１７の芳香族炭化水素基で置換された炭素数１～３の脂肪族炭化水素基を表す。
Ｒ⁵およびＲ⁶は、それぞれ独立に、好ましくは水素原子またはメチル基であり、より好ましくは水素原子である。
Ｒ⁷は、それぞれ独立に、好ましくは水素原子またはメチル基であり、より好ましくはメチル基である。
Ｒ⁸は、置換基を有していてもよいフェニル基、置換基を有していてもよいナフチル基、置換基を有していてもよいベンジル基が好ましく、置換基を有さないフェニル基および置換基を有さないナフチル基がより好ましく、置換基を有さないフェニル基がさらに好ましい。
置換基としては、ハロゲン原子（好ましくは塩素原子またはフッ素原子）、アルキル基（好ましくは炭素数１～３のアルキル基、より好ましくはメチル基）が例示される。置換基を有する場合、置換基の数は、芳香環１つに対し、１～３つであることが好ましく、１または２つであることがより好ましく、１つであることがさらに好ましい。
本発明における、（Ｃ）アクリル樹脂は、式（Ｘ）で表される構造単位（ｃ１）のみから構成される重合体であってもよいし、式（Ｘ）で表される構造単位（ｃ１）と（ｃ１）以外の構造単位（通常は、（メタ）アクリル酸エステル由来の構造単位）とから構成される共重合体であってもよく、後者の共重合体の方が好ましい。
本発明では、式（Ｘ）で表される構造単位（ｃ１）と、式（Ｘ１）で表される構造単位（ｃ２）を有する共重合体がさらに好ましい。
式（Ｘ１）

式（Ｘ１）中、Ｒ⁵、Ｒ⁶およびＲ⁷は、それぞれ独立に、水素原子または炭素数１～２０の炭化水素基を表し、Ｒ⁹は、水素原子または置換基を有していてもよい炭素数１～２０の脂肪族炭化水素基を示す（ただし、置換基が芳香族炭化水素基を含むものを除く）。
Ｒ⁵およびＲ⁶は、それぞれ独立に、水素原子またはメチル基が好ましく、水素原子がより好ましい。
Ｒ⁷は、それぞれ独立に、水素原子またはメチル基が好ましく、メチル基がより好ましい。
Ｒ⁹は、好ましくは水素原子または置換基を有していてもよい炭素数１～６の脂肪族炭化水素基が好ましく、水素原子または置換基を有さない炭素数１～６の脂肪族炭化水素基がより好ましく、水素原子またはメチル基、エチル基、ｎ－ブチル基がさらに好ましく、水素原子またはメチル基が一層好ましい。
また、前記（Ｃ）アクリル樹脂は、前記（ｃ１）／（ｃ２）の質量比が５～８０／９５～２０となる割合で含有することが好ましく、２０～７０／８０～３０となる割合で含有することがより好ましく、２５～４５／７５～５５となる割合で含有することがさらに好ましい。前記（ｃ１）の質量比が５以上であれば、（Ｃ）アクリル樹脂の透明性がより向上する傾向にあり、前記（ｃ１）の質量比が９５以下であれば、（Ａ）ポリカーボネート樹脂との相溶性をより適切なものとし、かつ、成形品表面への移行性をより効果的に抑制し、表面硬度がより向上する傾向にある。
また、本発明では、（ｃ１）の繰り返し単位を構成するモノマーの分子量が１００～９００であることが好ましく、１００～５００であることがより好ましく、１００～３００であることがさらに好ましい。さらに、本発明では、（ｃ２）の繰り返し単位を構成するモノマーの分子量が８０～９００であることが好ましく、８０～５００であることがより好ましく、８０～３００であることがさらに好ましい。 (C) Acrylic resin is preferably an acrylic resin having a structural unit represented by the following formula (X).
Formula (X)

In formula (X), R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ⁸ is an optionally substituted C 6 represents an aromatic hydrocarbon group of up to 20 or an aliphatic hydrocarbon group of 1 to 3 carbon atoms substituted with an optionally substituted aromatic hydrocarbon group of 6 to 17 carbon atoms.
R ⁵ and R ⁶ are each independently preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.
Each R ⁷ is independently preferably a hydrogen atom or a methyl group, more preferably a methyl group.
R ⁸ is preferably an optionally substituted phenyl group, an optionally substituted naphthyl group, an optionally substituted benzyl group, and an unsubstituted phenyl group. and an unsubstituted naphthyl group are more preferred, and an unsubstituted phenyl group is even more preferred.
Examples of substituents include halogen atoms (preferably chlorine atoms or fluorine atoms) and alkyl groups (preferably alkyl groups having 1 to 3 carbon atoms, more preferably methyl groups). When having a substituent, the number of substituents per aromatic ring is preferably 1 to 3, more preferably 1 or 2, and still more preferably 1.
The (C) acrylic resin in the present invention may be a polymer composed only of the structural unit (c1) represented by the formula (X), or may be a polymer composed of the structural unit (c1) represented by the formula (X) ) and a structural unit other than (c1) (usually a structural unit derived from a (meth)acrylic acid ester), and the latter copolymer is preferred.
In the present invention, a copolymer having a structural unit (c1) represented by formula (X) and a structural unit (c2) represented by formula (X1) is more preferable.
Formula (X1)

In formula (X1), R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ⁹ is a hydrogen atom or may have a substituent. A good aliphatic hydrocarbon group having 1 to 20 carbon atoms (excluding those containing an aromatic hydrocarbon group as a substituent).
R ⁵ and R ⁶ are each independently preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.
Each R ⁷ is independently preferably a hydrogen atom or a methyl group, more preferably a methyl group.
R ⁹ is preferably a hydrogen atom or an optionally substituted aliphatic hydrocarbon group having 1 to 6 carbon atoms, and an aliphatic hydrocarbon group having 1 to 6 carbon atoms which does not have a hydrogen atom or a substituent. A hydrogen group is more preferred, a hydrogen atom, a methyl group, an ethyl group, or an n-butyl group is even more preferred, and a hydrogen atom or a methyl group is even more preferred.
In addition, the (C) acrylic resin is preferably contained in a ratio in which the mass ratio of (c1) / (c2) is 5 to 80/95 to 20, and in a ratio of 20 to 70/80 to 30. It is more preferable to contain it, and it is even more preferable to contain it in a ratio of 25 to 45/75 to 55. If the mass ratio of (c1) is 5 or more, the transparency of (C) acrylic resin tends to be further improved, and if the mass ratio of (c1) is 95 or less, (A) polycarbonate resin and and more effectively inhibit migration to the surface of the molded product, thereby tending to further improve the surface hardness.
In the present invention, the molecular weight of the monomer constituting the repeating unit of (c1) is preferably 100-900, more preferably 100-500, even more preferably 100-300. Furthermore, in the present invention, the molecular weight of the monomer constituting the repeating unit (c2) is preferably 80-900, more preferably 80-500, even more preferably 80-300.

Examples of the monomer constituting the repeating unit of (c1) include phenyl (meth)acrylate, benzyl (meth)acrylate, and naphthyl (meth)acrylate. Phenyl methacrylate and benzyl methacrylate are preferred, and phenyl methacrylate is more preferred.
In addition, in the present invention, (meth)acrylate indicates acrylate and/or methacrylate.
Methyl methacrylate is preferable as the monomer constituting the repeating unit of (c2). By using methyl methacrylate as a monomer constituting the repeating unit of (c2), the dispersibility in (A) the polycarbonate resin is further improved, and since it migrates to the surface of the molded product, the surface hardness of the molded product can be further improved. .

(C) As a method for polymerizing a monomer for obtaining an acrylic resin, a known method such as an emulsion polymerization method, a suspension polymerization method, a solution polymerization method, or a bulk polymerization method can be used. A suspension polymerization method or a bulk polymerization method is preferable, and a suspension polymerization method is more preferable. Additives required for polymerization can be added as needed, and examples thereof include polymerization initiators, emulsifiers, dispersants, and chain transfer agents.

When the (C) acrylic resin used in the present invention contains a structural unit represented by formula (X), it is preferably 20% by mass or more, preferably 30% by mass, of the structural units constituting the (C) acrylic resin. It is more preferable to be above. The upper limit is preferably 95% by mass or less, more preferably 80% by mass or less. The structural unit represented by formula (X) may contain only one type, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

When the (C) acrylic resin used in the present invention contains the structural unit represented by the formula (X) and the structural unit represented by the formula (X1), the total amount of these is 90 mass of the (C) acrylic resin % or more.
In addition, the structural unit represented by Formula (X1) may contain only 1 type, and may contain 2 or more types. When two or more types are included, the total amount is preferably within the above range.

The weight average molecular weight of the (C) acrylic resin is preferably 5,000 or more, more preferably 10,000 or more, and even more preferably 13,000 or more. The upper limit of the weight average molecular weight is preferably 30,000 or less, more preferably 25,000 or less, even more preferably 20,000 or less. When the amount is within the above range, the compatibility with (A) the polycarbonate resin tends to be better, and the effect of improving the surface hardness tends to be more excellent.
The weight average molecular weight of the (C) acrylic resin is measured by gel permeation chromatography using tetrahydrofuran (THF) as a solvent. Incidentally, the weight average molecular weight is a value in terms of standard polystyrene resin (PS).

The content of (C) the acrylic resin is 1 to 100 parts by mass with respect to 100 parts by mass of the (A) polycarbonate resin. The lower limit of the content of the (C) acrylic resin is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, and further 7 parts by mass or more, 10 parts by mass or more, and 20 parts by mass or more. , 30 parts by mass or more. In addition, the upper limit of the content of the (C) acrylic resin is preferably 75 parts by mass or less, more preferably 55 parts by mass or less, still more preferably 45 parts by mass or less, and further 38 parts by mass. Below, it may be 30 mass parts or less and 20 mass parts or less. By setting it to the above range, the resin composition of the present invention can effectively improve surface hardness and fluidity while maintaining good transparency and maintaining a balance of physical properties such as impact resistance. whitening problem can be suppressed. In particular, by setting the upper limit of the content of the acrylic resin (C) to 38 parts by mass or less, it is possible to remarkably reduce the Δhaze before and after the light resistance test. On the other hand, by setting the upper limit of the content of the (C) acrylic resin to 20 parts by mass or more, the Δhaze before and after the abrasion reciprocating test can be further reduced.

Further, in the resin composition of the present invention, the ratio ((B) / (C) × 100) (% by mass) of (B) ester compound to (C) acrylic resin is preferably 3 to 200, and the lower limit is more preferably 5 or more, still more preferably 7 or more, still more preferably 8 or more, and the upper limit is more preferably 100 or less, still more preferably 50 or less, still more preferably 35 or less, and still more preferably 25 Below, more preferably 20 or less. With such a configuration, it is possible to achieve higher transparency and resistance to scratching nails at the initial stage and after wiping off the solvent.

In addition to the above, the (C) acrylic resin used in the present invention employs those described in WO2014/038500, WO2013/094898, JP-A-2006-199774, and JP-A-2010-116501. , the contents of which are incorporated herein.

<Other ingredients>
The resin composition of the present invention may optionally contain other components than those mentioned above as long as the desired physical properties are not significantly impaired. Examples of other components include thermoplastic resins other than the above-described (A) polycarbonate resin and (C) acrylic resin, various resin additives, and the like.
Although the resin composition of the present invention preferably contains no inorganic filler, it may contain an inorganic filler. By including the inorganic filler, the mechanical strength of the resulting molded article can be further improved. As an embodiment of the resin composition of the present invention, it does not contain an inorganic filler, or 8 parts by mass or less (preferably 6 parts by mass or less, more preferably 6 parts by mass or less) of an inorganic filler with respect to 100 parts by mass of the (A) polycarbonate resin. is 4 parts by mass or less, more preferably 1 part by mass or less). The transparency of the obtained molded article can be further improved by not including the inorganic filler or by setting the blending amount within the above range. As the inorganic filler, the descriptions in paragraphs 0075 to 0079 of JP-A-2017-110180 can be referred to, and the contents thereof are incorporated herein.
Examples of resin additives include stabilizers (heat stabilizers, antioxidants, etc.), ultraviolet absorbers, antistatic agents, flame retardants, flame retardant aids, dyes, pigments, antifog agents, lubricants, antiblocking agents. , fluidity improvers, plasticizers, dispersants, antibacterial agents, and the like. One resin additive may be contained, or two or more resin additives may be contained in any combination and ratio.

<<Stabilizer>>
Stabilizers include heat stabilizers and antioxidants.
Phosphorus-based stabilizers are preferably used as heat stabilizers.
Any known phosphorus stabilizer can be used. Specific examples include phosphorus oxo acids such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, and polyphosphoric acid; acid pyrophosphate metal salts such as sodium acid pyrophosphate, potassium acid pyrophosphate, and calcium acid pyrophosphate; phosphates of group 1 or group 2B metals such as potassium phosphate, sodium phosphate, cesium phosphate, zinc phosphate; is particularly preferred.

Examples of organic phosphite compounds include triphenylphosphite, tris(monononylphenyl)phosphite, tris(monononyl/dinonylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, monooctyl Diphenylphosphite, dioctylmonophenylphosphite, monodecyldiphenylphosphite, didecylmonophenylphosphite, tridecylphosphite, trilaurylphosphite, tristearylphosphite, 2,2-methylenebis(4,6-di- tert-butylphenyl)octyl phosphite and the like.
Specific examples of such organic phosphite compounds include, for example, “ADEKA STAB (registered trademark; hereinafter the same) 1178”, “ADEKA STAB 2112”, and “ADEKA STAB HP-10” manufactured by Johoku Chemical Industry Co., Ltd. "JP-351", "JP-360", "JP-3CP", BASF's "Irgafos (registered trademark; hereinafter the same) 168", and the like.

As the antioxidant, a hindered phenol stabilizer is preferably used.
Specific examples of hindered phenol stabilizers include pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3-(3,5-di-tert- Butyl-4-hydroxyphenyl)propionate, thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexane-1,6-diylbis[3-( 3,5-di-tert-butyl-4-hydroxyphenyl)propionamide], 2,4-dimethyl-6-(1-methylpentadecyl)phenol, diethyl [[3,5-bis(1,1-dimethylethyl )-4-hydroxyphenyl]methyl]phosphate, 3,3′,3″,5,5′,5″-hexa-tert-butyl-a,a′,a″-(mesitylene-2,4 ,6-triyl)tri-p-cresol, 4,6-bis(octylthiomethyl)-o-cresol, ethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl ) propionate], hexamethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,3,5-tris(3,5-di-tert-butyl-4-hydroxy benzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1, 3,5-triazin-2-ylamino)phenol, 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate and the like. be done.

Among them, pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate preferable. Specific examples of such hindered phenol-based stabilizers include, for example, "Irganox (registered trademark; hereinafter the same) 1010" and "Irganox 1076" manufactured by BASF, "ADEKA STAB AO-50" manufactured by ADEKA, "ADEKA STAB AO-60” and the like.

The content of the stabilizer in the resin composition of the present invention is usually 0.001 parts by mass or more, preferably 0.005 parts by mass or more, and more preferably 0.01 parts by mass or more with respect to 100 parts by mass of the polycarbonate resin. Also, it is usually 1 part by mass or less, preferably 0.5 parts by mass or less, and more preferably 0.3 parts by mass or less. By setting the content of the stabilizer within the above range, the effect of addition of the stabilizer is exhibited more effectively.

<<Ultraviolet absorber>>
As for the ultraviolet absorber, the descriptions in paragraphs 0059 to 0062 of JP-A-2016-216534 can be referred to, and the contents thereof are incorporated herein.

<<Antistatic agent>>
As the antistatic agent, the descriptions in paragraphs 0063 to 0067 of JP-A-2016-216534 can be referred to, and the contents thereof are incorporated herein.

<<flame retardant>>
As the flame retardant, the descriptions in paragraphs 0068 to 0075 of JP-A-2016-216534 can be referred to, and the contents thereof are incorporated herein.

<Characteristics of resin composition>
The resin composition of the present invention can achieve low haze. The haze of a molded product obtained by molding the resin composition of the present invention to a thickness of 2 mm is 5.0% or less, further 3.0% or less, 2.0% or less, 1.0% or less, or 0.5%. Below, it can also be 0.4% or less. The lower limit of haze is ideally 0%, but 0.01% or more, or even 0.07% or more is also a practical level. The method for measuring haze follows the description in Examples described later.

A test piece having a thickness of 2 mm (preferably a test piece having a length of 150 mm × width of 100 mm × thickness of 2 mm) formed from the resin composition of the present invention has a dynamic friction coefficient of 0.35 or less according to ISO 19252 under a load of 30 N. is. The lower limit of the coefficient of dynamic friction is ideally 0, but 0.01 or more, or even 0.10 or more is practical. The method for measuring the coefficient of dynamic friction follows the description of the examples described later.

A test piece having a thickness of 2 mm (preferably a test piece having a length of 150 mm, a width of 100 mm, and a thickness of 2 mm) formed from the resin composition of the present invention was subjected to a reciprocating abrasion test using bleached cloth (100% cotton, 20×20 count). Δhaze, which is the difference between the hazes before and after, is preferably 5.00% or less, more preferably 4.00% or less, even more preferably 3.50 or less, and 3.00% or less. more preferably 2.90% or less, even more preferably 2.80% or less, and even more preferably 2.00% or less. The lower limit of Δhaze before and after the reciprocating abrasion test is ideally 0%, but 0.01% or more, and even 0.07% or more are practical levels. The method for measuring Δhaze before and after the reciprocating abrasion test follows the description of the examples below.

When two or more kinds of (A) polycarbonate resin and/or (C) acrylic resin are included, the pencil hardness of (A) polycarbonate resin and (C) acrylic resin mixture, respectively, (A) polycarbonate resin and (C) acrylic It is assumed to be the pencil hardness of the resin.

The resin composition of the present invention has excellent light resistance. The change in color difference (ΔE) before and after the lightfastness test is, for example, 3.5 or less, preferably 3.0 or less, more preferably 2.8 or less, still more preferably 2.5 or less, and still more preferably 2.0 or less. is. The method of the lightfastness test and the method of measuring ΔE before and after the test are as described in Examples below.

<Method for producing resin composition>
The method for producing the resin composition of the present invention is not limited, and a wide range of known methods for producing a polycarbonate resin composition can be employed. After pre-mixing using various mixers such as a tumbler and Henschel mixer, a method of melt-kneading with a mixer such as a Banbury mixer, a roll, a Brabender, a single-screw kneading extruder, a twin-screw kneading extruder, and a kneader can be mentioned.
The melt-kneading temperature is not particularly limited, but is usually in the range of 240 to 320°C.

<Molded product>
The resin composition (for example, pellets) described above is molded by various molding methods to obtain molded articles. That is, the molded article of the present invention is molded from the resin composition of the present invention.
The shape of the molded product is not particularly limited and can be appropriately selected according to the use and purpose of the molded product. , odd-shaped products, hollow products, frame-shaped products, box-shaped products, panel-shaped products, button-shaped products, and the like. Among them, film-shaped, frame-shaped, panel-shaped, and button-shaped ones are preferable, and the thickness of the frame-shaped and panel-shaped ones is, for example, about 1 mm to 5 mm.

The method for molding the molded article is not particularly limited, and conventionally known molding methods can be employed, such as injection molding, injection compression molding, extrusion molding, profile extrusion, transfer molding, blow molding, Gas-assisted blow molding method, blow molding method, extrusion blow molding method, IMC (in-mold coating molding) method, rotational molding method, multi-layer molding method, two-color molding method, insert molding method, sandwich molding method, foam molding method , pressure molding, and the like. In particular, the resin composition of the present invention is suitable for moldings obtained by injection molding, injection compression molding, and extrusion molding. However, it goes without saying that the resin composition of the present invention is not limited to the molded articles obtained therefrom.

The molded article of the present invention is suitably used for parts such as electrical and electronic equipment, OA equipment, personal digital assistants, machine parts, household appliances, vehicle parts, various containers, lighting equipment and the like. Among these, it is particularly used for electrical and electronic equipment, OA equipment, information terminal equipment and housings of home appliances, lighting equipment and vehicle parts (especially vehicle interior parts), with vehicle interior parts being particularly preferred.

EXAMPLES The present invention will be described more specifically with reference to examples below. The materials, usage amounts, ratios, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the gist of the present invention. Accordingly, the scope of the present invention is not limited to the specific examples shown below.

1. Raw materials <Production Example 1: Production of polycarbonate resin A1>
26.14 mol (6.75 kg) of bisphenol C (BPC) and 26.79 mol (5.74 kg) of diphenyl carbonate were placed in a SUS reactor (inner volume: 10 liters) equipped with a stirrer and a distillate condenser. After the inside of the reactor was replaced with nitrogen gas, the temperature was raised to 220° C. over 30 minutes under a nitrogen gas atmosphere.
Next, the reaction solution in the reactor is stirred, and cesium carbonate (Cs ₂ CO ₃ ) as a transesterification reaction catalyst is added to the molten reaction solution in an amount of 1.5×10 ⁻⁶ mol per 1 mol of BPC. In addition, the reaction solution was stirred and brewed at 220° C. for 30 minutes in a nitrogen gas atmosphere. Next, at the same temperature, the pressure inside the reactor was reduced to 100 Torr over 40 minutes, and the reaction was continued for 100 minutes to distill off phenol.
Next, the temperature in the reactor was raised to 284° C. over 60 minutes and the pressure was reduced to 3 Torr to distill almost the entire theoretical amount of phenol. Next, the pressure in the reactor was kept below 1 Torr at the same temperature, and the reaction was continued for an additional 60 minutes to complete the polycondensation reaction. At this time, the stirring rotation speed of the stirrer was 38 rpm, the temperature of the reaction liquid immediately before the reaction was completed was 289° C., and the stirring power was 1.00 kW.
Next, the reaction liquid in a molten state is fed into a twin-screw extruder, and butyl p-toluenesulfonate in an amount four times the molar amount of cesium carbonate is fed from the first feed port of the twin-screw extruder, After kneading with the reaction liquid, the reaction liquid was extruded through a die of a twin-screw extruder into strands and cut with a cutter to obtain pellets of polycarbonate resin A1.

Materials shown in Table 1 below were used for the production of the resin composition of the present invention.

<Measurement of viscosity average molecular weight (Mv) of polycarbonate resin>
The viscosity-average molecular weight (Mv) of the polycarbonate resin is obtained by using methylene chloride as a solvent and using an Ubbelohde viscometer to determine the intrinsic viscosity (η) (unit: dL / g) at a temperature of 20 ° C., and the following Schnell viscosity Calculated from the formula.
η=1.23×10 ⁻⁴ Mv ^0.83

<Measurement of pencil hardness of thermoplastic resin>
After drying the polycarbonate resin pellets at 100 ° C. for 5 hours, using an injection molding machine (“α-2000i-150B” manufactured by Fanuc Co., Ltd.), the cylinder setting temperature is 260 ° C., the mold temperature is 70 ° C., and the screw rotation speed is 100 rpm. A flat test piece (150 mm×100 mm×2 mm thick) was prepared under the conditions of an injection speed of 30 mm/sec. With respect to this flat test piece, the pencil hardness measured with a load of 750 g was obtained using a pencil hardness tester according to ISO 15184.
A pencil hardness tester manufactured by Toyo Seiki Seisakusho Co., Ltd. was used.

<Measurement of hydroxyl value of ester compound>
The hydroxyl value is the mg number of potassium hydroxide required to neutralize the acetic acid bound to the hydroxyl group when 1 g of the sample is acetylated. Sometimes it is an indicator of the number of hydroxyl groups left unreacted.
The hydroxyl value was measured according to the method specified in JIS K 0070.

2. Examples 1 to 5, Comparative Examples 1 to 8
<Production of resin composition pellets>
Each component described in Table 1 above was blended in the proportions shown in Table 2 below (all expressed in parts by mass), mixed uniformly in a tumbler mixer, and then a twin-screw extruder (Nippon Steel Co., Ltd.) Using TEX30α manufactured by TEX30α), the resin composition was fed into the extruder from the barrel upstream of the extruder at a cylinder setting temperature of 260° C., a screw rotation speed of 180 rpm, and a discharge rate of 30 kg/hr, and melt-kneaded to obtain resin composition pellets. .

<Mole ratio of polycarbonate resin>
The molar ratio (mol%) in Table 2 described later is an index showing the content of the structural unit represented by formula (1) in the polycarbonate resin contained in the resin composition, and the mixing ratio and formula of the resin used It was calculated from the viscosity average molecular weight using the molecular weight of the structural unit represented by (1).

<Possibility of Extrusion>
In the production of the resin composition pellets, whether or not extrusion was possible was visually confirmed and evaluated as follows.
a: extrudable b: extrusion unstable c: extrudable (polycarbonate resin decomposes)

<Amount of extrusion gas generated>
In the production of the above resin composition pellets, the amount of gas generated in Comparative Example 1 was used as a standard, and when the amount of gas generated was equal to or less than that, it was evaluated as the standard amount of gas generation (a), and the extrusion was compared with the standard amount. The amount of gas generated was visually evaluated as follows.
a: gas generation standard b: slightly high c: high

<Comprehensive evaluation of extrudability>
Evaluation was made as follows based on the results of whether or not extrusion was possible and the amount of gas generated.
A: Both extrudability and gas generation rate are a.
B: Other than A above and C below.
C: At least one of whether or not extrusion is possible and the amount of gas generated is c.

<Production of test piece for evaluation as molded body>
After drying the resin composition pellets obtained above at 100 ° C. for 5 hours, an injection molding machine (“α-2000i-150B” manufactured by Fanuc Corporation) was used to set the cylinder temperature to 260 ° C., the mold temperature to 70 ° C., A flat test piece of 150 mm×100 mm×2 mm thickness was injection molded under conditions of a screw rotation speed of 100 rpm and an injection speed of 30 mm/sec.

<Measurement of haze>
The haze (unit: %) of the flat test piece obtained above was measured using a haze meter.
As the haze meter, NDH-2000 type haze meter manufactured by Nippon Denshoku Industries Co., Ltd. was used.

<Measurement of Pencil Hardness of Resin Composition>
For the flat test piece obtained above, the pencil hardness measured with a load of 1 kg was obtained using a pencil hardness tester according to ISO 15184.
A pencil hardness tester manufactured by Toyo Seiki Seisakusho Co., Ltd. was used.

<Coefficient of dynamic friction (30N)>
For the flat test piece obtained above, in accordance with ISO 19252, a scratch tester is used with a spherical terminal of 1 mmφ, the test speed is 100 mm / sec, the vertical load is variable from 1 N to 50 N during the test distance of 100 mm. The horizontal load and the vertical load were measured at the point where the load was 30 N, and the coefficient of dynamic friction (horizontal load/vertical load) was determined and evaluated as follows. A smaller coefficient of dynamic friction is preferable.
A scratch tester manufactured by Kato Tech Co., Ltd. was used.
a: 0.38 or less b: more than 0.38 and 0.40 or less c: more than 0.40

<Nail scratch resistance>
Sensory evaluation was performed by rubbing the flat test piece obtained above 10 times with a fingernail.
a: No scratches and good slipperiness.
b: Slightly scratched, but slippery.
c: Scratches less than d, but still damaged.
d: hurt.

<Δhaze before and after reciprocating wear test>
The haze of the flat test piece obtained above was measured in the same manner as described above (the haze at this time is referred to as haze a).
On the other hand, for the same flat test piece obtained above, using a flat abrasion tester, bleached cloth (100% cotton, 20 × 20 count cut to 15 cm × 33 cm) was folded 18 times, and flat abrasion was performed. It was attached to a jig of a testing machine, and tested with a reciprocating cycle of 40 times/min, a load of 1 kg, and a reciprocating number of 500 times. The haze of the flat test piece after the reciprocating abrasion test was measured in the same manner as described above (the haze at this time is referred to as haze b). "Haze b - haze a" was defined as Δhaze before and after the reciprocating abrasion test, and evaluation was made according to the following criteria.
The surface abrasion tester was manufactured by Daiei Kagaku Seiki Seisakusho.
The bleaching used was the bleaching made by Nankai Co., Ltd.
a: 4.00% or less b: more than 4.00% and 5.00% or less c: more than 5.00%

<Scratch resistance comprehensive evaluation>
Based on the above nail scratch resistance, dynamic friction coefficient, and Δhaze before and after the reciprocating abrasion test, evaluation was made as follows.
A: Both evaluations are a.
B: Other than A above and C below.
C: At least one rating is c or d.

<ΔE ^* before and after light resistance test>
A flat test piece having a thickness of 50 mm × 100 mm × 2 mm was cut from the flat test piece obtained above, and was irradiated for 300 hours under the conditions of an irradiation intensity of 0.55 w/m ² (at 340 nm) and a black panel temperature of 89°C. irradiated. In the flat test piece before and after this light resistance test, according to JIS K7105, using a spectral colorimeter, the difference in E ^* value (ΔE ^* ) was obtained by the reflection method with a D65/10 ° light source, and the following Evaluated according to categories.
Light irradiation was performed using Ci4000 manufactured by ATLAS.
As a spectral colorimeter, an SE6000 type spectral colorimeter manufactured by Nippon Denshoku Industries Co., Ltd. was used.
A: 3.0 or less B: more than 3.0 and 5.0 or less C: more than 5.0

<Comprehensive judgment>
Based on the comprehensive evaluation of extrudability, the comprehensive evaluation of scratch resistance, and the results of ΔE ^* (evaluation) before and after the weather resistance test, evaluation was made as follows.
A: All of the extrudability comprehensive evaluation, scratch resistance comprehensive evaluation, and ΔE ^* (evaluation) before and after the weather resistance test are A.
B: Other than A above and C below.
C: At least one evaluation of extrudability comprehensive evaluation, scratch resistance comprehensive evaluation, and ΔE ^* (evaluation) before and after the weather resistance test is C.

The results are shown in Table 2 below.

In the above table, the "proportion of formula (1)" is the proportion (mol%) of the structural unit represented by formula (1) among all the structural units constituting the polycarbonate resin.
As is clear from the above results, the resin composition of the present invention had excellent scratch resistance, in particular, had a high transparency retention rate before and after the abrasion test, and had excellent extrudability (Example 1 to Example 5). In particular, in Examples 1 to 3, the change in color tone (change in ΔE ^* ) before and after the lightfastness test was remarkably small.
When the proportion of the structural unit represented by formula (1) exceeded 50 mol %, the change in color tone (change in ΔE ^* ) before and after the lightfastness test increased (Comparative Examples 1 to 4).
Further, when the proportion of the structural unit represented by formula (1) is less than 5 mol%, the pencil hardness is low, the nail scratch resistance is poor, the Δhaze before and after the reciprocating abrasion test is also poor, and the scratch resistance is poor. was inferior (Comparative Examples 5 and 6).
On the other hand, when the acrylic resin did not contain the structural unit represented by the formula (X) (Comparative Example 4), the haze was increased. It turned out that it is not suitable for applications that require transparency in the first place.
Furthermore, when the amount of the ester compound was too large, the haze was lowered, and when it was too small, the Δhaze before and after the reciprocating abrasion test was inferior (Comparative Examples 7 and 8).

Claims (9)

(A) 100 parts by mass of a polycarbonate resin, (B) 0.5 to 10.0 parts by mass of an ester compound, and (C) a thermoplastic resin composition containing 1 to 100 parts by mass of an acrylic resin,
The (A) polycarbonate resin contains 5 mol% or more and less than 50 mol% of a structural unit represented by the following formula (1) among all structural units, and a structural unit represented by the formula (2): Containing at a ratio of 50 mol% or more and 95 mol% or less in all structural units,
(B) the ester compound is composed of an alcohol and a carboxylic acid,
The (C) acrylic resin is a copolymer of a structural unit (c1) represented by formula (X) and a structural unit (c2) represented by formula (X1),
A test piece having a thickness of 2 mm formed from the resin composition has a haze of 0% or more and 5.0% or less measured according to ISO 14782, and a dynamic friction coefficient according to ISO 19252 at a load of 30 N. is 0.01 or more and 0.38 or less,
A test piece with a thickness of 2 mm formed from the resin composition was obtained by drying the resin composition at 100 ° C. for 5 hours, using an injection molding machine ("α-2000i-150B" manufactured by Fanuc Corporation), and setting the cylinder temperature. A resin composition that is molded into a size of 150 mm × 100 mm × 2 mm thickness at 260 ° C., a mold temperature of 70 ° C., a screw rotation speed of 100 rpm, and an injection speed of 30 mm / sec.
formula (1)

In formula (1), R ¹ represents a methyl group, R ² represents a hydrogen atom or a methyl group, X ¹ represents any of the following formulas,

R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group, and Z is combined with C to form an alicyclic hydrocarbon having 6 to 12 carbon atoms, which may have a substituent. representing a group;
Formula (X)

In formula (X), R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ⁸ represents a phenyl group, naphthyl group or benzyl group.
formula (2)

In formula (2), X ² represents any of the following formulas,

R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group, and Z is combined with C to form an alicyclic hydrocarbon having 6 to 12 carbon atoms, which may have a substituent. represents a group.
Formula (X1)

In formula (X), R ⁶ and R ⁷ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R ⁸ represents a methyl group, R ¹⁰ represents a hydrogen atom or methyl represents a group. 2. The resin composition according to claim 1, wherein the (B) ester compound is formed from a monohydric carboxylic acid and a monohydric alcohol. 2. The resin composition according to claim 1 , wherein the (B) ester compound is at least one selected from monoester compounds, diester compounds, triester compounds, and tetraester compounds having a molecular weight of 2000 or less. 4. The resin composition according to any one of claims 1 to 3, wherein the mass ratio of (c1)/(c2) is from 5 to 80/95 to 20. The resin composition according to any one of claims 1 to 4, wherein (C) the acrylic resin has a weight average molecular weight of 5,000 to 30,000. The resin composition according to any one of claims 1 to 5, wherein the content of the acrylic resin (C) is 1 to 45 parts by mass per 100 parts by mass of the polycarbonate resin (A). The resin according to any one of claims 1 to 6, wherein the ratio ((B)/(C) × 100) (mass%) of (B) the ester compound to (C) the acrylic resin is 3 to 200. Composition. 8. Any one of claims 1 to 7, wherein a test piece having a thickness of 2 mm formed from the resin composition has a haze difference of 0% or more and 4.00% or less before and after a reciprocating abrasion test using a bleach. 1. The resin composition according to claim 1. A molded article formed from the resin composition according to any one of claims 1 to 8.