JP2019119846A - Resin composition and molded article - Google Patents

Abstract

To provide a resin composition extremely excellent in surface hardness, excellent in excoriation resistance, especially high in maintenance factor of transparency before and after an abrasion test, and excellent in extrudability, and a molded article using the resin composition.SOLUTION: There is provided a resin composition containing 100 pts.mass of (A) a polycarbonate resin, 0.5 to 10.0 pts.mass of (B) an ester compound, and 3 to 100 pts.mass of (C) an acrylic resin containing a structural unit derived from (meth)acrylate having an aromatic, in which the (A) polycarbonate resin contains 50 to 100 mol% of a structural unit represented by the following formula (1), the (B) ester resin is constituted by alcohol and carboxylic acid, a test piece with thickness of 2 mm formed from the resin composition has haze measured according to ISO 14782 of 5.0% or less, and dynamic friction coefficient according ISO 19252 at a load of 30 N of 0.35 or less; in the formula (1), Rrepresents a methyl group.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition and a molded article. In particular, the present invention relates to a resin composition capable of providing a molded article excellent in transparency and scratch resistance and excellent in surface hardness using a polycarbonate resin.

  Polycarbonate resins are excellent in mechanical strength, electrical properties, transparency and the like, and are widely used as engineering plastics in various fields such as electric and electronic equipment fields and automobile fields. In recent years, in these fields, thickness reduction, miniaturization and weight reduction of molded articles have progressed, and further performance improvement of molding materials is required, and some proposals have been made.

  For example, Patent Document 1 describes a graft copolymer 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) A polycarbonate resin composition is disclosed which is characterized by containing 0.1 to 12 parts by mass. The document also describes that the polycarbonate resin composition is excellent in scratch resistance in nails.

Unexamined-Japanese-Patent No. 2017-110180

Heretofore, polycarbonate resins containing a structural unit derived from bisphenol C are known to tend to have high pencil hardness. Here, it may be used as a product without processing such as painting (hereinafter sometimes referred to as "painting-less") on a molded article molded from a polycarbonate resin containing a structural unit derived from bisphenol C. However, as a result of investigations by the present inventor, it has been found that such molded articles have some problem in nail scratch resistance even though the pencil hardness is high. The resin composition described in Patent Document 1 is a resin composition excellent in nail scratch resistance, but in the examples of the same document, the jet clarity and the like are pursued. That is, for applications requiring transparency, development of new materials is required. Also, it is required to maintain high transparency even after the abrasion test.
Furthermore, even if the polycarbonate resin is compounded with an appropriate additive and excellent in abrasion resistance, and particularly, the transparency after the abrasion test can be maintained high, the extrudability is inferior if the blending amount of the additive is large. There is a possibility that
The object of the present invention is to solve the above-mentioned problems, and is very excellent in surface hardness and excellent in abrasion resistance, in particular, the maintenance rate of transparency after abrasion test is high, and extrudability It is an object of the present invention to provide a resin composition excellent in the above, 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、Ｒ⁶、Ｒ⁷およびＲ⁸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、飽和直鎖カルボン酸と飽和直鎖アルコール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Ｒ⁶、Ｒ⁷およびＲ⁸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Ｒ⁹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、Ｒ⁶、Ｒ⁷およびＲ⁸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、Ｒ¹⁰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７〜４５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＞前記（Ａ）ポリカーボネート樹脂中の式（１）で表される構造単位の含有割合が８０モル％以上である、＜１＞〜＜７＞のいずれか１つに記載の樹脂組成物。
＜９＞前記（Ｂ）エステル化合物の（Ｃ）アクリル樹脂に対する割合（（Ｂ）／（Ｃ）×１００）（％）が、３〜２００である、＜１＞〜＜８＞のいずれか１つに記載の樹脂組成物。
＜１０＞（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＞〜＜９＞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。
＜１１＞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３．００％以下である、＜１＞〜＜１０＞のいずれか１つに記載の樹脂組成物。
＜１２＞＜１＞〜＜１１＞のいずれか１つに記載の樹脂組成物から形成される成形品。 Based on the above problems, as a result of investigations by the present inventor, a predetermined polycarbonate resin is blended with a predetermined ester compound, and further, the predetermined haze and the dynamic friction coefficient are set to predetermined ranges, thereby solving the above problems. I found that I could do it. Specifically, the above problems are solved by the following means <1>, preferably <2> to <12>.
A resin composition comprising 0.5 to 10.0 parts by mass of (B) an ester compound and 3 to 100 parts by mass of (C) an acrylic resin with respect to 100 parts by mass of <1> (A) polycarbonate resin, The (A) polycarbonate resin contains 50 to 100 mol% of a structural unit represented by the following formula (1) in all structural units, and the (B) ester compound is composed of an alcohol and a carboxylic acid, C) An acrylic resin contains a structural unit represented by the following formula (X), and a test piece with a thickness of 2 mm formed from the resin composition has a haze of 5.0% or less measured in accordance with ISO 14782 A resin composition having a coefficient of dynamic friction according to ISO 19252 at a load of 30 N of 0.35 or less;
Formula (1)

In formula (1), R ¹ represents a methyl group, R ² represents a hydrogen atom or a methyl group, and X ¹ represents any 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 a substituted or unsubstituted alicyclic hydrocarbon having 6 to 12 carbon atoms Represents a group;
Formula (X)

In formula (X), R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ⁹ has 6 carbon atoms which may have a substituent. And an aliphatic hydrocarbon group of 1 to 20 carbon atoms or an aliphatic hydrocarbon group of 1 to 3 carbon atoms substituted with an aromatic hydrocarbon group of 6 to 17 carbon atoms which may have a substituent.
The resin composition as described in <1> in which the <2> above-mentioned (B) ester compound is formed from saturated linear carboxylic acid and saturated linear alcohol.
R ^6, R ⁷ and R ⁸ in <3> above formula (X) are each independently a hydrogen atom or a methyl group, <1> or the resin composition according to <2>.
<4> R ⁹ 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 as described in any one of <1>-<3>.
The <5> above-mentioned (C) acrylic resin is a copolymer which has a structural unit (c1) represented by Formula (X), and a structural unit (c2) represented by Formula (X1), and said (c1) The resin composition according to any one of <1> to <4>, which is contained at a ratio of 5 to 80/95 to 20) / (c2).
Formula (X1)

In formula (X1), R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ¹⁰ may have a hydrogen atom or a substituent A good C1-C20 aliphatic hydrocarbon group is shown (however, except that whose substituent contains an aromatic hydrocarbon group).
The resin composition as described in any one of <1>-<5> whose weight average molecular weights of <6> above-mentioned (C) acrylic resin are 5,000-30,000.
The resin composition as described in any one of <1>-<6> whose content of <7> said (C) acrylic resin is 7-45 mass parts with respect to 100 mass parts of (A) polycarbonate resin. .
The resin composition as described in any one of <1>-<7> whose content rate of the structural unit represented by Formula (1) in <8> said (A) polycarbonate resin is 80 mol% or more .
The ratio ((B) / (C) x 100) (%) of the <9> above-mentioned (B) ester compound to (C) acrylic resin is 3-200, any 1 of <1>-<8> The resin composition as described in one.
The resin composition as described in any one of <1>-<9> in which a <10> (A) polycarbonate resin contains the structural unit represented by following formula (2) further;
Formula (2)

In formula (2), X ² represents any 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 a substituted or unsubstituted alicyclic hydrocarbon having 6 to 12 carbon atoms Represents a group.
The test piece of thickness 2 mm formed from the <11> said resin composition is <1>-<10> whose delta haze which is a difference of the haze before and behind the reciprocation abrasion test which used salaci is 3.00% or less. The resin composition as described in any one of the above.
The molded article formed from the resin composition as described in any one of <12><1>-<11>.

  According to the present invention, it is possible to use a resin composition which is very excellent in surface hardness and excellent in scratch resistance, in particular, high in retention of transparency after abrasion test and excellent in extrudability, and the resin composition. Can be provided.

  Hereinafter, the contents of the present invention will be described in detail. In addition, in this specification, "-" is used in the meaning included including the numerical value described before and after that as a lower limit and an 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、Ｒ⁶、Ｒ⁷およびＲ⁸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、かつ、押出性に優れた樹脂組成物を提供可能になる。
以下、本発明の詳細について説明する。 The resin composition of the present invention is a resin containing 0.5 to 10.0 parts by mass of (B) an ester compound and 3 to 100 parts by mass of (C) an acrylic resin per 100 parts by mass of (A) polycarbonate resin It is a composition, Comprising: The said (A) polycarbonate resin contains 50-100 mol% of structural units represented by following formula (1) in all the structural units, The said (B) ester compound is from alcohol and carboxylic acid The (C) acrylic resin comprises a structural unit represented by the following formula (X), and the 2 mm-thick test piece formed from the resin composition has a haze measured according to ISO 14782 The dynamic friction coefficient according to ISO 19252 at 5.0% or less and at a load of 30 N is 0.35 or less.
Formula (1)

In formula (1), R ¹ represents a methyl group, R ² represents a hydrogen atom or a methyl group, and X ¹ represents any 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 a substituted or unsubstituted alicyclic hydrocarbon having 6 to 12 carbon atoms Represents a group.
Formula (X)

In formula (X), R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ⁹ has 6 carbon atoms which may have a substituent. And an aliphatic hydrocarbon group of 1 to 20 carbon atoms or an aliphatic hydrocarbon group of 1 to 3 carbon atoms substituted with an aromatic hydrocarbon group of 6 to 17 carbon atoms which may have a substituent.
With such a configuration, it is possible to provide a resin composition which is excellent in surface hardness and excellent in abrasion resistance, in particular, can maintain high transparency even after an abrasion test, and is excellent in extrudability.
Hereinafter, the 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 for the resin composition of the present invention contains the structural unit represented by the formula (1) in a proportion of 50 to 100% by mole 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, and X ¹ represents any 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 a substituted or unsubstituted alicyclic hydrocarbon having 6 to 12 carbon atoms Represents a group.

Two R ^{2 s} in the 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 the formula (1), X ¹ is

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

In the case of Z, Z bonds to carbon C bonded to 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, cyclododecylidene group and the like. Examples of the substituted ones include those having these methyl substituents and ethyl substituents. Among these, preferred are a cyclohexylidene group, a methyl-substituted form (preferably a 3,3,5-trimethyl-substituted form) of a cyclohexylidene group, and a cyclododecylidene group.
In Formula (1), X ¹ preferably has the following structure.

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

  The (A) polycarbonate resin in the present invention contains 50 mol% or more, preferably 60 mol% or more, more preferably 70 mol% or more, more preferably the structural unit represented by the formula (1) in all constituent units. It contains 80 mol% or more. Further, the upper limit value is 100% or less, preferably 95 mol% or less, more preferably 90 mol% or less.

  In the present invention, the (A) polycarbonate resin may contain only one type of structural unit represented by formula (1) or may contain two or more types. When it contains 2 or more types, it is preferable that a total amount becomes said 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 other structural units other than the structural unit represented by the formula (1). As another structural unit, the structural unit represented by following formula (2) is preferable.
Formula (2)

In formula (2), X ² represents any 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 a substituted or unsubstituted alicyclic hydrocarbon having 6 to 12 carbon atoms Represents a group.
Examples of the alicyclic hydrocarbon formed by bonding Z to C include cycloalkylidene groups such as cyclohexylidene group, cycloheptylidene group, cyclododecylidene group, adamantylidene group, cyclododecylidene group and the like Can be mentioned. As a cycloaliphatic hydrocarbon which has a substituent which Z is couple | bonded with C, and is formed, the methyl substitution of the alicyclic hydrocarbon group mentioned above, an ethyl substitution, etc. are mentioned. Among these, a cyclohexylidene group, a methyl-substituted form (preferably a 3,3,5-trimethyl-substituted form) 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) is the same as the preferred range of X ^{1 in} Formula (1). That is, in the 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 a methyl group.

As a preferable specific example of the structural unit represented by the said Formula (2), it is a structural unit (carbonate structural unit) comprised from 2, 2-bis (4-hydroxyphenyl) propane, ie, bisphenol-A.
In the present invention, the structural unit represented by the formula (2) is contained in preferably 5 mol% or more, more preferably 10 mol% or more, based on all the structural units. The upper limit value is preferably 50 mol% or less, more preferably 40 mol% or less, more preferably 30 mol% or less, still more preferably 20 mol% or less, based on all structural units.
In the present invention, (A) polycarbonate resin may not contain the structural unit represented by Formula (2), may contain only 1 type, and may contain 2 or more types. When it contains 2 or more types, it is preferable that a total amount becomes said range.

In the present invention, as the dihydroxy compound constituting the structural unit represented by the formula (1) and the structural unit other than the structural unit represented by the formula (2) in the present invention, for example, Such aromatic dihydroxy compounds can be mentioned;
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, 1,1-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) ring 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.

  In addition, as an embodiment of another structural unit, structural units represented by the formula (1) described in paragraph 0008 of WO 2017/0992226 pamphlet are also exemplified, and further, paragraphs 0043 to 0052 of WO 2017/0992226 brochure The description may also be taken into consideration, the contents of which are incorporated herein.

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

Wherein (3), R ¹⁵ ~R ¹⁸ independently represents 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, The alkoxy group having 1 to 5 carbon atoms, the alkenyl group having 2 to 5 carbon atoms or the aralkyl group having 7 to 17 carbon atoms is represented; n1, n2 and n3 each independently represent an integer of 0 to 4;
The detail of the structural unit represented by Formula (3) can consider the description of Unexamined-Japanese-Patent No. 2011-046769, and these content is integrated in this 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 (A) polycarbonate resin is 30 mol% in all structural units. It is preferably the following, more preferably 20% by mol or less, further preferably 10% by mol or less, and may be 5% by mol or less, or 1% by mol or less.

Hereinafter, an embodiment of the (A) polycarbonate resin in the present invention will be described.
(1) A polycarbonate resin containing 50 to 100 mol% of a structural unit represented by the formula (1) among all structural units (2) A structural unit represented by the formula (1) 95% by mol (preferably 60 to 95% by mol) and 50 to 5% by mol of a structural unit other than the structural unit represented by the formula (1) (preferably structural unit represented by the formula (2), more preferably Is a polycarbonate resin containing 40 to 5 mol%) When the polycarbonate resin used in the present invention contains a structural unit other than the structural unit represented by Formula (1) (preferably a structural unit represented by Formula (2)) The following blend forms are exemplified.
· A polycarbonate resin (A1) in which more than 50 mol% (preferably, 70 mol% or more, 95 mol% or more) of the total structural units is a structural unit represented by Formula (1), and 95 mol% of the total structural units Mixture of polycarbonate resin (A2) comprising structural units represented by formula (2):
Copolycarbonate resin (A3) in which the total of the structural unit represented by the formula (1) and the structural unit represented by the formula (2) accounts for more than 95 mol% of all structural units:
Mixture of the polycarbonate resin (A1), the polycarbonate resin (A2), and the copolycarbonate resin (A3):
A mixture of the polycarbonate resin (A1) and the copolycarbonate resin (A3);
A mixture of the copolycarbonate resin (A3) and the polycarbonate resin (A2);
In any of the above embodiments, a mixture containing two or more of at least one of polycarbonate resin (A1), polycarbonate resin (A2) and copolycarbonate resin (A3);
In any of the embodiments, the structural unit represented by the formula (1) in the polycarbonate resin (A) may be contained in a proportion of 50 mol% to 100 mol%, and further, the formula (1) It is preferable that the structural unit to be contained and the structural unit represented by the formula (2) be contained in all the structural units in a ratio that satisfies the above-mentioned preferable range.

    In the present invention, in the blend forms exemplified above, a form containing (A1) polycarbonate resin and (A2) polycarbonate resin is particularly preferable. When (A1) polycarbonate resin and (A2) polycarbonate resin are included, the mixing ratio of the two is preferably 50:50 to 100: 0 by mass ratio, and more preferably 50:50 to 95: 5. The ratio is more preferably 60:40 to 95: 5, still more preferably 60:40 to 90:10, and still more preferably 70:30 to 90:10. The resin composition of the present invention may contain only one type of (A1) polycarbonate resin and (A2) polycarbonate resin, or may contain two or more types. When it contains 2 or more types, it is preferable that a total amount becomes said range. By setting it as such a structure, the pencil hardness of the molded article obtained from a resin composition can be 2 H or more, and also 3 H or more. The upper limit of the pencil hardness is not particularly limited, but may be 4H or less, and 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 12,000 or more. More preferable. Further, the upper limit value of Mv is preferably 32,000 or less, more preferably 30,000 or less, and still more preferably 28,000 or less.
By setting the viscosity average molecular weight to the above lower limit value or more, the moldability is improved, and a molded article having a large mechanical strength can be obtained. Further, by setting the upper limit value or less, the flowability of the molded product is improved, and a thin-walled molded product can be efficiently produced.
The viscosity average molecular weight (Mv) is measured according to the method described in the examples described later (hereinafter the same for Mv). When two or more (A) polycarbonate resins are contained, the viscosity average molecular weight of each polycarbonate resin is taken as the sum of the value obtained by multiplying the mass fraction. Hereinafter, the viscosity average molecular weight is considered in the same manner.

  The pencil hardness of the (A) polycarbonate resin measured according to ISO 15184 is exemplified by 3B to 2H, preferably B to 2H, and more preferably HB to 2H. The pencil hardness is measured according to the method described in the examples described below (hereinafter the same as the pencil hardness). When two or more (A) polycarbonate resins are contained, the pencil hardness of the mixture is preferably in the above range.

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

  The resin composition of the present invention preferably contains (A) polycarbonate resin and (C) acrylic resin in total in a proportion of 80% by mass or more of the composition, and more preferably in a proportion of 85% by mass or more It is more preferable to include in a ratio of 90 mass% or more, and it is more preferable to include in a ratio of 93 mass% or more. The upper limit of the total of (A) polycarbonate resin and (C) acrylic resin is not particularly limited, but may 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 type and the like.

  An example of the embodiment of the ester compound in the present invention is, for example, an ester compound which is a fatty acid ester, and more specifically, formed of 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. Among them, monoester compounds are particularly preferable.

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

The monoester compound used in the present invention preferably has a hydroxyl value of 100 mg KOH / g or less and / or a carbon number of 42 or more.
By lowering the hydroxyl value, the monoester compound and the polycarbonate resin become difficult to be decomposed at the time of extrusion, and the generation of gas at the time of molding and the like can be effectively suppressed. The hydroxyl value is more preferably 80 mg KOH / g or less, still more preferably 50 mg KOH / g or less, and still more preferably 35 mg KOH / g or less.
A hydroxyl value is measured according to the method as described in the Example mentioned later.

In the present invention, the use of a monoester compound having a carbon number equal to or more than a predetermined value can effectively suppress the generation of gas during extrusion and molding.
The carbon number of the monoester compound is preferably 42 or more, and more preferably 44 or more. The upper limit of the carbon number of the monoester compound is not particularly limited, but is preferably 100 or less, and 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 of a monovalent carboxylic acid and a monohydric alcohol, it is a monovalent carboxylic acid and a monovalent valence. The total carbon number contained in the alcohol is the carbon number of the monoester compound.
When two or more types of monoester compounds are contained, the number of carbons is the sum of the number of carbons of each monoester compound multiplied 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 still more preferably 1200 or less. By adopting such a configuration, it is possible to obtain a molded article having an excellent balance of high transparency and high nail scratch resistance. The details of the structure etc. will be described in detail.

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

Next, carboxylic acid will be described.
In the present invention, the carboxylic acid may be any one of a saturated fatty acid, an unsaturated fatty acid and an aromatic carboxylic acid as long as it is a monovalent carboxylic acid, and may have a branched structure. The carboxylic acid in the present invention is preferably a saturated fatty acid, particularly preferably a linear saturated fatty acid.
Moreover, although a carboxylic acid may or may not have a substituent, it is preferable not to have a substituent. If there is no substituent, the transparency of the resulting molded article tends to be further improved.
Furthermore, the carboxylic acid is preferably composed only of an oxygen atom, a carbon atom and a hydrogen atom. The carbon number of the carboxylic acid is preferably 2 to 45, more preferably 10 to 40, still more preferably 15 to 36, and particularly preferably 20 to 30.
Specific examples of carboxylic acids (numbers in parentheses are carbon numbers) 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), eicosenic acid (unsaturated C20), behenic acid (saturated C22), erucic acid (unsaturated C22), lignocericic acid (saturated C24), serotin Examples are acids (saturated C26), montanic acid (saturated C28) and melisic acid (saturated C30).

Next, alcohol will be described.
In the present invention, the alcohol is preferably a monohydric alcohol and may be any of a saturated alcohol, an unsaturated alcohol and an aromatic alcohol, and may have a branched structure. The alcohol in the present invention is preferably a saturated alcohol, particularly preferably a linear saturated alcohol.
Moreover, although the alcohol may or may not have a substituent, it is preferable not to have a substituent. If there is no substituent, the transparency of the resulting molded article tends to be further improved.
Furthermore, the alcohol is preferably composed only of an oxygen atom, a carbon atom and a hydrogen atom.
The carbon number of the alcohol is preferably 2 to 45, and more preferably 5 to 36.
Specific examples of alcohols (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), Silyl alcohol (unsaturated C22) and montanyl alcohol (saturated C28) are exemplified.

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

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

  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% by mass or more, more preferably 70% by mass or more) Refer to the ester compound to be

The second embodiment of the ester compound (B) in the present invention is a diester compound.
The diester compound used in the present invention is a diester compound obtained from a polyvalent carboxylic 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), Preferred is 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.
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, etc. can be effectively suppressed, and the compatibility with the polycarbonate resin is excellent. For this reason, it is possible to obtain a resin composition which is excellent in extrudability, high in transparency, and capable of forming a molded article having excellent scratch resistance after wiping off with initial and ethanol impregnated cotton. .

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

In particular, the diester compound used in the present invention is a diester compound obtained from a divalent carboxylic acid having 3 to 10 carbon atoms and a monohydric alcohol having 16 to 40 carbon atoms, or a dihydric alcohol having 3 to 10 carbon atoms and a carbon number A diester compound obtained from 16 to 40 monovalent carboxylic acids, 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 It is more preferable that it is a compound or a diester compound obtained from a dihydric alcohol having 3 to 10 carbon atoms and a monohydric carboxylic acid having 16 to 30 carbon atoms, or a mixture thereof, and is a divalent carbon having 3 to 10 carbon atoms. It is more preferable that it is a diester compound or its mixture obtained from an acid and a C16-C30 monohydric alcohol.
Furthermore, it is preferable that carbon number of a monohydric alcohol is 10 or more larger than carbon number of a bivalent carboxylic acid, and the diester compound which consists of a bivalent carboxylic acid and monohydric alcohol used by this invention is 10-20 or more Is more preferred. Alternatively, in the diester compound consisting of a monovalent carboxylic acid and a dihydric alcohol used in the present invention, the carbon number of the dihydric alcohol is preferably 10 or more larger than the carbon number of the monovalent carboxylic acid, and is 10 to 20 larger Is more preferred. With such a configuration, gas is less likely to be generated during extrusion or molding, and the appearance and physical properties of the molded article tend to be further improved.

  Specific examples of monovalent carboxylic acids (number of carbon atoms in parentheses) include behenic acid (22), lignoceric acid (24), serotic acid (26), montanic acid (28), and melisic acid (30) Be

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

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

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

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

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% by mass or more, more preferably 70% by mass or more) We will refer to ester compounds.
The molecular weight is preferably 2000 or less, more preferably 1800 or less, still more preferably 1400 or less, still more preferably 1000 or less, and still more preferably 900 or less. The lower limit is preferably 200 or more, and more preferably 500 or more. If the molecular weight of the diester compound is in the above range, a molded article excellent in the balance between high transparency and high resistance to scratching can be obtained. In addition, when an ester compound is a mixture, it is set as a number average molecular weight.
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% by mass or more, more preferably 70% by mass or more) We will refer to ester compounds.

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) It is preferable that it is an ester compound obtained from several 20-50) monovalent | monohydric carboxylic acid, or the mixture of both.
When the resin composition of the present invention contains such a triester compound, decomposition of the polycarbonate resin is suppressed, generation of gas at the time of molding, etc. can be effectively suppressed, and furthermore, compatibility with the polycarbonate resin is excellent. . For this reason, it is possible to obtain a resin composition which is excellent in extrudability, high in transparency, and capable of forming a molded article excellent in initial scratch resistance after scratching with a solvent.

The triester compound is preferably a triester compound consisting of a trivalent carboxylic acid and a monohydric alcohol, a triester compound consisting of a monohydric carboxylic acid and a trivalent alcohol, or a mixture thereof.
The monohydric alcohol and the monobasic carboxylic acid may contain at least one of an aliphatic structure, an alicyclic structure and an aromatic structure, respectively, and include an aliphatic structure and / or an alicyclic structure, respectively. 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 monohydric carboxylic acid each have a carbon number of 20 or more, preferably 21 or more, and the upper limit of the carbon number is preferably 50 or less, more preferably 40 or less, and 32 or less. More preferably, 30 or less is more preferable.
The trivalent carboxylic acid and the trivalent alcohol may each include at least one of an aliphatic structure, an alicyclic structure and an aromatic structure, and the aliphatic structure and / or the alicyclic structure may be It is preferable to include.
The trivalent carboxylic acid and the trivalent alcohol are preferably composed of a linear or branched aliphatic structure or alicyclic structure and a carboxyl group or a hydroxyl group, respectively. The carbon number of each of the trivalent carboxylic acid and the trivalent alcohol is preferably 3 or more. 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 preferable that it is a triester compound obtained from several 20 to 40 monovalent carboxylic acids, 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 trihydric alcohol having 3 to 10 carbon atoms and a monohydric carboxylic acid having 20 to 30 carbon atoms, or a mixture of two or more thereof More preferably, 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 two or more thereof. More preferably a mixture of.
Furthermore, it is preferable that the carbon number of the monovalent carboxylic acid of the triester compound composed of the trihydric alcohol and the monovalent carboxylic acid used in the present invention is 10 or more larger than the carbon number of the trihydric alcohol. Larger is more preferable. With such a configuration, gas is less likely to be generated during extrusion or molding, and the appearance and physical properties of the molded article tend to be further improved.

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

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

  Specific examples of trivalent carboxylic acid (number of carbon atoms in parentheses) include tricarballylic acid (6), 1,2,3-benzenetricarboxylic acid (9), 1,3,5-benzenetricarboxylic acid (9), 1,2,4-benzenetricarboxylic acid (9), 5-methyl-1,2,4-benzenetricarboxylic acid (10), 1,2,3-cyclohexanetricarboxylic acid (9), 1,3,5-cyclohexane Tricarboxylic acid (9), 1,2,4-cyclohexane tricarboxylic acid (9) etc. are mentioned.

  Specific examples of trihydric alcohol (number of carbon atoms in parentheses) include glycerin (3), trimethylolpropane (6), trimethylolethane (5), triethylolethane (8), 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 mg KOH / g or less, more preferably 70 mg KOH / g or less, still more preferably 50 mg KOH / g or less, and further preferably 10 mg KOH / g or less. preferable. The lower limit value of the hydroxyl value of the triester compound is not particularly limited, and is, for example, 1 mg KOH / g or more. By setting the hydroxyl value of the triester compound to 100 mg KOH / g or less, the promotion of the decomposition of the polycarbonate resin is effectively suppressed, and it becomes difficult to generate gas during extrusion or molding, and the appearance and physical properties of the molded article It tends to improve and is preferable.
According to this aspect, the molded article obtained from the composition of the present invention is also excellent in nail scratch resistance after wiping off with cotton impregnated with ethanol.

  The molecular weight of the triester compound used in the present invention is preferably 2000 or less, more preferably 1800 or less, and still more preferably 1400 or less. The lower limit is preferably 1,000 or more. If the molecular weight of the triester compound is in the above range, a molded article excellent in the balance between high transparency and high resistance to scratching can be obtained.

  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% by mass or more, more preferably 70% by mass or more) Refer to the ester compound to be

The fourth embodiment of the ester compound (B) in the present invention is a tetraester compound.
The tetra ester 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) It is preferable that it is an ester compound obtained from several 20-50) monovalent | monohydric carboxylic acid, or the mixture of both.
When the resin composition of the present invention contains such a tetraester compound, decomposition of the polycarbonate resin is suppressed, and generation of gas during molding 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, high in transparency, and capable of forming a molded article having excellent scratch resistance after wiping off with initial and ethanol impregnated cotton. .

The tetra-ester compound is preferably a tetra-ester compound consisting of a tetravalent carboxylic acid and a monohydric alcohol, a tetra-ester compound consisting of a monovalent carboxylic acid derived and a tetrahydric alcohol, or a mixture thereof.
The monohydric alcohol and monohydric carboxylic acid may contain at least one of aliphatic structure, alicyclic structure and aromatic structure, respectively, and contain aliphatic structure and / or alicyclic structure, respectively. 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 monohydric carboxylic acid each have a carbon number of 20 or more, preferably 21 or more, and the upper limit of the carbon number is preferably 50 or less, more preferably 40 or less, and 32 or less. More preferably, 30 or less is more preferable.
The tetravalent carboxylic acid and the tetravalent alcohol may each include at least one of an aliphatic structure, an alicyclic structure, and an aromatic structure, and each have an aliphatic structure and / or an alicyclic structure. It is preferred to include a structure.
The tetravalent carboxylic acid and the tetravalent alcohol are preferably composed of a linear or branched aliphatic structure or alicyclic structure and a carboxyl group or a hydroxyl group, respectively. 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 still more preferably 5 or more. The carbon number of each of the tetravalent carboxylic acid and the tetravalent alcohol is preferably 10 or less, more preferably 8 or less.

In particular, the tetra ester compound used in the present invention is a tetra ester 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 It is preferable that it is a tetraester compound obtained from a C20 to C40 monovalent carboxylic acid, or a mixture thereof, and is composed of a C3 to C10 tetravalent carboxylic acid and a C20 to C30 monohydric alcohol. It is more preferable that it is a tetraester compound obtained, or a tetraester compound obtained from a tetrahydric alcohol having 3 to 10 carbon atoms and a monovalent carboxylic acid having 20 to 30 carbon atoms, or a mixture thereof, and having 3 to 10 carbon atoms. Or a mixture thereof, which is obtained from a tetrahydric alcohol of the formula and a monovalent carboxylic acid having 20 to 30 carbon atoms. Preferred.
Furthermore, it is preferable that the carbon number of the monovalent carboxylic acid of the tetraester compound composed of the tetrahydric alcohol and the monovalent carboxylic acid used in the present invention is 10 or more greater than the carbon number of the tetrahydric alcohol. Larger is more preferable. With such a configuration, gas is less likely to be generated during extrusion or molding, and the appearance and physical properties of the molded article tend to be further improved.
The tetravalent carboxylic acid may or may not have a substituent, but preferably does not have a substituent. If there is no substituent, the transparency of the resulting molded article tends to be further improved. The carboxylic acid is preferably composed only of an oxygen atom, a carbon atom and a hydrogen atom.

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

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

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

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

上記式中、波線は結合手を表す。 It is preferable that the tetra-ester compound used by this invention contains the partial structure represented by a following formula (B1).
Formula (B1)

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

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

In the above formulas, 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 carbon number of the aliphatic hydrocarbon group represented by RB ^{1 to} RB ⁴ is preferably 2 or more, more preferably 5 or more, still more preferably 10 or more, and particularly preferably 20 or more. preferable. The upper limit is preferably 45 or less, more preferably 40 or less, and still more preferably 36 or less. The number of carbon atoms of the aliphatic hydrocarbon group RB ¹ ~RB ⁴ represents is preferably independently 20 or more.

  The tetra-ester 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) Refer to the ester compound to be

The hydroxyl value of the tetraester compound is preferably 100 mg KOH / g or less, more preferably 70 mg KOH / g or less, still more preferably 50 mg KOH / g or less, and further preferably 10 mg KOH / g or less. preferable. The lower limit value of the hydroxyl value of the tetra-ester compound is not particularly limited, and is, for example, 1 mg KOH / g or more. By setting the hydroxyl value of the tetra-ester compound to 100 mg KOH / g or less, the promotion of the decomposition of the polycarbonate resin is effectively suppressed, and it becomes difficult to generate gas during extrusion or molding, and the appearance and physical properties of the molded article It tends to improve and is preferable.
According to this aspect, the molded article obtained from the composition of the present invention is also excellent in nail scratch resistance after wiping off with cotton impregnated with ethanol.

  The molecular weight of the tetraester compound used in the present invention is preferably 2200 or less, more preferably 2000 or less, and still more preferably 1800 or less. The lower limit is preferably 1400 or more. If the molecular weight of the tetraester compound is in the above range, a molded article excellent in balance between high transparency and high nail scratch resistance can be obtained.

  In the tetra-ester compound used by this invention, although the carboxylic acid which comprises the said ester structure may or may not have a substituent, the one which it does not have is preferable. If there is no substituent, the transparency of the resulting molded article tends to be further improved. The carboxylic acid is preferably composed only of an oxygen atom, a carbon atom and a hydrogen atom.

The resin composition of the present invention contains 0.5 to 10.0 parts by mass of the ester compound (B) with respect to 100 parts by mass of the polycarbonate resin (A).
The lower limit value 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 with respect to 100 parts by mass of the (A) polycarbonate resin. It is more preferably 1.0 parts by mass or more, further preferably 1.5 parts by mass or more, particularly preferably 1.8 parts by mass or more, and further preferably 2.0 parts by mass or more Is preferably 2.0 parts by mass or more and 2.2 parts by mass or more. By setting it as the said range, nail | claw damage resistance can be improved more.
The upper limit value of the compounding 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 with respect to 100 parts by mass of the (A) polycarbonate resin. It is more preferably 7.0 parts by mass or less, still more preferably 6.0 parts by mass or less, still more preferably 5.0 parts by mass or less, 4.0 parts by mass or less, 3.5 It may be up to 3.2 parts by mass or less. By setting it as a preferable range, hydrolysis resistance is improved, and mold contamination can be more effectively suppressed. In this invention, even if there are few compounding quantities of (B) ester compound, it can be set as the structure excellent in nail scratch resistance.
The resin composition of the present invention may contain only one type of ester compound (B) or may contain two or more types. When it contains 2 or more types, it is preferable that a total amount becomes said range.

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

式（Ｘ）中、Ｒ⁶、Ｒ⁷およびＲ⁸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。
Ｒ⁶および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、より好ましくは水素原子である。
Ｒ⁸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。
Ｒ⁹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、Ｒ⁶、Ｒ⁷およびＲ⁸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、Ｒ¹⁰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）。
Ｒ⁶および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、水素原子がより好ましい。
Ｒ⁸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。
Ｒ¹⁰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。 The (C) acrylic resin is preferably an acrylic resin having a structural unit represented by the following formula (X).
Formula (X)

In formula (X), R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ⁹ has 6 carbon atoms which may have a substituent. And an aliphatic hydrocarbon group of 1 to 20 carbon atoms or an aliphatic hydrocarbon group of 1 to 3 carbon atoms substituted with an aromatic hydrocarbon group of 6 to 17 carbon atoms which may have a substituent.
R ⁶ and R ⁷ are each independently preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.
Each R ⁸ independently is preferably a hydrogen atom or a methyl group, more preferably a methyl group.
R ⁹ 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 And the naphthyl group which does not have a substituent is more preferable, and the phenyl group which does not have a substituent is further more preferable.
As a substituent, 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) are exemplified. In the case of having a substituent, the number of substituents is preferably 1 to 3, more preferably 1 or 2, and still more preferably 1 to 1 aromatic ring.
In the present invention, the (C) acrylic resin 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) The copolymer may be composed of structural units other than (c1) and structural units other than (c1) (generally, structural units derived from (meth) acrylic acid ester), and the latter copolymer is preferable.
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 ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ¹⁰ may have a hydrogen atom or a substituent A good C1-C20 aliphatic hydrocarbon group is shown (however, except that whose substituent contains an aromatic hydrocarbon group).
Each of R ⁶ and R ⁷ independently is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.
Each R ⁸ is independently preferably a hydrogen atom or a methyl group, more preferably a methyl group.
R ¹⁰ is preferably a hydrogen atom or an aliphatic hydrocarbon group having 1 to 6 carbon atoms which may have a substituent, and a hydrogen atom or an aliphatic hydrocarbon having 1 to 6 carbon atoms having no substituent is preferable. A hydrogen group is more preferable, a hydrogen atom or a methyl group, an ethyl group or an n-butyl group is more preferable, and a hydrogen atom or a methyl group is more preferable.

Moreover, it is preferable to contain the said (C) acrylic resin by the ratio which becomes mass ratio 5-80 / 95-20 of said (c1) / (c2), and in the ratio which becomes 20-70 / 80-30. It is more preferable to contain, and it is still more preferable to contain in the ratio which becomes 25-45 / 75-55. If the mass ratio of the (c1) is 5 or more, the transparency of the (C) acrylic resin tends to be further improved, and if the mass ratio of the (c1) is 95 or less, the (A) polycarbonate resin and The compatibility of the above is more appropriate, the migration to the surface of the molded article is more effectively suppressed, and the surface hardness tends to be further improved.
In the present invention, the molecular weight of the monomer constituting the repeating unit of (c1) is preferably 100 to 900, more preferably 100 to 500, and still more preferably 100 to 300. Furthermore, in the present invention, the molecular weight of the monomer constituting the repeating unit of (c2) is preferably 80 to 900, more preferably 80 to 500, and still more preferably 80 to 300.

As a monomer which comprises the repeating unit of (c1), phenyl (meth) acrylate, a benzyl (meth) acrylate, and a naphthyl (meth) acrylate can be mentioned, A phenyl methacrylate and a benzyl methacrylate are preferable and a phenyl methacrylate is more preferable.
In the present invention, (meth) acrylate indicates acrylate and / or methacrylate.
As a monomer which comprises the repeating unit of (c2), a methyl methacrylate is preferable. By using methyl methacrylate as a monomer constituting the repeating unit of (c2), the dispersibility to the (A) polycarbonate resin is further improved, and the surface hardness of the molded product can be further improved because it is transferred to the surface of the molded product. .

  (C) As a polymerization method of the monomer for obtaining an acrylic resin, well-known methods, such as an emulsion polymerization method, a suspension polymerization method, a solution polymerization method, a block polymerization method, can be used. It is preferably a suspension polymerization method or a bulk polymerization method, and more preferably a suspension polymerization method. In addition, additives and the like necessary for polymerization can be appropriately added as needed, and examples thereof include a polymerization initiator, an emulsifying agent, a dispersing agent, and a chain transfer agent.

  When (C) acrylic resin used by this invention contains the structural unit represented by Formula (X), it is preferable that it is 20 mass% or more of the structural unit which comprises (C) acrylic resin, and 30 mass%. It is more preferable that it is more than. The upper limit value is preferably 95% by mass or less, and more preferably 80% by mass or less. The structural unit represented by Formula (X) may contain only 1 type, and may contain 2 or more types. When it contains 2 or more types, it is preferable that a total amount becomes said range.

When the (C) acrylic resin used in the present invention contains the structural unit represented by the formula (X) and the structural unit represented by the formula (X1), the total amount of these is 90 mass of the (C) acrylic resin It is preferable to occupy% or more.
The structural unit represented by the formula (X1) may contain only one type, or two or more types. When it contains 2 or more types, it is preferable that a total amount becomes said range.

The weight average molecular weight of the (C) acrylic resin is preferably 5,000 or more, more preferably 10,000 or more, and still more preferably 13,000 or more. The upper limit of the weight average molecular weight is preferably 30,000 or less, more preferably 25,000 or less, and still more preferably 20,000 or less. By setting it as the said range, compatibility with (A) polycarbonate resin tends to become more favorable, and the improvement effect of surface hardness also tends to be more excellent.
In addition, the weight average molecular weight of (C) acrylic resin is measured using the gel permeation chromatography which used tetrahydrofuran (THF) as a solvent. In addition, a weight average molecular weight is a value of standard polystyrene resin (PS) conversion.

  The content of the (C) acrylic resin is 3 to 100 parts by mass with respect to 100 parts by mass of the (A) polycarbonate resin. The lower limit value of the content of the (C) acrylic resin is preferably 5 parts by mass or more, more preferably 7 parts by mass or more, still more preferably 10 parts by mass or more, still more preferably 20 parts by mass or more Furthermore, 30 mass parts or more may be sufficient. The upper limit value of the content of the (C) acrylic resin is preferably 75 parts by mass or less, more preferably 55 parts by mass or less, still more preferably 45 parts by mass or less, and further 38 parts by mass The amount may be 30 parts by mass or less and 20 parts by mass or less. Within the above range, the resin composition of the present invention effectively improves the surface hardness and flowability while maintaining the balance of physical properties such as impact resistance while maintaining good transparency, and further at the time of molding Can suppress the problem of whitening of In particular, by setting the upper limit value of the content of the (C) acrylic resin to 38 parts by mass or less, Δ haze before and after the abrasion reciprocation test can be further reduced.

  In the resin composition of the present invention, the ratio of (B) ester compound to (C) acrylic resin ((B) / (C) × 100) (% by mass) is preferably 3 to 200, and the lower limit Is more preferably 5 or more, still more preferably 7 or more, more preferably 8 or more, and the upper limit is more preferably 100 or less, still more preferably 50 or less, still more preferably 35 or less, still more preferably 25 The following is even more preferably 20 or less. With such a configuration, higher transparency and scratch resistance after initial and solvent wiping can be achieved.

  As the (C) acrylic resin used in the present invention, in addition to the above, those described in WO 2014/038500, WO 2013/094898, JP 2006-199774, JP 2010-116501 are adopted. The contents of which are incorporated herein.

<Other ingredients>
The resin composition of the present invention may contain other components other than the above, as needed, as long as the desired physical properties are not significantly impaired. Examples of the other components include thermoplastic resins other than the above-described (A) polycarbonate resin and (C) acrylic resin, various resin additives, and the like.
The resin composition of the present invention also preferably contains no inorganic filler, but may contain an inorganic filler. By including an inorganic filler, the mechanical strength of the resulting molded article can be further improved. As an embodiment of the resin composition of the present invention, the inorganic filler is not contained, or 8 parts by mass or less (preferably 6 parts by mass or less, more preferably) of the inorganic filler with respect to 100 parts by mass of the (A) polycarbonate resin. Is exemplified by a resin composition containing 4 parts by mass or less, more preferably 1 part by mass or less. The transparency of the resulting molded article can be further improved by not including the inorganic filler or by setting it in the above-mentioned range. 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.), UV absorbers, antistatic agents, flame retardants, flame retardant aids, dyes, pigments, antifogging agents, lubricants, antiblocking agents And flow 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 by arbitrary combinations and ratios.

<< Stabilizer >>
Stabilizers include heat stabilizers and antioxidants.
As a heat stabilizer, a phosphorus stabilizer is preferably used.
Any known phosphorus-based stabilizer can be used. As specific examples, phosphorus oxo acids such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, polyphosphoric acid, etc .; acid pyrophosphate metal salts such as acid sodium pyrophosphate, potassium acid pyrophosphate and calcium acid pyrophosphate; phosphorus Phosphates of Group 1 or 2 B metals such as potassium phosphate, sodium phosphate, cesium phosphate, zinc phosphate; organic phosphate compounds, organic phosphite compounds, organic phosphonite compounds, etc., but organic phosphite compounds Is particularly preferred.

Examples of organic phosphite compounds include triphenyl phosphite, tris (monononylphenyl) phosphite, tris (monononyl / dinonyl phenyl) 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-dibis- tert-Butylphenyl) octyl phosphite etc. are mentioned.
As such an organic phosphite compound, specifically, for example, “ADEKA STAB (registered trademark; the same as the following) 1178”, “ADEKA STAB 2112”, “ADEKA STAB HP-10”, manufactured by Johoku Chemical Industry Co., Ltd. "JP-351", "JP-360", "JP-3 CP", "IRGAFOS (registered trademark; the same shall apply hereinafter) 168" manufactured by BASF, etc. may be mentioned.

As the antioxidant, hindered phenol stabilizers are preferably used.
As a specific example of the hindered phenol type stabilizer, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert- Butyl-4-hydroxyphenyl) propionate, thiodiethylene bis [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, ethylene bis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate], hexamethylene bis [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], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate are preferred. preferable. Specific examples of such hindered phenol stabilizers include, for example, “Irganox (registered trademark; the same in the following) 1010” manufactured by BASF, “Irganox 1076”, “Adekastab AO-50” manufactured by ADEKA, “Adekastab AO-60 "etc. is mentioned.

  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, more preferably 0.01 parts by mass or more with respect to 100 parts by mass of the polycarbonate resin. Also, it is usually 1 part by mass or less, preferably 0.5 parts by mass or less, more preferably 0.3 parts by mass or less. By making content of a stabilizer into the said range, the addition effect of a stabilizer is exhibited more effectively.

<< UV Absorbent >>
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 a 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 a 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% Below, it can also be 0.4% or less. As the lower limit value of the haze, 0% is ideal, but 0.01% or more, further 0.07% or more is a practical level. The measurement method of haze follows the description of the Example mentioned later.

  The test piece of 2 mm in thickness (preferably a test piece of 150 mm long × 100 mm wide × 2 mm thick) formed from the resin composition of the present invention has a dynamic friction coefficient of 0.35 or less according to ISO 19252 at a load of 30 N And is preferably 0.34 or less, more preferably 0.30 or less, still more preferably 0.29 or less, and still more preferably 0.28 or less. As the lower limit value of the dynamic friction coefficient, 0 is ideal, but 0.01 or more, further 0.10 or more is a practical level. The measurement method of the dynamic friction coefficient follows the description of the Example mentioned later.

A test piece of 2 mm in thickness (preferably a test piece of 150 mm in length × 100 mm in width × 2 mm in thickness) formed from the resin composition of the present invention is a reciprocal abrasion test using larch (100% cotton, 20 × 20 count) The Δ haze which is the difference between the front and rear haze is 3.00% or less, preferably 2.90% or less, more preferably 2.80% or less, and 2.70% or less More preferably, it is more preferably 2.60% or less. The lower limit value of ΔHaze before and after the reciprocating abrasion test is ideally 0%, but 0.01% or more, and even 0.07% or more is a practical level.
The measurement method of ΔHaze before and after the reciprocating abrasion test follows the description of Examples described later.

  The resin composition of the present invention can be made into a resin composition having a pencil hardness of 3H by blending (A) polycarbonate resin having a pencil hardness of 2H and (C) acrylic resin having a pencil hardness of 2H. When two or more types of (A) polycarbonate resin and / or (C) acrylic resin are contained, (A) polycarbonate resin, (C) acrylic resin, (C) acrylic resin, and (C) acrylic, respectively, with pencil hardness of (A) polycarbonate resin, (C) acrylic resin mixture The pencil hardness of the resin.

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

<Molded item>
The above-mentioned resin composition (for example, pellet) is molded by various molding methods to be a molded article. That is, the molded article of the present invention is molded from the resin composition of the present invention.
There is no restriction | limiting in particular as a shape of a molded article, According to the use of a molded article, and the objective, it can select suitably, For example, film shape, rod shape, cylindrical shape, cyclic | annular shape, circular shape, elliptical shape, polygonal shape And odd-shaped articles, hollow articles, frames, boxes, panels, buttons, and the like. Among them, film-like, frame-like, panel-like or button-like ones are preferable, and the thickness is, for example, about 1 mm to 5 mm in the case of frame-like or panel-like.

  The method for molding the molded product is not particularly limited, and conventionally known molding methods can be adopted. For example, injection molding method, injection compression molding method, extrusion molding method, profile extrusion method, transfer molding method, hollow molding method, Gas-assisted hollow molding method, blow molding method, extrusion blow molding, IMC (in-mold coating molding) molding method, rotational molding method, multilayer molding method, two-color molding method, insert molding method, sandwich molding method, foam molding method And pressure molding methods. 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 products obtained therefrom.

  The molded article of the present invention is suitably used for parts such as electric and electronic equipment, OA equipment, portable information terminals, machine parts, home appliances, vehicle parts, various containers, lighting equipment and the like. Among these, in particular, it is used for casings of electric and electronic devices, OA devices, information terminal devices and home electric appliances, lighting devices and vehicle parts (particularly, vehicle interior parts), and among them, vehicle interior parts are preferable.

  Hereinafter, the present invention will be more specifically described by way of examples. The materials, amounts used, proportions, treatment contents, treatment procedures and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Accordingly, 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 moles (6.75 kg) of bisphenol C (BPC) and 26.79 moles (5.74 kg) of diphenyl carbonate in a SUS reactor (having an internal volume of 10 liters) equipped with a stirrer and a distillation condenser The reactor was charged with nitrogen gas, and the temperature was raised to 220 ° C. in 30 minutes under a nitrogen gas atmosphere.
Next, the reaction solution in the reactor is stirred, and cesium carbonate (Cs ₂ CO ₃ ) is added to the reaction solution in the molten state so as to be 1.5 × 10 ⁻⁶ moles per mole of BPC as a transesterification catalyst. In addition, the reaction mixture was stirred and grown at 220 ° C. for 30 minutes under a nitrogen gas atmosphere. Next, the pressure in the reactor was reduced to 100 Torr over 40 minutes under the same temperature, and the reaction was further performed for 100 minutes to distil out phenol.
Next, the temperature in the reactor was raised to 284 ° C. over 60 minutes, and the pressure was reduced to 3 Torr to distil out phenol corresponding to almost all the theoretical amount of distillation. Next, the pressure in the reactor was maintained at less than 1 Torr under the same temperature, and the reaction was continued for another 60 minutes to complete the polycondensation reaction. At this time, the stirring rotation number of the stirrer was 38 revolutions / minute, the temperature of the reaction solution immediately before the completion of the reaction was 289 ° C., and the stirring power was 1.00 kW.
Next, the reaction liquid in the molten state is fed into a twin-screw extruder, and a 4-fold molar amount of butyl p-toluenesulfonate is supplied 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 in the form of 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 to produce the resin composition of the present invention.

<Measurement of viscosity average molecular weight (Mv) of polycarbonate resin>
The viscosity average molecular weight (Mv) of polycarbonate resin uses methylene chloride as a solvent, and determines the intrinsic viscosity (デ) (unit: dL / g) at a temperature of 20 ° C. using a Ubbelohde viscometer, and the viscosity of Schnell below Calculated from the equation.
η = 1.23 × 10 ^-4 Mv ^0.83

<Measurement of pencil hardness of thermoplastic resin>
After drying the polycarbonate resin pellet at 100 ° C. for 5 hours, using an injection molding machine (“α-2000i-150B” manufactured by FANUC Co., Ltd.), screw rotation speed 100 rpm at a cylinder setting temperature of 260 ° C. and a mold temperature of 70 ° C. A flat test piece (150 mm × 100 mm × 2 mm thick) was produced under conditions of an injection speed of 30 mm / sec. The pencil hardness measured at a load of 750 g was determined for this flat test piece using a pencil hardness tester in accordance with ISO 15184.
The pencil hardness tester used was made by Toyo Seiki Seisaku-sho.

<Measurement of hydroxyl value of ester compound>
The hydroxyl value is the number of milligrams of potassium hydroxide required to neutralize the acetic acid bound to the hydroxyl group when the 1 g sample is acetylated, and the alcohol as the raw material of the ester compound is esterified with the carboxylic acid compound Occasionally, it is an indicator that indicates the number of unreacted hydroxyl groups.
The hydroxyl value was measured according to the method defined in JIS K 0070.

2. Example 1 to Example 3, Comparative Example 1 to Comparative Example 6, Reference Example 1
<Production of Resin Composition Pellets>
Each component listed in the above Table 1 is compounded at a ratio shown in Table 2 below (all expressed by mass) and uniformly mixed by a tumbler mixer, and then a twin-screw extruder (manufactured by Japan Steel Corp.) Using a TEX30α product, supplied to the extruder from the barrel at the upstream portion of the extruder at a cylinder setting temperature of 260 ° C, a screw rotation speed of 180 rpm, and a discharge rate of 30 kg / hr, melt kneading was performed to obtain resin composition pellets .

<Molar ratio of polycarbonate resin>
The molar ratio (mol%) in the table described later is an index indicating 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 used resin and the formula ( It computed from the viscosity average molecular weight using the molecular weight of the structural unit represented by 1).

<Is extrusion possible?>
In the production of the above resin composition pellets, the possibility of extrusion was visually confirmed and evaluated as follows.
a: extrudable b: extrusion unstable c: non-extrudable (polycarbonate resin is decomposed)

<Extruded gas generation amount>
Based on the amount of gas generated in Comparative Example 1 in the production of the above resin composition pellets, an equivalent amount or less of the generated amount was evaluated as a gas generation amount standard (a), and extrusion was compared with the reference amount. The amount of generated gas was visually evaluated as follows.
a: Gas generation standard b: Somewhat more c: Many

<Extrusion property comprehensive evaluation>
Based on the results of the above-mentioned extrudability and gas generation amount, the following evaluation was made.
A: Both extrudability and gas generation are a.
B: other than the above A and the following C.
C: At least one of extrudability and gas generation amount is c.

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

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

<Dynamic friction coefficient (30 N)>
The flat test piece obtained above is conformed to ISO 19252 and can be changed from a test speed of 100 mm / sec and a test distance of 100 mm from a vertical load of 1 N to 50 N using a scratch tester and using a scratch tester. 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 determined and evaluated as follows. The dynamic friction coefficient is preferably small.
As the scratch tester, one manufactured by Kato Tech Co., Ltd. was used.
a: 0.30 or less b: more than 0.30 and 0.35 or less c: more than 0.35

<Measurement of pencil hardness of resin composition>
The pencil hardness measured under a load of 1 kg was determined using the pencil hardness tester according to ISO 15184, for the flat test piece obtained above.
The pencil hardness tester used was made by Toyo Seiki Seisaku-sho.

<Nail scratch resistance>
The plate-like test pieces obtained above were rubbed back and forth 10 times with a nail and subjected to sensory evaluation.
a: No scratches, good sliding.
b: Slightly scratched but slippery.
c: There are fewer scratches than d, but they get hurt.
d: get hurt.

<ΔHaze before and after reciprocating wear test>
The haze of the plate-like test piece obtained above was measured in the same manner as above (the haze at this time is referred to as the haze a).
On the other hand, with respect to the same flat-plate-like test piece obtained above, a flat wear tester was used to fold a salaci (100% cotton, a 20 × 20 count salaci cut into 15 cm × 33 cm) into 18 folds and flat wear It attached to the jig | tool of the tester, and tested by 40 cycles of reciprocation cycles, 1 kg of loads, and 500 reciprocations. The haze of the plate-like test pieces after the reciprocating abrasion test was measured in the same manner as described above (the haze at this time is referred to as the haze b). "Haze b-haze a" was made into (DELTA) haze before and behind a reciprocation abrasion test, and it evaluated according to the following divisions.
The flat wear tester used was made by Daiei Kagaku Seiki.
As the sala, a sala from Nankai Co., Ltd. was used.
a: 2.00% or less b: more than 2.00% 3.00% or less c: 3.00% or more

<Scratch resistance comprehensive evaluation>
Based on the results of the above-mentioned nail scratch resistance, dynamic friction coefficient, and Δ haze before and after the reciprocation wear test, evaluations were made as follows.
A: All evaluations are a.
B: other than the above A and the following C.
C: At least one evaluation is c or d.

  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 unit represented by the formula (1) to the total structural units constituting the polycarbonate resin.
As is clear from the above results, the resin composition of the present invention was excellent in abrasion resistance, and in particular, the rate of maintaining the transparency before and after the abrasion test was high, and the extrudability was excellent (Example 1 to Example) 3). In particular, the effect of the present invention is surprising in that a resin composition having a pencil hardness of 3H is obtained although a polycarbonate resin having a pencil hardness of 2H and an acrylic resin having a pencil hardness of 2H are blended. It is a thing.
On the other hand, even when the haze was low, when the dynamic friction coefficient was high, the haze before and after the abrasion test significantly decreased and the abrasion resistance was inferior (Comparative Examples 1 to 3 and 5).
On the other hand, when the acrylic resin did not contain the structural unit represented by Formula (X) (comparative example 4), the haze became high.

Claims (12)

(A) A resin composition containing 0.5 to 10.0 parts by mass of (B) an ester compound and 3 to 100 parts by mass of (C) an acrylic resin with respect to 100 parts by mass of a polycarbonate resin,
(A) The polycarbonate resin contains 50 to 100 mol% of a structural unit represented by the following formula (1) in all structural units,
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),
The test piece of 2 mm in thickness formed from the resin composition has a haze of 5.0% or less measured in accordance with ISO 14782 and a coefficient of dynamic friction in accordance with ISO 19252 at a load of 30 N of 0. A resin composition of 35 or less;
Formula (1)

In formula (1), R ¹ represents a methyl group, R ² represents a hydrogen atom or a methyl group, and X ¹ represents any 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 a substituted or unsubstituted alicyclic hydrocarbon having 6 to 12 carbon atoms Represents a group;
Formula (X)

In formula (X), R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ⁹ has 6 carbon atoms which may have a substituent. And an aliphatic hydrocarbon group of 1 to 20 carbon atoms or an aliphatic hydrocarbon group of 1 to 3 carbon atoms substituted with an aromatic hydrocarbon group of 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 saturated linear carboxylic acid and a saturated linear alcohol. The resin composition according to claim 1, wherein R ⁶ , R ⁷ and R ⁸ in the formula (X) are each independently a hydrogen atom or a methyl group. R ⁹ 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 of any one of 1-3. 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) / (above) The resin composition according to any one of claims 1 to 4, which is contained at a ratio such that the mass ratio of c2) is 5 to 80/95 to 20;
Formula (X1)

In formula (X1), R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ¹⁰ may have a hydrogen atom or a substituent A good C1-C20 aliphatic hydrocarbon group is shown (however, except that whose substituent contains an aromatic hydrocarbon group). The resin composition according to any one of claims 1 to 5, wherein the weight average molecular weight of the (C) acrylic resin is 5,000 to 30,000. The resin composition according to any one of claims 1 to 6, wherein the content of the (C) acrylic resin is 7 to 45 parts by mass with respect to 100 parts by mass of the (A) polycarbonate resin. The resin composition according to any one of claims 1 to 7, wherein the content ratio of the structural unit represented by the formula (1) in the (A) polycarbonate resin is 80 mol% or more. The resin according to any one of claims 1 to 8, wherein a ratio ((B) / (C) x 100) (%) of (B) an ester compound to (C) an acrylic resin is 3 to 200. Composition. The resin composition according to any one of claims 1 to 9, wherein the polycarbonate resin (A) further comprises a structural unit represented by the following formula (2):
Formula (2)

In formula (2), X ² represents any 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 a substituted or unsubstituted alicyclic hydrocarbon having 6 to 12 carbon atoms Represents a group. The test piece of thickness 2 mm formed from the said resin composition is (DELTA) haze which is a difference of the haze before and behind the reciprocation abrasion test which used salaci is 3.00% or less in any one of Claims 1-10. The resin composition as described in. The molded article formed from the resin composition of any one of Claims 1-11.