JP2020063332A - Resin composition and molding - Google Patents

Abstract

To provide a resin composition having very excellent surface hardness, excellent excoriation resistance, a particularly high transparency maintenance factor before and after a wear test, and excellent light resistance and a molding including the resin composition.SOLUTION: A heat composition contains, based on 100 pts.mass of a (A) polycarbonate resin, 0.5-10.0 pts.mass of a (B) ester compound, and 1-100 pts.mass of a (C) acrylic resin having a predetermined structure. The (A) poly carbonate resin contains, in all the structural units, 5 mol% or more and less than 50 mol% of a structural unit represented by the following formula (1). The (B) ester compound is composed of alcohol and carboxylic acid. A test piece that is formed from the resin composition and of 2 mm in thickness has a haze of 5.0% or less. A coefficient of dynamic friction of the resin composition at a load of 30 N is 0.35 or less. In the formula (1), Ris a methyl group.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition and a molded product. In particular, the present invention relates to a resin composition using a polycarbonate resin, which is excellent in transparency, scratch resistance, light resistance and the like, and which can provide a molded article having extremely excellent surface hardness.

  Polycarbonate resin is excellent in mechanical strength, electrical characteristics, transparency, and the like, and is widely used as an engineering plastic in various fields such as electric and electronic devices and automobiles. In recent years, in these fields, molded products have become thinner, smaller and lighter, and further improvement in performance of molding materials has been required, and some proposals have been made.

  For example, in Patent Document 1, a graft copolymer (B) having a polyethylene polymer as a main chain and a vinyl polymer segment as a side chain with respect to 100 parts by mass of a polycarbonate resin (A) having a predetermined structure (B ) Disclosed is a polycarbonate resin composition containing 0.1 to 12 parts by mass. The document also describes that the polycarbonate resin composition has excellent resistance to scratches on the nail.

JP, 2017-110180, A

It has been conventionally known that a polycarbonate resin containing a structural unit derived from bisphenol C tends to have a high pencil hardness. Here, there is a case where a molded product 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, may be referred to as "paintless"). However, as a result of examination by the present inventor, it has been found that such a molded product has a slight problem in resistance to scratches on the nails even though the pencil hardness is high. The resin composition described in Patent Document 1 is a resin composition having excellent resistance to scratches on nails, but in Examples of the document, jet blackness and the like are pursued. That is, for applications requiring transparency, development of new materials is required. Further, it is required to maintain high transparency even after the abrasion test.
Furthermore, although light resistance is required depending on the application, even if it is excellent in scratch resistance by blending a suitable additive in polycarbonate resin, especially even after maintaining high transparency after abrasion test, no coating It was in a situation where the light resistance was inferior to that of using it.
The present invention is intended to solve the above problems, very excellent surface hardness, excellent scratch resistance, in particular, high transparency retention rate before and after the abrasion test also light resistance An object 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。 Under the above-mentioned problems, as a result of the present inventors' investigation, as a result of blending an ester compound with a predetermined polycarbonate resin, further, by setting the haze and the dynamic friction coefficient within a predetermined range, it is possible to solve the above problems. I found it. Specifically, the above problem has been solved by the following means <1>, preferably <2> to <11>.
<1> A thermoplastic resin composition containing 0.5 to 10.0 parts by mass of an ester compound (B) and 1 to 100 parts by mass of an acrylic resin (C) with respect to 100 parts by mass of a polycarbonate resin (A). 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 an alcohol and a carboxylic acid. The (C) acrylic resin contains a structural unit represented by the following formula (X), and a 2 mm-thick test piece formed from the resin composition has a haze measured according to ISO 14782. Of 5.0% or less and a dynamic friction coefficient according to ISO 19252 at a load of 30 N of 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 one of the following formulas,

R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group, and Z is bonded to C to form an alicyclic hydrocarbon having 6 to 12 carbon atoms and optionally having 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 has 6 carbon atoms which may have a substituent. To an aromatic hydrocarbon group having 20 to 20 carbon atoms or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, which is substituted with an aromatic hydrocarbon group having 6 to 17 carbon atoms which may have a substituent.
<2> The resin composition according to <1>, wherein the (B) ester compound is formed from a monovalent carboxylic acid and a monohydric alcohol.
<3> The resin composition according to <1> or <2>, wherein R ⁵ , R ⁶ and R ⁷ in the formula (X) are each independently a hydrogen atom or a methyl group.
<4> R ⁸ in the formula (X) is a phenyl group which may have a substituent, a naphthyl group which may have a substituent or a benzyl group which may have a substituent. 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) in 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 may have a hydrogen atom or a substituent. A good aliphatic hydrocarbon group having 1 to 20 carbon atoms is shown (provided that the substituent does not include an aromatic hydrocarbon group).
<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>, in which 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. .
Any one of <1> to <7> in which the ratio ((B) / (C) × 100) (mass%) of the <8> (B) ester compound to the (C) acrylic resin is 3 to 200. The resin composition described in 1.
<9> (A) polycarbonate resin further contains a structural unit represented by the following formula (2), the resin composition according to any one of <1> to <8>;
Formula (2)

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

R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group, and Z is bonded to 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 Δhaze that is 4.00% or less, which is a difference in haze before and after a reciprocating abrasion test using a saliva, <1> to <9>. The resin composition according to any one of 1.
<11> A molded product formed from the resin composition according to any one of <1> to <10>.

  According to the present invention, a resin composition having excellent surface hardness, excellent scratch resistance, and a high maintenance rate of transparency after an abrasion test, and also having excellent light resistance, and the resin composition are used. The existing molded products can now be provided.

  Hereinafter, the content of the present invention will be described in detail. In addition, in this specification, "-" is used in the meaning including the numerical values described before and after it 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 contains 100 parts by mass of (A) polycarbonate resin, 0.5 to 10.0 parts by mass of (B) ester compound, and 1 to 100 parts by mass of (C) acrylic resin. A plastic resin composition, wherein 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 2 mm-thick test piece 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 one of the following formulas,

R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group, and Z is bonded to C to form an alicyclic hydrocarbon having 6 to 12 carbon atoms and optionally having 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 has 6 carbon atoms which may have a substituent. To an aromatic hydrocarbon group having 20 to 20 carbon atoms or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, which is substituted with an aromatic hydrocarbon group having 6 to 17 carbon atoms which may have a substituent.
With such a configuration, it is possible to provide a resin composition having excellent surface hardness and excellent scratch resistance, which can maintain particularly high transparency even after an abrasion test, and further has excellent light resistance. Become. Further, it becomes possible to improve the extrudability.
Hereinafter, details of the present invention will be described.

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 the formula (1) in an amount 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 one of the following formulas,

R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group, and Z is bonded to C to form an alicyclic hydrocarbon having 6 to 12 carbon atoms and optionally having a substituent. Represents a group.

Two R ^{2 s 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 a methyl group, both are preferably a methyl group.
Also X ¹ is

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

Specific examples of preferred structural units of the above formula (1) include the following i) to iv).
i) A structural unit composed of 2,2-bis (3-methyl-4-hydroxyphenyl) propane, that is, R ¹ is a methyl group, R ² is a hydrogen atom, and X ¹ is —C (CH ₃ ) ₂ —. A structural unit, which is
ii) A structural unit composed of 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, that is, R ¹ is a methyl group, R ² is a methyl group, and X ¹ is —C (CH ₃ ). A structural unit that is _2- ,
iii) A structural unit composed of 2,2-bis (3-methyl-4-hydroxyphenyl) cyclohexane, that is, 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, that is, 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 preferable, the above i) and iii) are more preferable, and the above i) is further preferable.

  The polycarbonate resin (A) in the present invention contains 5 mol% or more, preferably 10 mol% or more, more preferably 15 mol% or more, still more preferably the structural unit represented by the formula (1) in all structural units. 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, and even 45 mol% or less, 43 mol% or less, 40 mol% or less. Good. When the content is 5 mol% or more, the surface hardness of the molded product tends to be improved. When it is less than 50 mol%, the light resistance tends to be improved.

  In the present invention, the polycarbonate resin (A) may include only one type of structural unit represented by formula (1), or may include two or more types. When two or more kinds are contained, 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, the (A) polycarbonate resin may have a structural unit other than the structural unit represented by the formula (1). As the other structural unit, a structural unit represented by the following formula (2) is preferable.
Formula (2)

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

R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group, and Z is bonded to C to form an alicyclic hydrocarbon having 6 to 12 carbon atoms and optionally having a substituent. Represents a group.
Examples of the alicyclic hydrocarbon formed by combining Z with C include 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 the methyl-substituted and ethyl-substituted alicyclic hydrocarbon groups described above. Among these, a cyclohexylidene group, a methyl-substituted product (preferably a 3,3,5-trimethyl-substituted product) of a cyclohexylidene group, and a cyclododecylidene group are preferable.

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) has the same meaning as 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, and 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 (carbonate structural unit) composed of bisphenol-A.
In the present invention, the structural unit represented by the formula (2) is preferably 50 mol% or more, more preferably 52 mol% or more, still more preferably 53 mol% or more, still more preferably 55 mol% in all structural units. The above content is more preferably 57 mol% or more, still more preferably 60 mol% or more. Further, the upper limit value is 95 mol% or less, preferably 90 mol% or less, more preferably 85 mol% or less, and further preferably 80 mol% or less in all structural units.
In the present invention, the (A) polycarbonate resin preferably contains the structural unit represented by the formula (2), and may contain only one kind or two or more kinds. When two or more kinds are contained, the total amount is preferably within the above range.

In the present invention, the (A) polycarbonate resin may be, for example, the following dihydroxy compound as a structural unit other than the structural unit represented by the formula (1) and the structural unit represented by the formula (2). Mention may be made of such aromatic dihydroxy compounds;
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-methyl) Propyl) phenyl) cyclohexane, 1,1-bis (4-hydroxy-3-cyclohexylphenyl) cyclohexane, , 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) si Clopentane, 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 another embodiment of the other structural unit, the structural unit represented by the formula (1) described in paragraph 0008 of WO2017 / 099926 pamphlet is also exemplified, and further, in paragraphs 0043 to 0052 of WO2017 / 099226 pamphlet. The description can be referred to, and the content thereof is incorporated in the present specification.

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 are each independently 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, It 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; n1, n2 and n3 each independently represent an integer of 0 to 4.
Details of the structural unit represented by the formula (3) can be referred to the description in JP2011-046769A, and the contents thereof are incorporated in the present specification.

  In the present invention, the content of the structural unit other than the structural unit represented by the formula (1) and the structural unit represented by the formula (2) in the polycarbonate resin (A) is 30 mol% in all the structural units. It is preferably the following, more preferably 20% by mol or less, further preferably 10% by mol or less, 5% by mol or less, or 1% by mol or less.

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

In the present invention, the blend form exemplified above is preferably a form containing (A1) polycarbonate resin and (A2) polycarbonate resin. When the polycarbonate resin (A1) and the polycarbonate resin (A2) are contained, the mixing ratio of the two is preferably 5:95 to 48:52, and more preferably 10:90 to 47:53 by mass ratio. It is more 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 include only one type of (A1) polycarbonate resin and (A2) polycarbonate resin, or may include two or more types thereof. When two or more kinds are contained, the total amount is preferably within the above range. With such a configuration, the pencil hardness of the molded product obtained from the resin composition can be HB or higher, and further F or higher. The upper limit of the pencil hardness is not particularly limited, but may be 4H or less, further 3H or less.

In the present invention, the lower limit of the viscosity average molecular weight (Mv) of the (A) polycarbonate resin is preferably 9,000 or more, more preferably 10,000 or more, and more preferably 12,000 or more. More preferable. Further, the upper limit of Mv is preferably 32,000 or less, more preferably 30,000 or less, and further preferably 28,000 or less.
By setting the viscosity average molecular weight to be the above lower limit or more, a molded product having improved moldability and high mechanical strength can be obtained. Further, when the content is not more than the above upper limit, the fluidity of the molded product is improved, and a thin molded product or the like can be efficiently manufactured.
The viscosity average molecular weight (Mv) is measured according to the method described in Examples below (hereinafter, the same applies to Mv). When two or more (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 is exemplified to have a pencil hardness of 3B to 2H measured according to ISO 15184, preferably B to 2H, and more preferably HB to 2H. The pencil hardness is measured according to the method described in Examples described later (hereinafter, the same applies to the pencil hardness). When two or more (A) polycarbonate resins are included, the pencil hardness of the mixture is preferably within the above range.

  The method for producing the above (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-state transesterification method of a prepolymer. Among these, the interfacial polymerization method and the melt transesterification method are preferable.

  The resin composition of the present invention preferably contains (A) a polycarbonate resin and (C) an acrylic resin in a proportion of 80% by mass or more of the total composition, and more preferably in a proportion of 85% by mass or more, The content is more preferably 90 mass% or more, and further preferably 93 mass% or more. The upper limit of the total of the (A) polycarbonate resin and the (C) acrylic resin is not particularly limited, but can be, for example, 99.4 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 kind or the like.

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

  The first embodiment of the (B) 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 thus reducing the number of ester groups, the transparency of the obtained 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, further preferably 50 mgKOH / g or less, and further preferably 35 mgKOH / g or less.
The hydroxyl value is measured according to the method described in Examples below.

Further, 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 carbon number of the monoester compound is preferably 42 or more, more preferably 44 or more. The upper limit of the number of carbon atoms of the monoester compound is not particularly limited, but is preferably 100 or less, more preferably 90 or less. (The carbon number of the 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 monovalent alcohol, The total number of carbon atoms contained in the alcohol is the carbon number of the monoester compound.
When two or more monoester compounds are included, the carbon number is the total value of the values obtained by multiplying the carbon number of each monoester compound by the mass fraction.

  The molecular weight of the monoester compound used in the present invention is preferably 2000 or less, more preferably 1500 or less, and further preferably 1200 or less. With such a structure, it is possible to obtain a molded product having an excellent balance between high transparency and high resistance to scratching by nails. Details of the structure will be described in detail.

  The monoester compound used in the present invention may have a linear structure or a branched structure, but preferably has a linear structure and both ends thereof have an alkyl group having 15 or more carbon atoms (preferably carbon atoms). 15 to 30 alkyl groups). With such a configuration, it becomes easy to obtain a molded product having an excellent balance between high transparency and high resistance to scratching by nails.

Next, the carboxylic acid will be described.
In the present invention, the carboxylic acid may be any of saturated fatty acids, unsaturated fatty acids, and aromatic carboxylic acids 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, and particularly preferably a linear saturated fatty acid.
The carboxylic acid may or may not have a substituent, but preferably does not have a substituent. The one having no substituent tends to further improve the transparency of the obtained molded article.
Further, the carboxylic acid is preferably composed only of oxygen atom, carbon atom and hydrogen atom. The carbon number of the carboxylic acid is preferably 2 to 45, more preferably 10 to 40, further preferably 15 to 36, and particularly preferably 20 to 30.
Specific examples of the carboxylic acid (the number in parentheses is the carbon number) 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), serotonin Examples are acids (saturated C26), montanic acid (saturated C28), and melissic acid (saturated C30).

Next, alcohol will be described.
In the present invention, the alcohol is preferably a monohydric alcohol, which 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 saturated alcohol, and particularly preferably linear saturated alcohol.
The alcohol may or may not have a substituent, but preferably does not have a substituent. The one having no substituent tends to further improve the transparency of the obtained molded article.
Further, the alcohol is preferably composed only of oxygen atom, carbon atom and hydrogen atom.
The carbon number of the alcohol is preferably 2 to 45, more preferably 5 to 36.
Specific examples of alcohols (the numbers in parentheses are carbon numbers) include octanol (saturated C8), dodecanol (saturated C12), stearyl alcohol (saturated C18), oleyl alcohol (unsaturated C18), behenyl alcohol (saturated C22), L. Examples include silalcohol (unsaturated C22) and montanyl alcohol (saturated C28).

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

  Specific examples of the monoester compound (carbon number in parentheses) used in the present invention include behenyl behenate (C44), montanyl montanate (C56), stearyl montanate (C46), montanyl stearate (C46), Examples thereof include behenyl montanate (C50) and montanyl behenate (C50), with montanyl montanate (C56) and behenyl behenate (C44) being particularly preferable.

  The monoester compound used in the present invention is often a mixture of a plurality of compounds having different carbon numbers, but in the present invention, it is contained as a main component (preferably 50 mass% or more, more preferably 70 mass% or more). The ester compound of

The 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 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 preferable.
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 at the time of molding or the like can be effectively suppressed, and the compatibility with the polycarbonate resin is excellent. Therefore, it is possible to obtain a resin composition which is excellent in extrudability, has high transparency, and is capable of forming a molded article excellent in resistance to scratches on the initial stage and after being wiped with cotton soaked with ethanol. .

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

Particularly, 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 carbon numbers. A diester compound obtained from a monohydric carboxylic acid having 16 to 40 or a mixture thereof is preferable, 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. A compound, 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 is more preferable, and a divalent carboxylic acid having 3 to 10 carbon atoms. A diester compound obtained from an acid and a monohydric alcohol having 16 to 30 carbon atoms or a mixture thereof is more preferable.
Further, in the diester compound composed of a divalent carboxylic acid and a monohydric alcohol used in the present invention, the carbon number of the monohydric alcohol is preferably 10 or more, more preferably 10 to 20 greater than the carbon number of the divalent carboxylic acid. Is more preferable. Alternatively, in the diester compound composed of a monovalent carboxylic acid and a divalent alcohol used in the present invention, the number of carbon atoms of the divalent alcohol is preferably 10 or more and more than 10 to 20 larger than the number of carbon atoms of the monovalent carboxylic acid. Is more preferable. With 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 the monovalent carboxylic acid (number of carbon atoms in parentheses) include behenic acid (22), lignocellicinic acid (24), cerotic acid (26), montanic acid (28), melicinic acid (30), and the like. To be

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

  Specific examples of the divalent carboxylic acid (the 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), Examples thereof include 1,3-cyclohexanedicarboxylic acid (8) and 1,2-cyclohexanedicarboxylic acid (8).

  Specific examples of the dihydric alcohol (the number of carbon atoms in parentheses) are ethylene glycol (2), propylene glycol (3), tetramethylene glycol (4), diethylene glycol (4), 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, further preferably 50 mgKOH / g or less, and further preferably 10 mgKOH / g or less. . The lower limit of the hydroxyl value of the diester compound is not particularly limited, but 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 or molding, and the appearance and physical properties of the molded product are improved. It tends to occur and is preferable.
According to this aspect, the molded article obtained from the composition of the present invention has excellent resistance to scratching with a nail after being wiped off with ethanol-soaked cotton.

The diester compound used in the present invention is often a mixture of a plurality of compounds having different carbon numbers, but in the present invention, it is contained as a main component (preferably 50 mass% or more, more preferably 70 mass% or more). An ester compound will be referred to.
The molecular weight is preferably 2000 or less, more preferably 1800 or less, even more preferably 1400 or less, even more preferably 1000 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, it is possible to obtain a molded article having an excellent balance between high transparency and high resistance to scratching by nails. When the ester compound is a mixture, the number average molecular weight is used.
The diester compound used in the present invention is often a mixture of a plurality of compounds having different carbon numbers, but in the present invention, it is contained as a main component (preferably 50 mass% or more, more preferably 70 mass% or more). An ester compound will be referred to.

The 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 polyvalent 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 atoms). It is preferably an ester compound obtained from a monovalent carboxylic acid of formula (20 to 50) or a mixture of both.
By containing such a triester compound in the resin composition of the present invention, the decomposition of the polycarbonate resin is suppressed, the generation of gas at the time of molding or the like can be effectively suppressed, and further the compatibility with the polycarbonate resin is excellent. . For this reason, it is possible to obtain a resin composition which is excellent in extrudability, has high transparency, and can form a molded article having excellent resistance to nail scratches at the initial stage and after solvent wiping.

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 trivalent alcohol, or a mixture thereof.
The monohydric alcohol and the monovalent carboxylic acid may each contain at least one of an aliphatic structure, an alicyclic structure and an aromatic structure, and each of them contains an aliphatic structure and / or an alicyclic structure. Is preferred. The monohydric alcohol and the monocarboxylic acid are preferably composed of a linear or branched aliphatic structure or alicyclic structure and a carboxyl group or a hydroxyl group, respectively.
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 carbon number is preferably 50 or less, more preferably 40 or less, and 32 or less. More preferably, it is even more preferably 30 or less.
The trivalent carboxylic acid and the trihydric alcohol may each include at least one of an aliphatic structure, an alicyclic structure and an aromatic structure, and each of them may have an aliphatic structure and / or an alicyclic structure. It is preferable to include.
The trivalent carboxylic acid and the trihydric alcohol are each preferably composed of a linear or branched aliphatic structure or alicyclic structure and a carboxyl group or a hydroxyl group. It is preferable that the trivalent carboxylic acid and the trivalent alcohol each have 3 or more carbon atoms. Further, the carbon number of each of the trivalent carboxylic acid and the trivalent alcohol is preferably 10 or less, and 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 trivalent 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, and a trivalent carboxylic acid having 3 to 10 carbon atoms and 20 to 30 carbon atoms. A triester compound obtained from a monohydric alcohol, a triester compound obtained from a trivalent 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 preferred is a triester compound obtained from a trihydric alcohol having 3 to 10 carbon atoms and a monohydric carboxylic acid having 20 to 30 carbon atoms, or two or more thereof. More preferably a mixture of.
Further, the triester compound composed of a trivalent alcohol and a monovalent carboxylic acid used in the present invention is preferably such that the monovalent carboxylic acid has 10 or more carbon atoms larger than the carbon number of the trihydric alcohol. Larger is more preferable. With 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 the monovalent carboxylic acid having 20 or more carbon atoms (the number in the parentheses is the number of carbon atoms) include behenic acid (22), lignocericinic acid (24), cerotic acid (26), montanic acid (28), and melicinic acid 30) and the like.

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

  Specific examples of the trivalent carboxylic acid (carbon number 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 Examples thereof include tricarboxylic acid (9) and 1,2,4-cyclohexanetricarboxylic acid (9).

  Specific examples of the trihydric alcohol (carbon number in parentheses) include glycerin (3), trimethylolpropane (6), trimethylolethane (5), trimethylolethane (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, further preferably 50 mgKOH / g or less, and further preferably 10 mgKOH / g or less. preferable. The lower limit of the hydroxyl value of the triester compound is not particularly limited, but is, for example, 1 mgKOH / g or more. By setting the hydroxyl value of the triester compound to 100 mgKOH / g or less, 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. It tends to improve and is preferable.
According to this aspect, the molded article obtained from the composition of the present invention has excellent resistance to scratching with a nail after being wiped off with ethanol-soaked cotton.

  The molecular weight of the triester compound used in the present invention is preferably 2000 or less, more preferably 1800 or less, and further preferably 1400 or less. The lower limit is preferably 1000 or more. When the molecular weight of the triester compound is in the above range, it is possible to obtain a molded article having an excellent balance of high transparency and high scratch resistance.

  The triester compound used in the present invention is often a mixture of a plurality of compounds having different carbon numbers, but in the present invention, it is contained as a main component (preferably 50 mass% or more, more preferably 70 mass% or more). The ester compound of

The fourth embodiment of the (B) 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 polyvalent 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 atoms). It is preferably an ester compound obtained from a monovalent carboxylic acid of formula (20 to 50) or a mixture of both.
By containing such a tetraester compound in the resin composition of the present invention, 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 which is excellent in extrudability, has high transparency, and is capable of forming a molded article excellent in resistance to scratches on the initial stage and after being wiped with cotton soaked with ethanol. .

The tetraester compound is preferably a tetraester compound composed of a tetravalent carboxylic acid and a monohydric alcohol, a tetraester compound composed of a monovalent carboxylic acid and a tetravalent alcohol, or a mixture thereof.
The monohydric alcohol and the monovalent 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. It is preferable. The monohydric alcohol and the monocarboxylic acid are preferably composed of a linear or branched aliphatic structure or alicyclic structure and a carboxyl group or a hydroxyl group, respectively.
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 carbon number is preferably 50 or less, more preferably 40 or less, and 32 or less. More preferably, it is even more preferably 30 or less.
The tetravalent carboxylic acid and the tetrahydric alcohol may each include at least one of an aliphatic structure, an alicyclic structure, and an aromatic structure, and each of them may have an aliphatic structure and / or an alicyclic structure. It is preferable to include a structure.
It is preferable that each of the tetravalent carboxylic acid and the tetravalent alcohol is composed of a linear or branched aliphatic structure or an alicyclic structure and a carboxyl group or a hydroxyl group. The carbon number of each of the tetravalent carboxylic acid and the tetravalent alcohol is preferably 3 or more, more preferably 4 or more, and further preferably 5 or more. Further, the carbon number of each of the tetravalent carboxylic acid and the tetravalent alcohol is preferably 10 or less, and 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 tetravalent alcohol having 3 to 10 carbon atoms. A tetraester compound obtained from a monovalent carboxylic acid having 20 to 40 carbon atoms or a mixture thereof is preferable, and a tetravalent carboxylic acid having 3 to 10 carbon atoms and a monohydric alcohol having 20 to 30 carbon atoms are used. The obtained tetraester compound, the tetraester compound obtained from a C4 to C10 tetrahydric alcohol and a C20 to C30 monocarboxylic acid, or a mixture thereof is more preferable, and a C3 to C10. Is a tetraester compound obtained from the tetrahydric alcohol and a monovalent carboxylic acid having 20 to 30 carbon atoms, or a mixture thereof. Preferred.
Furthermore, in the tetraester compound composed of a tetravalent alcohol and a monovalent carboxylic acid used in the present invention, the carbon number of the monovalent carboxylic acid is preferably 10 or more larger than the carbon number of the tetravalent alcohol, and is 10 to 20. Larger is more preferable. With 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 preferably does not have a substituent. The one having no substituent tends to further improve the transparency of the obtained molded article. The carboxylic acid is preferably composed only of oxygen atoms, carbon atoms and hydrogen atoms.

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

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

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

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

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 group represented by RB ^{1 to} RB ⁴ is preferably a saturated aliphatic hydrocarbon group, and more preferably a linear saturated aliphatic hydrocarbon group. The number of carbon atoms of the aliphatic hydrocarbon group represented by RB ^{1 to} RB ⁴ is preferably 2 or more, more preferably 5 or more, even 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 further preferably 36 or less. It is preferable that the aliphatic hydrocarbon groups represented by RB ^{1 to} RB ⁴ 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 having different carbon numbers, but in the present invention, it is contained as a main component (preferably 50 mass% or more, more preferably 70 mass% or more). The ester compound of

The hydroxyl value of the tetraester compound is preferably 100 mgKOH / g or less, more preferably 70 mgKOH / g or less, further preferably 50 mgKOH / g or less, and further preferably 10 mgKOH / g or less. preferable. The lower limit of the hydroxyl value of the tetraester compound is not particularly limited, but is, for example, 1 mgKOH / g or more. By setting the hydroxyl value of the tetraester compound to 100 mgKOH / g or less, 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. It tends to improve and is preferable.
According to this aspect, the molded article obtained from the composition of the present invention has excellent resistance to scratching with a nail after being wiped off with ethanol-soaked cotton.

  The molecular weight of the tetraester compound used in the present invention is preferably 2200 or less, more preferably 2000 or less, and further preferably 1800 or less. The lower limit is preferably 1400 or more. When the molecular weight of the tetraester compound is in the above range, it is possible to obtain a molded product having an excellent balance of high transparency and high resistance to scratches by nails.

  In the tetraester compound used in the present invention, the carboxylic acid constituting the above ester structure may or may not have a substituent, but it is preferable not to have it. The one having no substituent tends to further improve the transparency of the obtained molded article. 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 the (B) ester compound with respect to 100 parts by mass of the (A) polycarbonate resin.
The lower limit of the blending amount of the (B) ester compound is preferably 0.6 parts by mass or more, and more preferably 0.8 parts by mass or more, relative to 100 parts by mass of the (A) polycarbonate resin. Particularly preferably 1.0 part by mass or more, 1.5 parts by mass or more, 1.8 parts by mass or more, and more preferably 2.0 parts by mass or more, more than 2.0 parts by mass. By setting the above range, which may be 2.2 parts by mass or more, the resistance to scratches by nails can be further improved.
The upper limit of the blending amount of the (B) ester compound is preferably 9.0 parts by mass or less, and more preferably 8.0 parts by mass or less, relative to 100 parts by mass of the (A) polycarbonate resin. The amount is more preferably 7.0 parts by mass or less, further preferably 6.0 parts by mass or less, further preferably 5.0 parts by mass or less, 4.0 parts by mass or less, 3.5. It may be not more than 3.2 parts by mass. When the content is in the preferred range, the hydrolysis resistance is improved and the mold contamination can be suppressed more effectively. In the present invention, even if the compounding amount of the ester compound (B) is small, it is possible to obtain a structure excellent in nail scratch resistance.
The resin composition of the present invention may contain only one type of (B) ester compound, or may include two or more types. When two or more kinds are contained, 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。 The acrylic resin (C) 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 has 6 carbon atoms which may have a substituent. To an aromatic hydrocarbon group having 20 to 20 carbon atoms or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, which is substituted with an aromatic hydrocarbon group having 6 to 17 carbon atoms which may have a substituent.
R ⁵ and R ⁶ are each independently preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.
R ^7's are each independently preferably a hydrogen atom or a methyl group, and more preferably a methyl group.
R ⁸ is preferably a phenyl group which may have a substituent, a naphthyl group which may have a substituent, or a benzyl group which may have a substituent, and a phenyl group which does not have a substituent. Further, a naphthyl group having no substituent is more preferable, and a phenyl group having no substituent is further preferable.
Examples of the substituent include a halogen atom (preferably chlorine atom or fluorine atom) and an alkyl group (preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group). When it has a substituent, the number of the substituent is preferably 1 to 3 per one aromatic ring, more preferably 1 or 2, and even more preferably 1.
The (C) acrylic resin in the present invention may be a polymer composed of only the structural unit (c1) represented by the formula (X), or the structural unit (c1) represented by the formula (X). And a structural unit other than (c1) (generally, a structural unit derived from a (meth) acrylic acid ester), and the latter copolymer is preferred.
In the present invention, a copolymer having the structural unit (c1) represented by the formula (X) and the structural unit (c2) represented by the 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 may have a hydrogen atom or a substituent. A good aliphatic hydrocarbon group having 1 to 20 carbon atoms is shown (provided that the substituent does not include an aromatic hydrocarbon group).
R ⁵ and R ⁶ are each independently preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.
R ^7's are each independently preferably a hydrogen atom or a methyl group, and more preferably a methyl group.
R ⁹ is preferably a hydrogen atom or an aliphatic hydrocarbon group having 1 to 6 carbon atoms which may have a substituent, 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 or 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 such that the mass ratio of (c1) / (c2) is 5 to 80/95 to 20, and preferably 20 to 70/80 to 30. It is more preferable to contain it, and it is more preferable to contain it in a ratio of 25 to 45/75 to 55. When the mass ratio of (c1) is 5 or more, the transparency of the (C) acrylic resin tends to be further improved, and when the mass ratio of (c1) is 95 or less, it is (A) a polycarbonate resin. There is a tendency that the compatibility of is more appropriate, the transferability to the surface of the molded product is more effectively suppressed, and the surface hardness is further improved.
Further, in the present invention, the molecular weight of the monomer constituting the repeating unit (c1) is preferably 100 to 900, more preferably 100 to 500, and further preferably 100 to 300. Furthermore, in the present invention, the molecular weight of the monomer constituting the repeating unit (c2) is preferably 80 to 900, more preferably 80 to 500, and further preferably 80 to 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 preferable, and phenyl methacrylate is more preferable.
In addition, in this invention, (meth) acrylate shows an acrylate and / or a methacrylate.
Methyl methacrylate is preferred as the monomer constituting the repeating unit (c2). By using methyl methacrylate as the monomer constituting the repeating unit of (c2), the dispersibility in the polycarbonate resin (A) is further improved, and the surface of the molded product is further improved because it is transferred to the surface of the molded product. .

  As a method for polymerizing the monomer (C) to obtain the 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. The suspension polymerization method and the bulk polymerization method are preferable, and the suspension polymerization method is more preferable. Further, additives and the like necessary for polymerization can be appropriately added as needed, and examples thereof include a polymerization initiator, an emulsifier, a dispersant, and a chain transfer agent.

  When the (C) acrylic resin used in the present invention contains the structural unit represented by the formula (X), it is preferably 20% by mass or more, and 30% by mass of the structural unit constituting the (C) acrylic resin. The above is more preferable. The upper limit is preferably 95% by mass or less, and more preferably 80% by mass or less. The structural unit represented by the formula (X) may include only one type, or may include two or more types. When two or more kinds are contained, 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 thereof is 90 mass of the (C) acrylic resin. It is preferable to occupy at least%.
The structural unit represented by the formula (X1) may include only one type, or may include two or more types. When two or more kinds are contained, 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 further 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. Within the above range, the compatibility with the (A) 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 acrylic resin (C) is measured by gel permeation chromatography using tetrahydrofuran (THF) as a solvent. The weight average molecular weight is a value converted into standard polystyrene resin (PS).

  The content of the acrylic resin (C) is 1 to 100 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A). 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, 20 parts by mass or more. , 30 parts by mass or more. 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, further preferably 45 parts by mass or less, and further 38 parts by mass. Hereinafter, it may be 30 parts by mass or less and 20 parts by mass or less. When the content is within the above range, the resin composition of the present invention effectively improves surface hardness and fluidity while maintaining good transparency while maintaining physical property balance such as impact resistance, and further during molding. The problem of whitening 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, the Δhaze before and after the light resistance test can be significantly reduced. 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 reciprocation test can be further reduced.

  Further, in the resin composition of the present invention, the ratio ((B) / (C) × 100) (mass%) of the (B) ester compound to the (C) acrylic resin is preferably 3 to 200, and the lower limit is set. 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, further preferably 50 or less, still more preferably 35 or less, still more preferably 25. Hereafter, it is even more preferably 20 or less. With such a structure, higher transparency and resistance to scratching of the nails at the initial stage and after solvent wiping can be achieved.

  As the (C) acrylic resin used in the present invention, in addition to the above, those described in WO2014 / 038500, WO2013 / 094898, JP2006-199774A, JP2010-116501A are adopted. And their contents are incorporated herein.

<Other ingredients>
The resin composition of the present invention may contain components other than the above components, if necessary, as long as desired physical properties are not significantly impaired. Examples of other components include thermoplastic resins other than the above-mentioned (A) polycarbonate resin and (C) acrylic resin, various resin additives, and the like.
The resin composition of the present invention preferably contains no inorganic filler, but may contain an inorganic filler. By including the inorganic filler, the mechanical strength of the obtained molded product can be further improved. As one embodiment of the resin composition of the present invention, no inorganic filler is contained, or the inorganic filler is 8 parts by mass or less (preferably 6 parts by mass or less, more preferably 100 parts by mass of the (A) polycarbonate resin. Is 4 parts by mass or less, more preferably 1 part by mass or less). When the inorganic filler is not included or the content is within the above range, the transparency of the obtained molded article can be further improved. As the inorganic filler, the description in paragraphs 0075 to 0079 of JP-A-2017-110180 can be referred to, and the contents thereof are incorporated in the present specification.
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. In addition, 1 type may be contained in the resin additive and 2 or more types may be contained in arbitrary combinations and ratios.

<< Stabilizer >>
Examples of the stabilizer include a heat stabilizer and an antioxidant.
A phosphorus-based stabilizer is preferably used as the heat stabilizer.
Any known phosphorus stabilizer may be used. Specific examples thereof include phosphorus oxo acids such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, and polyphosphoric acid; metal acid pyrophosphate salts such as sodium acid pyrophosphate, potassium acid pyrophosphate, and calcium acid pyrophosphate; phosphorus Phosphates of Group 1 or Group 2B metals such as potassium phosphate, sodium phosphate, cesium phosphate, zinc phosphate; organic phosphate compounds, organic phosphite compounds, organic phosphonite compounds, and the like, but organic phosphite compounds Is particularly preferable.

Examples of the organic phosphite compound include triphenyl phosphite, tris (monononylphenyl) phosphite, tris (monononyl / dinonylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, monooctyl. Diphenyl phosphite, dioctyl monophenyl phosphite, monodecyl diphenyl phosphite, didecyl monophenyl phosphite, tridecyl phosphite, trilauryl phosphite, tristearyl phosphite, 2,2-methylenebis (4,6-di- tert-butylphenyl) octyl phosphite and the like.
As such an organic phosphite compound, specifically, for example, "ADEKA STAB (registered trademark; the same applies below) 1178", "ADEKA STAB 2112", "ADEKA STAB HP-10" manufactured by ADEKA, manufactured by Johoku Chemical Industry Co., Ltd. "JP-351", "JP-360", "JP-3CP", "Irgafos (registered trademark, the same applies hereinafter) 168" manufactured by BASF, and the like can be mentioned.

As the antioxidant, a hindered phenol stabilizer is preferably used.
Specific examples of the hindered phenol stabilizer include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and 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-bu Tyl-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-hydroxybenzyl) -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) Chill] -4,6-di -tert- pentylphenyl acrylate.

  Among them, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate are available. preferable. Specific examples of such hindered phenol-based stabilizers include "Irganox (registered trademark; the same applies hereinafter) 1010", "Irganox 1076" manufactured by BASF, "Adeka Stab AO-50", and "Adeka Stub" manufactured by ADEKA. 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. And usually 1 part by mass or less, preferably 0.5 part by mass or less, and more preferably 0.3 part by mass or less. By setting the content of the stabilizer within the above range, the effect of adding the stabilizer is more effectively exhibited.

<< UV absorber >>
As the ultraviolet absorber, the description in paragraphs 0059 to 0062 of JP-A-2016-216534 can be referred to, and the contents thereof are incorporated in the present specification.

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

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

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

  The 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 has a dynamic friction coefficient of 0.35 or less in accordance with ISO 19252 at a load of 30 N. Is. As a lower limit of the dynamic friction coefficient, 0 is ideal, but 0.01 or more, and even 0.10 or more is a practical level. The method of measuring the dynamic friction coefficient is as described in the examples below.

  A test piece having a thickness of 2 mm (preferably 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 is a reciprocating wear test using smoothness (100% cotton, 20 × 20 count). Δ haze, which is the difference between the front and back haze, is preferably 5.00% or less, more preferably 4.00% or less, further preferably 3.50 or less, and 3.00% or less. It is more preferable that it is 2.90% or less, still more preferably, 2.80% or less, still more preferably 2.00% or less. The lower limit of Δ haze before and after the reciprocating wear test is ideally 0%, but 0.01% or more, and even 0.07% or more is at a practical level. The method for measuring the Δhaze before and after the reciprocating wear test is as described in the examples below.

  When two or more kinds of (A) polycarbonate resin and / or (C) acrylic resin are contained, (A) polycarbonate resin and (C) acrylic resin have the pencil hardness of (A) polycarbonate resin and (C) acrylic resin mixture, respectively. The pencil hardness of the resin.

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

<Method for producing resin composition>
There is no limitation on the method for producing the resin composition of the present invention, a well-known method for producing a polycarbonate resin composition can be widely adopted, and the above-mentioned polycarbonate resin and ester compound, and other components to be blended as necessary, for example, Examples include a method of previously mixing using various mixers such as a tumbler and a Henschel mixer, and then melt-kneading with a mixer such as a Banbury mixer, roll, Brabender, single-screw kneading extruder, twin-screw kneading extruder, and kneader.
The temperature of melt kneading is not particularly limited, but is usually in the range of 240 to 320 ° C.

<Molded products>
The resin composition (for example, pellets) described above is molded by various molding methods to obtain a molded product. 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 depending on the use and purpose of the molded product, for example, film shape, rod shape, cylindrical shape, ring shape, circular shape, elliptical shape, polygonal shape. , Shaped products, hollow products, frame-shaped, box-shaped, panel-shaped, button-shaped products and the like. Among them, those having a film shape, a frame shape, a panel shape, and a button shape are preferable, and the thickness is, for example, about 1 mm to 5 mm in the case of a frame shape or a panel shape.

  The method for molding the molded product is not particularly limited and can be a conventionally known molding method, for example, an injection molding method, an injection compression molding method, an extrusion molding method, a profile extrusion method, a transfer molding method, a hollow molding method, Gas-assisted blow molding method, blow molding method, extrusion blow molding method, IMC (in-mold coating molding) molding method, rotational molding method, multi-layer molding method, two-color molding method, insert molding method, sandwich molding method, foam molding method. , A pressure molding method and the like. In particular, the resin composition of the present invention is suitable for molded articles 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 from these.

  The molded product of the present invention is suitably used for electric and electronic equipment, OA equipment, portable information terminals, mechanical parts, home appliances, vehicle parts, various containers, parts such as lighting equipment, and the like. Among these, in particular, they are used for electric and electronic equipment, office automation equipment, information terminal equipment and housings of home electric appliances, lighting equipment and vehicle parts (particularly vehicle interior parts), and vehicle interior parts are particularly preferable.

  Hereinafter, the present invention will be described more specifically with reference to examples. Materials, usage amounts, ratios, processing contents, processing procedures, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

1. Raw Material <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 (internal volume 10 liter) equipped with a stirrer and a distilling condenser. After charging and purging the inside of the reactor with nitrogen gas, the temperature was raised to 220 ° C. over 30 minutes in a nitrogen gas atmosphere.
Then, the reaction liquid in the reactor is stirred, and cesium carbonate (Cs ₂ CO ₃ ) as a transesterification reaction catalyst is added to the reaction liquid in a molten state so that the amount becomes 1.5 × 10 ⁻⁶ mol per mol of BPC. In addition, the reaction solution was stirred and cultivated at 220 ° C. for 30 minutes under a nitrogen gas atmosphere. Next, at the same temperature, the pressure in the reactor was reduced to 100 Torr over 40 minutes, and the reaction was continued for 100 minutes to distill 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 phenol corresponding to almost all the theoretical amount of distillate. Next, under the same temperature, the pressure in the reactor was kept below 1 Torr, and the reaction was continued for another 60 minutes to complete the polycondensation reaction. At this time, the stirring rotation speed of the stirrer was 38 rotations / minute, the reaction liquid temperature immediately before the end of the reaction was 289 ° C., and the stirring power was 1.00 kW.
Next, the reaction liquid in the molten state was fed into a twin-screw extruder, and a 4-fold molar amount of butyl p-toluenesulfonate was fed from the first feed port of the twin-screw extruder with respect to cesium carbonate. After kneading with the reaction liquid, the reaction liquid was extruded into a strand through a die of a twin-screw extruder and cut with a cutter to obtain pellets of polycarbonate resin A1.

The 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 determining the intrinsic viscosity (η) (unit: dL / g) at a temperature of 20 ° C. using a Ubbelohde viscometer using methylene chloride as a solvent, and the viscosity of the following Schnell. 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, an injection molding machine (“α-2000i-150B” manufactured by FANUC CORPORATION) was used to set the cylinder temperature at 260 ° C. and the mold temperature at 70 ° C., and the screw rotation speed was 100 rpm. A flat plate-shaped test piece (150 mm × 100 mm × 2 mm thickness) was produced under the condition of an injection speed of 30 mm / sec. With respect to this flat plate-shaped test piece, the pencil hardness measured with a 750 g load was determined using a pencil hardness tester in accordance with ISO 15184.
The pencil hardness tester used was manufactured by Toyo Seiki Seisakusho.

<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 was acetylated, and the alcohol as the raw material of the ester compound was esterified with the carboxylic acid compound. Sometimes, it is an index showing the number of unreacted and remaining hydroxyl groups.
The hydroxyl value was measured according to the method specified in JIS K0070.

2. Examples 1 to 5, Comparative Examples 1 to 8
<Production of resin composition pellets>
The components shown in Table 1 above were blended in the proportions shown in Table 2 below (all are shown in parts by mass) and uniformly mixed with a tumbler mixer, and then a twin-screw extruder (Nippon Steel Works, Ltd.) TEX30α) manufactured by Tokoro Co., Ltd., a cylinder set temperature of 260 ° C., a screw rotation speed of 180 rpm, and a discharge rate of 30 kg / hr were fed into the extruder through a barrel upstream of the extruder and melt-kneaded to obtain resin composition pellets. .

<Molar 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 the formula (1) in the polycarbonate resin contained in the resin composition, and the mixing ratio of the resin used and the formula It was calculated from the viscosity average molecular weight using the molecular weight of the structural unit represented by (1).

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

<Amount of extruded 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, the gas generation standard (a) was evaluated, and the amount of gas generated was compared with the standard amount. The gas generation amount was visually evaluated as follows.
a: Gas generation standard b: Somewhat c: Many

<Comprehensive evaluation of extrudability>
The following evaluation was made based on the results of the above extrudability and gas generation amount.
A: Both extrudability and gas generation amount are a.
B: Other than the above A and the following C.
C: At least one of the extrudability and the gas generation amount is c.

<Manufacture of test pieces for evaluation as molded articles>
After drying the resin composition pellets obtained above at 100 ° C. for 5 hours, using an injection molding machine (“α-2000i-150B” manufactured by FANUC CORPORATION), a cylinder setting temperature of 260 ° C., a mold temperature of 70 ° C., Under the conditions of a screw rotation speed of 100 rpm and an injection speed of 30 mm / sec, a 150 mm × 100 mm × 2 mm thick flat plate test piece was injection-molded.

<Measurement of haze>
The haze (unit:%) of the flat plate 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>
With respect to the flat plate-shaped test piece obtained above, a pencil hardness measured with a load of 1 kg was determined using a pencil hardness tester according to ISO 15184.
The pencil hardness tester used was manufactured by Toyo Seiki Seisakusho.

<Dynamic friction coefficient (30N)>
Regarding the flat plate-shaped test piece obtained above, a vertical load of 1N to 50N can be varied between a test speed of 100 mm / sec and a test distance of 100 mm using a scratch tester with a spherical terminal of 1 mmφ according to ISO 19252. While scanning, the horizontal load and the vertical load were measured at a load of 30 N, and the dynamic friction coefficient (horizontal load / vertical load) was obtained and evaluated as follows. The smaller the dynamic friction coefficient, the better.
A scratch tester manufactured by Kato Tech Co., Ltd. was used.
a: 0.38 or less b: 0.38 or more and 0.40 or less c: 0.40 or more

<Nail scratch resistance>
The tabular test piece obtained above was rubbed 10 times with a nail and sensory evaluation was performed.
a: No scratches and good sliding.
b: Slightly scratched but slippery.
There are fewer scratches than c: d, but they are scratched.
d: Hurt.

<Δ haze before and after reciprocating wear test>
The haze of the flat plate-shaped test piece obtained above was measured in the same manner as above (haze at this time is referred to as haze a).
On the other hand, with respect to the same flat plate-shaped test piece obtained above, a flat wear tester was used to fold flat (18% cut, 15 × 33 cm, 100% cotton, flat 20 × 20) flat wear The test piece was mounted on a jig of a tester and tested at 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 wear test was measured in the same manner as above (haze at this time is referred to as haze b). “Haze b-haze a” was taken as Δhaze before and after the reciprocating wear test, and evaluated according to the following categories.
The plane wear tester used was manufactured by Daiei Kagaku Seiki Seisakusho.
As the sashimi, sashimi made by Nankai Co., Ltd. was used.
a: 4.00% or less b: 4.00% or more but 5.00% or less c: 5.00% or more

<Comprehensive evaluation of scratch resistance>
The following evaluation was performed based on the results of the above-mentioned nail scratch resistance, dynamic friction coefficient, and Δhaze before and after the reciprocating wear test.
A: All evaluations are a.
B: Other than the above A and the following C.
C: At least one evaluation is c or d.

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

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

  The results are shown in Table 2 below.

In the above table, the "ratio of the formula (1)" is the ratio (mol%) of the structural units represented by the formula (1) to all the structural units constituting the polycarbonate resin.
As is clear from the above results, the resin composition of the present invention was excellent in scratch resistance, in particular, the transparency retention ratio before and after the abrasion test was high, and the extrudability was excellent (Examples 1 to 1 5). In particular, in Examples 1 to 3, the change in color tone (change in ΔE ^* ) before and after the light resistance test was significantly small.
If the proportion of the structural unit represented by the formula (1) exceeds 50 mol%, the change in color tone (change in ΔE ^* ) before and after the light resistance test becomes large (Comparative Examples 1 to 4).
When the proportion of the structural unit represented by the formula (1) is less than 5 mol%, pencil hardness is low, nail scratch resistance is poor, and Δ haze before and after reciprocating abrasion test is also poor, resulting in scratch resistance. 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 high. It turned out that it is not suitable for applications that require transparency.
Furthermore, when the amount of the ester compound was too large, the haze decreased, and when it was too small, the Δhaze before and after the reciprocating wear test was poor (Comparative Examples 7 and 8).

Claims (11)

A thermoplastic resin composition containing (B) an ester compound in an amount of 0.5 to 10.0 parts by mass and (C) an acrylic resin in an amount of 1 to 100 parts by mass with respect to 100 parts by mass of a polycarbonate resin (A),
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,
The (B) ester compound is composed of alcohol and carboxylic acid,
The (C) acrylic resin contains a structural unit represented by the following formula (X),
A 2 mm-thick test piece formed from the resin composition has a haze of 5.0% or less measured according to ISO 14782 and a dynamic friction coefficient of 0. 0 according to ISO 19252 at a load of 30 N. A resin composition of 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 one of the following formulas,

R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group, and Z is bonded to C to form an alicyclic hydrocarbon having 6 to 12 carbon atoms and optionally having 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 has 6 carbon atoms which may have a substituent. To an aromatic hydrocarbon group having 20 to 20 carbon atoms or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, which is substituted with an aromatic hydrocarbon group having 6 to 17 carbon atoms which may have a substituent. The resin composition according to claim 1, wherein the (B) ester compound is formed from a monovalent carboxylic acid and a monohydric alcohol. The resin composition according to claim 1, wherein R ⁵ , R ⁶ and R ⁷ in the formula (X) are each independently a hydrogen atom or a methyl group. R ⁸ in the formula (X) is a phenyl group which may have a substituent, a naphthyl group which may have a substituent, or a benzyl group which may have a substituent. The resin composition according to any one of 1 to 3. 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) / ( The resin composition according to any one of claims 1 to 4, wherein the resin composition is contained in a proportion that the mass ratio of c2) is 5 to 80/95 to 20;
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 may have a hydrogen atom or a substituent. A good aliphatic hydrocarbon group having 1 to 20 carbon atoms is shown (provided that the substituent does not include an aromatic hydrocarbon group). The resin composition according to any one of claims 1 to 5, wherein the (C) acrylic resin has a weight average molecular weight of 5,000 to 30,000. Content of the said (C) acrylic resin is 1-45 mass parts with respect to 100 mass parts of (A) polycarbonate resin, The resin composition of any one of Claims 1-6. The resin according to any one of claims 1 to 7, wherein the ratio ((B) / (C) x 100) (mass%) of the ester compound (B) to the acrylic resin (C) is 3 to 200. Composition. The resin composition according to any one of claims 1 to 8, wherein the polycarbonate resin (A) further contains a structural unit represented by the following formula (2):
Formula (2)

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

R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group, and Z is bonded to C to form an alicyclic hydrocarbon having 6 to 12 carbon atoms and optionally having a substituent. Represents a group. 10. The test piece having a thickness of 2 mm formed from the resin composition has a Δhaze of 4.00% or less, which is a difference in haze before and after a reciprocating abrasion test using a saliva. The resin composition according to. A molded article formed from the resin composition according to claim 1.