JP7101465B2 - Resin compositions and molded products - Google Patents

Description

The present invention relates to resin compositions and molded articles. In particular, the present invention relates to a resin composition using a polycarbonate resin, which has excellent resistance to nail scratches and can provide a molded product having excellent transparency.

Polycarbonate resin has excellent mechanical strength, electrical properties, transparency, etc., and is widely used as an engineering plastic in various fields such as electrical and electronic equipment fields and automobile fields. In recent years, in these fields, the thickness, miniaturization, and weight reduction of molded products have progressed, and further improvement in the performance of molded materials is required, and some proposals have been made.

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

Japanese Unexamined Patent Publication No. 2017-110180

Conventionally, it has been known that a polycarbonate resin containing a structural unit derived from bisphenol C tends to have a high pencil hardness. Here, there are cases where a molded product molded from a polycarbonate resin containing a structural unit derived from bisphenol C is used as a product without being subjected to a treatment such as painting (hereinafter, may be referred to as "paintless"). However, as a result of the study by the present inventor, it was found that such a molded product has a slight problem in nail scratch resistance despite its high pencil hardness. The resin composition described in Patent Document 1 is a resin composition having excellent resistance to nail scratches, but in the examples of the same document, jet blackness and the like are pursued. That is, the development of new materials is required for applications that require transparency. In addition, for products without paint, fingerprints may be wiped off with a cleaner or the like. Therefore, resistance to nail scratches after wiping off the solvent is also required.
Further, even if an appropriate additive is added to the polycarbonate resin to improve the transparency and scratch resistance of the resin composition, the extrudability and transparency may be inferior depending on the type of the additive.
An object of the present invention is to solve such a problem, and a resin composition having excellent extrudability, high transparency, and excellent resistance to scratches on nails at the initial stage and after wiping off a solvent, and It is an object of the present invention to provide a molded product 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。
＜２＞前記（Ｂ）脂肪酸モノエステルが、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＞（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＞または＜２＞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。
＜４＞前記（Ａ）ポリカーボネート樹脂は、前記式（１）で表される構造単位を５～９５モル％と、前記式（２）で表される構造単位９５～５モル％を含む、＜３＞に記載の樹脂組成物。
＜５＞厚さ２ｍｍの成形品に成形した時のヘイズが５．０％以下である、＜１＞～＜４＞のいずれか１つに記載の樹脂組成物。
＜６＞前記樹脂組成物が無機充填材を含まないか、前記（Ａ）ポリカーボネート樹脂１００質量部に対し、無機充填材を８質量部以下の割合で含む、＜１＞～＜５＞のいずれか１つに記載の樹脂組成物。
＜７＞＜１＞～＜６＞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。
＜８＞前記成形品がパネル状である、＜７＞に記載の成形品。 As a result of studies by the present inventor based on the above problems, it has been found that the above problems can be solved by blending a specific fatty acid ester with the polycarbonate resin. Specifically, the above problems were solved by the following means <1>, preferably <2> to <8>.
<1> A structure in which 0.5 to 10.0 parts by mass of (B) fatty acid monoester is contained with respect to 100 parts by mass of (A) polycarbonate resin, and the (A) polycarbonate resin is represented by the following formula (1). The resin composition containing 5 mol% or more of units, and the (B) fatty acid monoester has a hydroxyl value of 100 mgKOH / g or less and a carbon number of 42 or more;
Equation (1)

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

R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group, and Z binds to C to form an alicyclic hydrocarbon having 6 to 12 carbon atoms and which may have a substituent. Represents a group.
<2> The resin composition according to <1>, wherein the (B) fatty acid monoester is formed of a saturated linear carboxylic acid and a saturated linear alcohol.
<3> The resin composition according to <1> or <2>, wherein the (A) polycarbonate resin further contains a structural unit represented by the following formula (2);
Equation (2)

In equation (2), X ² represents one of the following equations.

R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group, and Z binds to C to form an alicyclic hydrocarbon having 6 to 12 carbon atoms and which may have a substituent. Represents a group.
<4> The polycarbonate resin (A) contains 5 to 95 mol% of the structural unit represented by the formula (1) and 95 to 5 mol% of the structural unit represented by the formula (2). 3> The resin composition according to.
<5> The resin composition according to any one of <1> to <4>, wherein the haze when molded into a molded product having a thickness of 2 mm is 5.0% or less.
<6> Any of <1> to <5>, wherein the resin composition does not contain an inorganic filler, or contains an inorganic filler in a proportion of 8 parts by mass or less with respect to 100 parts by mass of the polycarbonate resin (A). The resin composition according to one.
<7> A molded product formed from the resin composition according to any one of <1> to <6>.
<8> The molded product according to <7>, wherein the molded product is in the form of a panel.

INDUSTRIAL APPLICABILITY According to the present invention, it has become possible to provide a resin composition having excellent extrudability, high transparency, and excellent resistance to nail scratches at the initial stage and after wiping off a solvent, and a molded product using the resin composition. ..

Hereinafter, the contents of the present invention will be described in detail. In addition, in this specification, "-" is used in the meaning which includes the numerical values described before and after it as the lower limit value and the upper limit value.

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。
このような構成とすることにより、押出性に優れ、透明性が高く、かつ、初期および溶媒拭き取り後の爪傷付き耐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 contains 0.5 to 10.0 parts by mass of (B) fatty acid monoester with respect to 100 parts by mass of (A) polycarbonate resin, and the above-mentioned (A) polycarbonate resin has the following formula (1). The structural unit represented by (B) contains 5 mol% or more, and the fatty acid monoester (B) is characterized by having a hydroxyl value of 100 mgKOH / g or less and a carbon number of 42 or more.
Equation (1)

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

R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group, and Z binds to C to form an alicyclic hydrocarbon having 6 to 12 carbon atoms and which may have a substituent. Represents a group.
With such a configuration, it becomes possible to provide a resin composition having excellent extrudability, high transparency, and excellent resistance to nail scratches at the initial stage and after wiping off the solvent.
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 resin composition of the present invention contains 5 mol% or more of the structural units represented by the formula (1).
Equation (1)

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

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

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

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。 In the formula (1), X ¹ preferably has the following structure.

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

The polycarbonate resin (A) in the present invention contains the structural unit represented by the formula (1) in an amount of 5 mol% or more, preferably 10 mol% or more, more preferably 20 mol% or more, still more preferably 40 mol% or more. It further preferably contains 50 mol% or more, further preferably 60 mol% or more, and even more preferably 65 mol% or more. The upper limit is not limited, but is preferably 95 mol% or less, more preferably 90 mol% or less, still more preferably 85 mol% or less, still more preferably 80 mol% or less, still more preferably 76 mol. Including% or less. Further, it may be 40 mol% or less.

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

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

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は、上記式（２）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の二価の脂環式炭化水素基を形成するが、二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。 In the present invention, the polycarbonate resin (A) may have a structural unit other than the structural unit represented by the formula (1). As the other structural unit, the structural unit represented by the following formula (2) is preferable.
Equation (2)

In equation (2), X ² represents one of the following equations.

R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group, and Z binds to C to form an alicyclic hydrocarbon having 6 to 12 carbon atoms and which may have a substituent. Represents a group.
Z is bonded to carbon C bonded to the two phenyl groups in the above formula (2) to form a divalent alicyclic hydrocarbon group having 6 to 12 carbon atoms, which is a divalent alicyclic. Examples of the formula hydrocarbon group include a cycloalkylidene group such as a sikilohexylidene group, a cycloheptylidene group, a cyclododecylidene group, an adamantylidene group and a cyclododecylidene group. Examples of the substituted substance include those having a methyl substituent and an ethyl substituent. Among these, a cyclohexylidene group, a methyl substituent (preferably a 3,3,5-trimethyl substituent) of a cycliohexylidene 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。 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 methyl groups.

A preferable specific example of the structural unit represented by the above formula (2) is 2,2-bis (4-hydroxyphenyl) propane, that is, a structural unit (carbonate structural unit) composed of bisphenol-A.
In the present invention, the structural unit represented by the formula (2) is contained in the polycarbonate resin (A) in an amount of preferably 5 mol% or more, more preferably 10 mol% or more, still more preferably 15 mol% or more, still more preferably. It contains 20 mol% or more, more preferably 24 mol% or more. Further, it may contain 60 mol% or more. Further, the structural unit represented by the formula (2) is preferably contained in the polycarbonate resin (A) in an amount of 95 mol% or less, more preferably 90 mol% or less, still more preferably 80 mol% or less. , 60 mol% or less is more preferably contained, 50 mol% or less is further preferably contained, 40 mol% or less is further preferably contained, and 35 mol% or less is particularly preferably contained.
In the present invention, the polycarbonate resin (A) may not contain the structural unit represented by the formula (2), may contain only one kind, or may contain two or more kinds. When two or more kinds are contained, it is preferable that the total amount is within the above range.

In the present invention, the polycarbonate resin (A) is, for example, the following 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). Aromatic dihydroxy compounds such as;
Bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) -4-methyl Pentan, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3-) (1-Methylethyl) phenyl) propane, 2,2-bis (4-hydroxy-3-tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3- (1-methylpropyl) phenyl) propane , 2,2-bis (4-hydroxy-3-cyclohexylphenyl) propane, 2,2-bis (4-hydroxy-3-phenylphenyl) propane, 1,1-bis (4-hydroxyphenyl) decane, 1, 1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) phenylmethane, 1,1-bis (4-) Hydroxy-3-methylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3- (1-methylethyl) phenyl) cyclohexane, 1,1-bis (4-hydroxy-3-tert-butylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3- (1-methylpropyl) phenyl) cyclohexane, 1,1-bis (4-hydroxy) -3-Cyclohexylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3-phenylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3-methylphenyl) -1-phenylethane, 1,1- Bis (4-hydroxy-3 , 5-dimethylphenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3- (1-methylethyl) phenyl) -1-phenylethane, 1,1-bis (4-Hydroxy-3-tert-butylphenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3- (1-methylpropyl) phenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3- (1-methylpropyl) phenyl) 4-Hydroxy-3-cyclohexylphenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3-phenylphenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) ) Cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclooctane, 4,4'-(1,3-phenylenediisopropyridene) bisphenol, 4,4'-(1,4-phenylenediisopropyridene) 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 the present invention, in the (A) polycarbonate resin, the structural unit other than the structural unit represented by the above formula (1) and the structural unit represented by the formula (2) is preferably 30 mol% or less, more preferably. It is preferably 20% mol or less, more preferably 10 mol% or less, 5 mol% or less, or 1 mol% or less.

Hereinafter, embodiments of the (A) polycarbonate resin in the present invention will be described.
(1) Polycarbonate resin containing more than 95 mol% of the structural units represented by the formula (1) among all the structural units (2) Of all the structural units, 5 to 5 to the structural units represented by the formula (1). Polycarbonate resin containing 95 mol% and 95 to 5 mol% or more of structural units other than the structural unit represented by the formula (1) (preferably the structural unit represented by the formula (2)) Polycarbonate resin used in the present invention. However, when the structural unit other than the structural unit represented by the formula (1) is included (preferably the structural unit represented by the formula (2)), the following blend form is exemplified.
• Polycarbonate resin (A1) consisting of structural units represented by the formula (1) in which more than 50 mol% (preferably 70 mol% or more, 95 mol% or more) of all structural units and 95 mol% of all structural units. Mixture of polycarbonate resin (A2) consisting of structural units represented by the formula (2):
Copolymerized polycarbonate resin (A3) in which the total of the structural units represented by the formula (1) and the structural units represented by the formula (2) accounts for more than 95 mol% of the total structural units:
A mixture of the polycarbonate resin (A1), the carbonate resin (A2), and the copolymerized polycarbonate resin (A3):
-A mixture of the above-mentioned polycarbonate resin (A1) and the above-mentioned copolymerized polycarbonate resin (A3);
-A mixture of the above-mentioned copolymerized polycarbonate resin (A3) and the above-mentioned polycarbonate resin (A2);
-A mixture containing two or more of at least one of a polycarbonate resin (A1), a polycarbonate resin (A2), and a copolymerized polycarbonate resin (A3) in any of the above embodiments;
In any of the embodiments, the structural unit represented by the formula (1) in (A) the polycarbonate resin may be contained in a proportion of 5 mol% or more, and further, the structure represented by the formula (1). It is preferable that the unit and the structural unit represented by the formula (2) are contained in all the structural units in a ratio satisfying the above-mentioned preferable range.

In the present invention, in the blend form exemplified above, the form containing (A1) polycarbonate resin and (A2) polycarbonate resin is particularly preferable. When the (A1) polycarbonate resin and the (A2) polycarbonate resin are contained, the mixing ratio of both is preferably 5:95 to 95: 5, and more preferably 10:90 to 95: 5. It is more preferably 15:85 to 95: 5, and even more preferably 15:85 to 90:10. The resin composition of the present invention may contain only one type of (A1) polycarbonate resin and (A2) polycarbonate resin, respectively, or may contain two or more types. When two or more kinds are contained, it is preferable that the total amount is within the above range. With such a configuration, the pencil hardness can be set to B to 2H.

In the present invention, the viscosity average molecular weight (Mv) of the polycarbonate resin (A) is preferably a lower limit of 9,000 or more, more preferably 10,000 or more, and more preferably 12,000 or more. More preferred. The upper limit of Mv is preferably 32,000 or less, more preferably 30,000 or less, and even more preferably 28,000 or less.
By setting the viscosity average molecular weight to the above lower limit value or more, a molded product having improved moldability and high mechanical strength can be obtained. Further, by setting the value to the upper limit or less, the fluidity of the molded product is improved, and a thin-walled molded product or the like can be efficiently manufactured.
The viscosity average molecular weight (Mv) is measured according to the method described in Examples described later (hereinafter, the same applies to Mv).

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

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

The resin composition of the present invention preferably contains the (A) polycarbonate resin in a proportion of 80% by mass or more, more preferably in an proportion of 85% by mass or more, and in a proportion of 90% by mass or more. It is more preferable, and it is more preferable to contain it in a proportion of 93% by mass or more. (A) The upper limit of the polycarbonate resin is not particularly specified, but can be, for example, 99.4% by mass or less.
The resin composition of the present invention may contain only one type (A) polycarbonate resin, or may contain two or more types. When two or more kinds are contained, it is preferable that the total amount is within the above range.

<(B) Fatty acid monoester>
The resin composition of the present invention contains (B) a fatty acid monoester. (B) The fatty acid monoester has a hydroxyl value of 100 mgKOH / g or less and a carbon number of 42 or more.
By lowering the hydroxyl value, the fatty acid ester and the polycarbonate resin are less likely to be decomposed during extrusion, and the generation of gas during molding or the like can be effectively suppressed. The hydroxyl value is preferably 80 mgKOH / g or less, more preferably 50 mgKOH / g or less, still more preferably 35 mgKOH / g or less.
The hydroxyl value is measured according to the method described in Examples described later.

The (B) fatty acid monoester used in the present invention has one ester group, and by reducing the number of ester groups in this way, the transparency of the obtained molded product can be improved.

Further, in the present invention, by using a fatty acid ester having a carbon number of a predetermined value or more, it is possible to effectively suppress the generation of gas during extrusion and molding.
(B) The carbon number of the fatty acid monoester is 42 or more, preferably 44 or more. (B) The upper limit of the carbon number of the fatty acid monoester is not particularly specified, but is preferably 150 or less, more preferably 100 or less, and further preferably 90 or less. (B) The carbon number of the fatty acid monoester is the total number of carbon atoms contained in one molecule. Therefore, when the (B) fatty acid monoester is formed from the fatty acid and the monohydric alcohol, the total number of carbon atoms contained in the fatty acid and the monohydric alcohol is the carbon number of the (B) fatty acid monoester.
When two or more kinds of (B) fatty acid monoesters are contained, the carbon number is the total value of the carbon number of each (B) fatty acid monoester multiplied by the mass fraction.

The molecular weight of the (B) fatty acid monoester used in the present invention is preferably 2000 or less, more preferably 1500 or less, and even more preferably 1200 or less. With such a configuration, it is possible to obtain an excellent molded product with a balance between high transparency and high resistance to nail scratches. Details such as the structure will be described in detail.

The (B) fatty acid monoester used in the present invention is usually formed from a fatty acid and a monohydric alcohol, and is preferably formed from a saturated linear carboxylic acid and a saturated linear alcohol. The (B) fatty acid monoester used in the present invention preferably has a linear structure and has an alkyl group having 15 or more carbon atoms at both ends (preferably an alkyl group having 15 to 30 carbon atoms). With such a configuration, it becomes easy to obtain an excellent molded product due to the balance between high transparency and high resistance to nail scratches.

Next, fatty acids will be described.
In the present invention, the fatty acid is preferably a saturated fatty acid. In particular, in the present invention, the fatty acid is preferably a saturated linear carboxylic acid.
Further, the fatty acid may or may not have a substituent, but it is preferable that the fatty acid does not have a substituent. The transparency of the obtained molded product tends to be further improved when it does not have a substituent.
Further, the fatty acid is preferably composed only of an oxygen atom, a carbon atom and a hydrogen atom.
The carbon number of the fatty acid is preferably 2 to 45, more preferably 10 to 40, and even more preferably 15 to 36.
Specific examples of fatty acids (number of carbon atoms in parentheses) include lauric acid (C12), melissic acid (C14), palmitic acid (C16), stearic acid (C18), arachidic acid (C20), and behenic acid (C22). Examples thereof include lignoseric acid (C24), cerotic acid (C26), montanic acid (C28), and melissic acid (C30).

Next, the monohydric alcohol will be described.
In the present invention, the monohydric alcohol is preferably a linear alcohol. Further, the monohydric alcohol is preferably a saturated alcohol. In the present invention, the monohydric alcohol is particularly preferably a monohydric saturated linear alcohol.
Further, the monohydric alcohol may or may not have a substituent, but it is preferable that the monohydric alcohol does not have a substituent. The transparency of the obtained molded product tends to be further improved when it does not have a substituent.
Further, the monohydric alcohol is preferably composed of only an oxygen atom, a carbon atom and a hydrogen atom.
The carbon number of the monohydric alcohol is preferably 2 to 45, more preferably 5 to 36.
Specific examples of the monohydric alcohol (the number of carbon atoms in parentheses) include octanol (C8), dodecanol (C12), stearyl alcohol (C18), behenyl alcohol (C22) and montanyl alcohol (C28).

In the (B) fatty acid monoester, the difference between the carbon number of the fatty acid and the carbon number of the monovalent alcohol is preferably 12 or less, more preferably 10 or less, and may be 5 or less, and 2 or less. There may be no difference in the number of carbon atoms, that is, the number of carbon atoms may be the same.

Specific examples of the (B) fatty acid monoester (number of carbon atoms in parentheses) used in the present invention include behenyl behenate (C44), montanyl montanate (C56), stearyl montanate (C46), and montanyl stearate ( C46), behenyl montanate (C50), montanil behenate (C50), and in particular, montanil montanate (C56) and behenyl behenate (C44) are preferred, and behenyl behenate (C44). Is even more preferable.

The resin composition of the present invention contains 0.5 to 10.0 parts by mass of (B) fatty acid monoester with respect to 100 parts by mass of (A) polycarbonate resin.
The lower limit of the blending amount of the (B) fatty acid monoester 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. .. Within the above range, the resistance to nail scratches can be further improved.
The upper limit of the blending amount of the (B) fatty acid monoester is preferably 9.0 parts by mass or less, and 8.0 parts by mass or less and 7.0 parts by mass with respect to 100 parts by mass of the (A) polycarbonate resin. Hereinafter, it may be 6.0 parts by mass or less, 5.0 parts by mass or less, and 3.0 parts by mass or less. By setting it in a preferable range, hydrolysis resistance can be improved and mold contamination can be suppressed more effectively. In the present invention, even if the blending amount of (B) fatty acid monoester is small, the structure can be excellent in nail scratch resistance.
The resin composition of the present invention may contain only one type (B) fatty acid monoester, or may contain two or more types. When two or more kinds are contained, it is preferable that the total amount is within the above range.

<Other ingredients>
The resin composition of the present invention may contain other components other than the above, if necessary, as long as the desired physical properties are not significantly impaired. Examples of other components include thermoplastic resins other than the above-mentioned polycarbonate resin, various resin additives, and the like.
The resin composition of the present invention may also contain an inorganic filler. By including the inorganic filler, the mechanical strength of the obtained molded product can be further improved. As one embodiment of the resin composition of the present invention, the inorganic filler is not contained, or the amount of the inorganic filler is 8 parts by mass or less (preferably 6 parts by mass or less, more preferably 6 parts by mass or less) with respect to 100 parts by mass of the (A) polycarbonate resin. Is 4 parts by mass or less, more preferably 1 part by mass or less). By not including the inorganic filler or setting the blending amount within the above range, the transparency of the obtained molded product can be further improved. As the inorganic filler, the descriptions in paragraphs 0075 to 0079 of JP-A-2017-110180 can be referred to, and these contents are incorporated in the present specification.
Examples of the resin additive include stabilizers (heat stabilizers, antioxidants, etc.), ultraviolet absorbers, antistatic agents, flame retardants, flame retardant aids, dyes, pigments, antifogging agents, lubricants, and antiblocking agents. , Flow improver, plasticizer, dispersant, antibacterial agent and the like. In addition, 1 type may be contained in the resin additive, and 2 or more types may be contained in arbitrary combinations and ratios.
The resin composition of the present invention can be configured to be substantially free of a mold release agent other than the above-mentioned (B) fatty acid monoester. The term "substantially free" means that the amount of the other release agent is less than 0.5 parts by mass, preferably 0.3 parts by mass or less, based on 100 parts by mass of the (A) polycarbonate resin. It is more preferably 0.1 part by mass or less, further preferably 0.01 part by mass or less, further preferably 0.001 part by mass or less, and further preferably 0.0001 part by mass or less. More preferred.

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

Examples of the organic phosphite compound include triphenylphosphite, tris (monononylphenyl) phosphite, tris (monononyl / dinonyl-phenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, and monooctyl. Diphenylphosphite, dioctylmonophenylphosphite, monodecyldiphenylphosphite, didecylmonophenylphosphite, tridecylphosphite, trilaurylphosphite, tristearylphosphite, 2,2-methylenebis (4,6-di-) tert-butylphenyl) octylphosphite and the like can be mentioned.
Specific examples of such an organic phosphite compound include, for example, "ADEKA STAB 1178", "ADEKA STAB 2112", "ADEKA STAB HP-10" manufactured by ADEKA, and "JP-351" manufactured by Johoku Chemical Industry Co., Ltd. Examples thereof include "JP-360", "JP-3CP", and "Irgafos 168" manufactured by BASF.

Examples of the antioxidant include hindered phenol-based stabilizers.
Specific examples of the hindered phenolic stabilizer include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and octadecyl-3- (3,5-di-tert-). Butyl-4-hydroxyphenyl) propionate, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N'-hexane-1,6-diylbis [3-( 3,5-Di-tert-butyl-4-hydroxyphenyl) propionamide], 2,4-dimethyl-6- (1-methylpentadecyl) phenol, diethyl [[3,5-bis (1,1-dimethylethyl) ) -4-Hydroxyphenyl] methyl] phosphate, 3,3', 3'', 5,5', 5''-hex-tert-butyl-a, a', a''-(methicylene-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], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris (3,5-di-tert-butyl-4-hydroxy) Benzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert-butyl-4- (4,6-bis (octylthio) -1, 3,5-Triazine-2-ylamino) phenol, 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate and the like. Be done.

Among them, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate are among them. preferable. Specific examples of such a hindered phenol-based stabilizer include "Irganox 1010" and "Irganox 1076" manufactured by BASF, "ADEKA STAB AO-50" and "ADEKA STAB AO-60" manufactured by ADEKA. ..

The content of the stabilizer in the resin composition of the present invention is usually 0.001 part by mass or more, preferably 0.005 part by mass or more, and more preferably 0.01 part 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 part by mass or less, and more preferably 0.3 part by mass or less. By setting the content of the stabilizer in the above range, the effect of adding the stabilizer is more effectively exhibited.

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

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

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

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

<Manufacturing method of resin composition>
The method for producing the resin composition of the present invention is not limited, and a known method for producing a polycarbonate resin composition can be widely adopted, and the above-mentioned polycarbonate resin and fatty acid ester, and other components to be blended as necessary can be used, for example. Examples thereof include a method of premixing using various mixers such as a tumbler and a henschel mixer, and then melt-kneading with a mixer such as a Banbury mixer, a roll, a brabender, a single-screw kneading extruder, a twin-screw kneading extruder, and a kneader.
The temperature of melt-kneading is not particularly limited, but is usually in the range of 240 to 320 ° C.

<Molded product>
The above-mentioned resin composition (for example, pellets) is molded by various molding methods to obtain a molded product. That is, the molded product of the present invention is molded from the resin composition of the present invention.
The shape of the molded product is not particularly limited and may be appropriately selected depending on the intended use and purpose of the molded product. For example, a film shape, a rod shape, a cylindrical shape, an annular shape, a circular shape, an elliptical shape, or a polygonal shape. , Deformed products, hollow products, frame-shaped products, box-shaped products, panel-shaped products, and the like. Among them, a panel-shaped one is preferable, and the thickness is, for example, about 1 mm to 5 mm.

The method for molding the molded product is not particularly limited, and a conventionally known molding method can be adopted. For example, an injection molding method, an injection compression molding method, an extrusion molding method, a deformed extrusion method, a transfer molding method, a hollow molding method, etc. Gas assist hollow molding method, blow molding method, extrusion blow molding, IMC (in-mold coating) molding method, rotary molding method, multi-layer molding method, two-color molding method, insert molding method, sandwich molding method, foam molding method. , Pressurization molding method and the like. In particular, the resin composition of the present invention is suitable for molded products obtained by an injection molding method, an injection compression molding method, or an extrusion molding method. However, it goes without saying that the resin composition of the present invention is not limited to the molded products obtained by these.

The molded product of the present invention is suitably used for parts such as electrical and electronic equipment, OA equipment, personal digital assistants, mechanical parts, home appliances, vehicle parts, various containers, lighting equipment and the like. Among these, particularly, it is used for electric / electronic equipment, OA equipment, housings of information terminal equipment and home electric appliances, lighting equipment and vehicle parts (particularly vehicle interior parts), and vehicle interior parts are particularly preferable.

Hereinafter, the present invention will be described in more detail with reference to examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

1. 1. Raw material <Production example 1: Production of polycarbonate resin A1>
26.14 mol (6.75 kg) of bisphenol C (BPC) and 26.79 mol (5.74 kg) of diphenyl carbonate were placed in a SUS reactor (internal volume 10 liters) equipped with a stirrer and a distillate condensing device. After the reactor was replaced with nitrogen gas, the temperature was raised to 220 ° C. over 30 minutes in a nitrogen gas atmosphere.
Next, the reaction solution in the reactor is stirred, and cesium carbonate (Cs ₂ CO ₃ ) as an ester exchange reaction catalyst is added to the reaction solution in a molten state so as to be 1.5 × 10 ^-6 mol with respect to 1 mol of BPC. In addition, the reaction solution was stirred and cultivated at 220 ° C. for 30 minutes under a nitrogen gas atmosphere. Next, at the same temperature, the pressure in the reactor was reduced to 100 Torr over 40 minutes, and the reaction was further carried out for 100 minutes to distill off phenol.
Next, the temperature in the reactor was raised to 284 ° C. over 60 minutes and reduced to 3 Torr to distill off phenol corresponding to almost the entire theoretical distillate amount. Next, the pressure in the reactor was kept below 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 speed of the stirrer was 38 rotations / minute, the reaction liquid temperature immediately before the end of the reaction was 289 ° C., and the stirring power was 1.00 kW.
Next, the reaction solution in the molten state is fed into the twin-screw extruder, and a 4-fold molar amount of butyl p-toluenesulfonate with respect to cesium carbonate is supplied from the first supply port of the twin-screw extruder. After kneading with the reaction solution, the reaction solution was extruded into a strand shape through a die of a twin-screw extruder and cut with a cutter to obtain pellets of polycarbonate resin A1.

The materials shown in Table 1 below were used for producing the resin composition of the present invention.

<Measurement of viscosity average molecular weight (Mv) of polycarbonate resin>
For the viscosity average molecular weight (Mv) of the polycarbonate resin, methylene chloride was used as a solvent, and the ultimate viscosity (η) (unit: dL / g) at a temperature of 20 ° C. was determined using a Ubbelohde viscometer. Calculated from the formula.
η = 1.23 × 10 ^-4 Mv ^0.83

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

<Measurement of hydroxyl value of fatty acid ester and its substitute>
The hydroxyl value is the number of mg of potassium hydroxide required to neutralize acetic acid bonded to the hydroxyl group when 1 g of the sample is acetylated, and the alcohol that is the raw material of the ester compound is esterified with the carboxylic acid compound. Sometimes, it is an index showing the number of hydroxyl groups remaining unreacted.
The hydroxyl value was measured according to the method specified in JIS K 0070.

2. 2. Examples 1 to 5, Comparative Examples 1 to 15
<Manufacturing of resin composition pellets>
Each component listed in Table 1 above is blended in the proportion shown in Table 2 or Table 3 below (all are indicated by parts by mass), mixed uniformly with a tumbler mixer, and then a twin-screw extruder (Co., Ltd.). ) Using TEX30α) manufactured by Japan Steel Works, feed the extruder from the barrel at the upstream of the extruder at a cylinder set temperature of 260 ° C., screw rotation speed of 180 rpm, and discharge rate of 30 kg / hr, melt and knead, and resin composition pellets. (However, extrusion was not possible for some comparative examples).

<Mole ratio of polycarbonate resin>
The molar ratio (mol%) in Table 2 or Table 3 described later is an index showing the content of the structural unit represented by the formula (1) in the polycarbonate resin contained in the resin composition, and is a mixture of the resins used. It was calculated from the viscosity average molecular weight using the ratio.

<Extrusion availability>
In the production of the above resin composition pellets, the propriety of extrusion was visually confirmed and evaluated as follows.
a: Extrudable b: Extruded unstable c: Unextrudable (polycarbonate resin decomposes)

<Amount of extruded gas generated>
In the production of the above resin composition pellets, the amount of gas generated was visually evaluated as follows.
a: Gas generation standard b: Slightly large c: Large

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

<Measurement of Haze>
After drying the resin composition pellets obtained above at 100 ° C. for 5 hours, an injection molding machine (“α-2000i-150B” manufactured by FANUC Corporation) was used to set the cylinder temperature at 270 ° C. and the mold temperature at 70 ° C. Under the conditions of a screw rotation speed of 100 rpm and an injection speed of 30 mm / sec, a flat plate-shaped test piece having a thickness of 150 mm × 100 mm × 2 mm was injection-molded. The haze (unit:%) of the obtained flat plate-shaped test piece was measured with an NDH-2000 type haze meter manufactured by Nippon Denshoku Kogyo Co., Ltd.

<Nail scratch resistance (initial)>
The flat plate-shaped test piece produced above was rubbed 10 times with a nail and subjected to sensory evaluation.
a: It is not scratched and slippery.
b: Slightly scratched but slippery.
There are fewer scratches than c: d, but they hurt.
d: It hurt.

<Resistance to scratches on nails after wiping off solvent>
The surface of the flat plate-shaped test piece produced above was wiped with a cotton soaked with an ethanol solution, and a sensory evaluation was performed in the same manner as the above-mentioned resistance to nail scratches.

<Comprehensive evaluation>
Comprehensive evaluation was made based on extrudability, haze, and resistance to nail scratches.
1: Extrudability comprehensive evaluation is A, haze is 5.0% or less, and nail scratch resistance (initial) and nail scratch resistance after solvent wiping are a.
2: Other than 1 above and 3 below.
3: Satisfy one or more of the following.
The overall extrudability evaluation is C.
Haze is over 5.0%.
Nail scratch resistance is c or d.
The resistance to nail scratches after wiping off the solvent is c or d.

The results are shown in Tables 2 and 3 below.

In the above table, the "ratio of the formula (1)" is the ratio (mol%) of the structural unit represented by the formula (1) among all the structural units constituting the polycarbonate resin.
As is clear from the above results, the resin composition of the present invention was excellent in extrudability, low haze, and excellent resistance to nail scratches at the initial stage and after wiping off the solvent (Examples 1 to 5).
On the other hand, when the structural unit represented by the formula (1) was not included (Comparative Example 1 and Comparative Example 4), the resistance to nail scratches at the initial stage and after wiping off the solvent was inferior.
Further, as the fatty acid ester, one having a hydroxyl value of more than 100 mgKOH / g, one having 41 or less carbon atoms, one having a plurality of ester groups, or a substitute for a fatty acid ester is blended (Comparative Examples 1 to 13). It tended to have poor extrudability, high haze, and poor scratch resistance at the initial stage and after wiping with solvent.
Further, when the blending amount of the fatty acid ester was out of the range of the present invention (Comparative Example 14 and Comparative Example 15), the resistance to nail scratches at the initial stage and after wiping off the solvent was inferior, and the extrudability was inferior.

Claims (8)

The (A) polycarbonate resin contains 0.5 to 10.0 parts by mass of the (B) fatty acid monoester with respect to 100 parts by mass of the polycarbonate resin, and the (A) polycarbonate resin is a structural unit represented by the following formula (1) and the following formula . The structural unit represented by (2) is contained, the structural unit represented by the following formula (1) is contained in an amount of 31 mol% or more, and the fatty acid monoester (B) has a hydroxyl value of 100 mgKOH / g or less and has a hydroxyl value of 100 mgKOH / g or less. , A resin composition having 42 or more carbon atoms;
Equation (1)

In formula (1), R ¹ represents a methyl group, R ² represents a hydrogen atom, and X ¹ represents −C (CH ₃ ) ₂ − .
Equation (2)

In equation (2), X ² represents −C (CH ₃ ) ₂ −. The resin composition according to claim 1, wherein the (B) fatty acid monoester is formed of a saturated linear carboxylic acid and a saturated linear alcohol. The polycarbonate resin according to claim 1 or contains the structural unit represented by the formula (1) in an amount of 40 to 95 mol% and the structural unit represented by the formula (2) in an amount of 60 to 5 mol%. 2. The resin composition according to 2. The resin composition according to any one of claims 1 to 3 , wherein the haze when molded into a molded product having a thickness of 2 mm is 5.0% or less. The invention according to any one of claims 1 to 4 , wherein the resin composition does not contain an inorganic filler, or contains an inorganic filler in a proportion of 8 parts by mass or less with respect to 100 parts by mass of the polycarbonate resin (A). Resin composition. The resin composition according to any one of claims 1 to 5 , which is used for nail scratch resistance. A molded product formed from the resin composition according to any one of claims 1 to 6 . The molded product according to claim 7 , wherein the molded product is in the form of a panel.