JP6865102B2 - Polycarbonate resin composition and molded article - Google Patents

Description

The present invention relates to a polycarbonate resin composition and a molded product obtained by molding the polycarbonate resin composition.

Polycarbonate resin is excellent in strength and electrical characteristics, and the obtained molded product is also excellent in dimensional stability, etc. Therefore, it is suitable for housings of electrical and electronic equipment, interior parts for automobiles, or precision molded parts. It is widely used as a raw material resin for manufacturing, and in particular, in parts of home appliances, electronic devices, liquid crystal display display devices, etc., it is possible to obtain products with high commercial value by taking advantage of its beautiful appearance.

（一般式（１）中、Ｒ¹はメチル基、Ｒ²は水素原子またはメチル基を表し、Ｘは、

を表し、Ｒ³およびＲ⁴は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。）

（一般式（２）のＸは、前記一般式（１）のＸと同義である。） For example, Patent Document 1 describes a polycarbonate resin (A) having a structural unit of the following general formula (1) and having a viscosity average molecular weight (Mv) of 20,000 to 35,000 and a structural unit of the following general formula (2). A polycarbonate resin (B) having a viscosity average molecular weight (Mv) of 16,000 to 28,000 is contained in a mass ratio of (A) / (B) at a ratio of 80/20 to 20/80, according to ASTM D2794. A polycarbonate resin composition characterized in that the Dupont impact strength at 25 ° C. measured is 10 J or more and the pencil hardness measured according to JIS K5600 is F or more is disclosed.

(In the general formula (1), R ¹ represents a methyl group, R ² represents a hydrogen atom or a methyl group, and X is.

^{R 3} and R ⁴ represent a hydrogen atom or a methyl group, and Z represents a group that is bonded to C to form an alicyclic hydrocarbon that may have a substituent having 6 to 12 carbon atoms. .. )

(X in the general formula (2) is synonymous with X in the general formula (1).)

Japanese Unexamined Patent Publication No. 2013-064045

However, as a result of examining Patent Document 1, it was found that it is not always suitable for applications requiring heat resistance.
An object of the present invention is to solve such a problem, and the present invention is formed from a polycarbonate resin composition having high surface hardness and transparency and excellent heat resistance, and the polycarbonate resin composition. It is an object of the present invention to provide a molded product.

式（１）中、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（２）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、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。
＜２＞前記式（１）におけるＸ¹が下記式で表される、＜１＞に記載のポリカーボネート樹脂組成物；

上記式において、Ｒ³およびＲ⁴はメチル基である。
＜３＞前記式（２）におけるＲ²がいずれも水素原子である、＜１＞または＜２＞に記載のポリカーボネート樹脂組成物。
＜４＞前記（２）ポリカーボネート樹脂のＩＳＯ １５１８４に従って測定した鉛筆硬度がＨ以上である、＜１＞〜＜３＞のいずれか１つに記載のポリカーボネート樹脂組成物。
＜５＞前記（３）ポリエステル樹脂のガラス転移温度が１６０〜２２０℃である、＜１＞〜＜４＞のいずれか１つに記載のポリカーボネート樹脂組成物。
＜６＞前記（１）ポリカーボネート樹脂、（２）ポリカーボネート樹脂および（３）ポリエステル樹脂の質量比が１０〜７５：１２〜８３：５〜７０である、＜１＞〜＜５＞のいずれか１つに記載のポリカーボネート樹脂組成物。
＜７＞前記ポリカーボネート樹脂組成物を２ｍｍ厚さに成形した成形品のヘイズが１０％以下であり、ＩＳＯ １５１８４に従って測定した鉛筆硬度がＨＢ以上であり、ＩＳＯ ７５−２に従って測定した荷重たわみ温度が１１５℃以上である、＜１＞〜＜６＞のいずれか１つに記載のポリカーボネート樹脂組成物。
＜８＞＜１＞〜＜７＞のいずれか１つに記載のポリカーボネート樹脂組成物を成形してなる成形品。 As a result of studies by the present inventor based on the above problems, in addition to the above-mentioned two types of polycarbonate resins, a polyester resin having a high glass transition temperature is further blended, and the amount of terminal hydroxyl groups of the polycarbonate resin is adjusted. By doing so, it has been found that a polycarbonate resin composition having excellent heat resistance while maintaining high surface hardness and transparency can be obtained, and the present invention has been completed. Specifically, the above problems were solved by the following means <1>, preferably by <2> to <8>.
<1> (1) A polycarbonate resin containing more than 50 mol% of the structural unit represented by the following formula (1) and (2) 50 mol% or more of the structural unit represented by the following formula (2). The polycarbonate resin containing the polycarbonate resin and the polyester resin having a glass transition temperature of 160 ° C. or higher are included, and the amount of terminal hydroxyl groups of the (1) polycarbonate resin is 600 to 2000 mass ppm. A polycarbonate resin composition having a mass ratio of 2) polycarbonate resin and (3) polyester resin of 10 to 80: 10 to 85: 5 to 70 (however, the total is 100 parts by mass);

In equation (1), X ¹ represents one of the following equations.

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

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

R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group, and Z combines with C to form an alicyclic hydrocarbon having 6 to 12 carbon atoms and which may have a substituent. Represents a group.
<2> The polycarbonate resin composition according to <1>, ^{wherein X 1} in the above formula (1) is represented by the following formula;

In the above formula, R ³ and R ⁴ are methyl groups.
<3> The polycarbonate resin composition according to <1> or <2>, wherein ^{R 2} in the formula (2) is a hydrogen atom.
<4> The polycarbonate resin composition according to any one of <1> to <3>, wherein the pencil hardness measured according to the ISO 15184 of the (2) polycarbonate resin is H or more.
<5> The polycarbonate resin composition according to any one of <1> to <4>, wherein the glass transition temperature of the polyester resin (3) is 160 to 220 ° C.
<6> Any one of <1> to <5>, wherein the mass ratio of the (1) polycarbonate resin, (2) polycarbonate resin, and (3) polyester resin is 10 to 75: 12 to 83: 5 to 70. The polycarbonate resin composition according to 1.
<7> The haze of the molded product obtained by molding the polycarbonate resin composition to a thickness of 2 mm is 10% or less, the pencil hardness measured according to ISO 15184 is HB or more, and the deflection temperature under load measured according to ISO 75-2 is. The polycarbonate resin composition according to any one of <1> to <6>, which has a temperature of 115 ° C. or higher.
<8> A molded product obtained by molding the polycarbonate resin composition according to any one of <1> to <7>.

INDUSTRIAL APPLICABILITY According to the present invention, it has become possible to provide a polycarbonate resin composition having high surface hardness and transparency and excellent heat resistance, and a molded product molded from the polycarbonate 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、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（２）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、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。 The polycarbonate resin composition of the present invention comprises (1) a polycarbonate resin containing more than 50 mol% of the structural unit represented by the following formula (1), and (2) the structural unit represented by the following formula (2). (3) Polycarbonate resin having a glass transition temperature of 160 ° C. or higher, and (1) the amount of terminal hydroxyl groups of the polycarbonate resin is 600 to 2000 mass ppm. It is characterized in that the mass ratio of 1) polycarbonate resin, (2) polycarbonate resin and (3) polyester resin is 10 to 80: 10 to 85: 5 to 70 (however, the total is 100 parts by mass).

In equation (1), X ¹ represents one of the following equations.

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

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

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

With the above configuration, a polycarbonate resin composition and a molded product having high surface hardness and transparency and excellent heat resistance can be obtained.

式（１）中、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。
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。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。 <Polycarbonate resin containing the structural unit represented by the formula (1) (1)>
The polycarbonate resin composition of the present invention contains a polycarbonate resin containing the structural unit represented by the formula (1) (1) in an amount of more than 50 mol% and having an amount of terminal hydroxyl groups of 600 to 2000 mass ppm. ..

In equation (1), X ¹ represents one of the following equations.

R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group, and Z combines with C to form an alicyclic hydrocarbon having 6 to 12 carbon atoms and which may have a substituent. Represents a group.
Z combines with carbon C, which is bonded to two phenyl groups in the above formula (1), 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 cyclohexylidene group, a cycloheptilidene group, a cyclododecylidene group, an adamantylidene group and a cyclododecylidene group. Examples of the substituted product include those having a methyl substituent and an ethyl substituent. Among these, a cyclohexylidene group, a methyl substituent of a cyclohexylidene group (preferably a 3,3,5-trimethyl substituent), 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 (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.

A preferable specific example of the structural unit represented by the above formula (1) is 2,2-bis (4-hydroxyphenyl) propane, that is, a structural unit (carbonate structural unit) composed of bisphenol-A.
In the present invention, the above-mentioned (1) polycarbonate resin contains a structural unit represented by the formula (1) in an amount of more than 50 mol%. It is preferably 55 mol% or more, more preferably 60 mol% or more, still more preferably 70 mol% or more, still more preferably 80 mol% or more, still more preferably 90 mol% or more, still more preferably 95 mol. % Or more is the structural unit represented by the formula (1).
The above-mentioned (1) polycarbonate resin may contain only one type of structural unit represented by the formula (1), or may contain two or more types. When two or more types are included, the total amount is preferably in the above range.

The polycarbonate resin (1) may have a structural unit other than the structural unit represented by the formula (1). Examples of the dihydroxy compound constituting such another structural unit include the following aromatic dihydroxy compounds;
Bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) -4-methyl Pentan, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3-3) (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-hydroxyphenyl) 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-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 ..

The copolymerization amount of the structural unit other than the structural unit represented by the formula (1) in the above (1) polycarbonate resin is less than 50 mol%, preferably 45 mol% or less, more preferably 40 mol%. Below, it is more preferably 30 mol% or less, still more preferably 20 mol% or less, even more preferably 10 mol% or less, still more preferably 5 mol% or less.
The polycarbonate resin (1) may contain only one type of structural unit other than the structural unit represented by the formula (1), or may contain two or more types. When two or more types are included, the total amount is preferably in the above range.

The lower limit of the viscosity average molecular weight (Mv) of the polycarbonate resin (1) is preferably 9,000 or more, more preferably 10,000 or more, and further preferably 12,000 or more. The upper limit of Mv is preferably 30,000 or less, more preferably 25,000 or less, and even more preferably 23,000 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 above 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 lower limit of the amount of the terminal hydroxyl group of the polycarbonate resin (1) is 600 mass ppm or more, and more preferably 800 mass ppm or more. The upper limit of the amount of terminal hydroxyl groups is 2000 mass ppm or less, preferably 1800 mass ppm or less, more preferably 1600 mass ppm or less, and may be 1200 mass ppm or less, 1000 mass ppm or less. It may be as follows.
By setting the amount of the terminal hydroxyl group to the above lower limit value or more, the haze can be significantly reduced.
The amount of the terminal hydroxyl group is measured according to the method described in Examples described later (hereinafter, the same applies to the amount of the terminal hydroxyl group).
Further, when two or more kinds of (1) polycarbonate resins are used in combination, the amount of terminal hydroxyl groups after mixing two or more kinds of (1) polycarbonate resins means the amount of terminal hydroxyl groups. The amount of terminal hydroxyl groups when two or more types of (1) polycarbonate resins may be measured after mixing, or calculated as the mass average of the amounts of terminal hydroxyl groups of each (1) polycarbonate resin used. You may. Other physical properties of (1) polycarbonate resin, which will be described later, are also the physical characteristics after mixing of two or more types of (1) polycarbonate resin. The same applies to the physical characteristics such as the amount of terminal hydroxyl groups of (2) polycarbonate resin and (3) polyester resin, which will be described later.
In the present invention, as preferred embodiments of (1) polycarbonate resin, (1) polycarbonate resin having a terminal hydroxyl group amount of 300 mass ppm or more and less than 800 mass ppm and (1) having a terminal hydroxyl group amount of 800 mass ppm or more and 1300 mass ppm or less. A form of blending with a polycarbonate resin is exemplified, and a form of blending (1) a polycarbonate resin having a terminal hydroxyl group amount of 300 to 700 mass ppm and (1) a polycarbonate resin having a terminal hydroxyl group amount of 900 to 1300 mass ppm is preferable. .. In the above preferred embodiment, the blend ratio (mass ratio) of the (1) polycarbonate resin having the smaller amount of terminal hydroxyl groups and the (1) polycarbonate resin having the larger amount of terminal hydroxyl groups is 1: 1.5 to 2.5. Is preferable.

The above-mentioned (1) polycarbonate resin is exemplified by a pencil hardness of 3B to B measured according to ISO 15184, and further exemplified by 2B. The pencil hardness is measured according to the method described in Examples described later (hereinafter, the same applies to the pencil hardness).

The above-mentioned (1) polycarbonate resin preferably has a glass transition temperature of 130 ° C. or higher, more preferably 135 ° C. or higher, and even more preferably 140 ° C. or higher. The upper limit of the glass transition temperature is not particularly determined, but is usually less than 160 ° C, further 155 ° C or lower, and particularly 150 ° C or lower. The glass transition temperature is measured according to the method described in Examples described later (hereinafter, the same applies to the glass transition temperature).

The method for producing the above-mentioned (1) polycarbonate resin is not particularly limited, and any known method can be adopted. Examples thereof include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid phase transesterification method of a prepolymer. Among these, the interfacial polymerization method and the melt transesterification method are preferable, and the melt transesterification method is more preferable.

The polycarbonate resin composition of the present invention preferably contains the above-mentioned (1) polycarbonate resin in the range of 10 to 80% by mass of the composition. However, the total amount of (1) polycarbonate resin, (2) polycarbonate resin and (3) polyester resin does not exceed 100% by mass.
The polycarbonate resin composition of the present invention may contain only one type of the above-mentioned (1) polycarbonate resin, or may contain two or more types. When two or more types are included, the total amount is preferably in the above range.

式（２）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、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。 <Polycarbonate resin containing the structural unit represented by the formula (2) (2)>
The polycarbonate resin composition of the present invention contains a polycarbonate resin containing 50 mol% or more of the structural units represented by the formula (2) and (2).

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

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

Two R ² in the formula (2) are also respectively identical or different, preferably identical. R ² is preferably a hydrogen atom.
The above X ^{2 has the same meaning as the X 1} described in the above formula (1), and the preferable range is also the same.

Preferred specific examples of the above (2) polycarbonate resin include the following polycarbonate resins i) to iv).
i) Those having 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). ) Those with structural units that are _2-
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 ). Those with structural units that are _2-
iii) A structural unit composed of 2,2-bis (3-methyl-4-hydroxyphenyl) cyclohexane, that is, a structural unit in which R ¹ is a methyl group, R ² is a hydrogen atom, and X ² is a cyclohexylidene group. Have
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 cyclododecylene group. Those with structural units.
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.

In the present invention, the (2) polycarbonate resin contains 50 mol% or more of the structural unit represented by the formula (2). It preferably exceeds 50 mol%, more preferably 60 mol% or more, still more preferably 70 mol% or more, still more preferably 80 mol% or more, still more preferably 90 mol% or more, still more preferably. 95 mol% or more is the structural unit represented by the formula (2).
The above-mentioned (2) polycarbonate resin may contain only one type of structural unit represented by the formula (2), or may contain two or more types. When two or more types are included, the total amount is preferably in the above range.

The polycarbonate resin (2) may have a structural unit other than the structural unit represented by the formula (2). Examples of the dihydroxy compound constituting such another structural unit include structural units other than the structural unit represented by the formula (1) described in (1) Polycarbonate resin described above (however, however). Excluding those corresponding to the structural unit represented by the formula (2)).

The copolymerization amount of the structural unit other than the structural unit represented by the formula (2) in the above (2) polycarbonate resin is 50 mol% or less, preferably less than 50 mol%, and more preferably 40 mol%. Below, it is more preferably 30 mol% or less, still more preferably 20 mol% or less, even more preferably 10 mol% or less, still more preferably 5 mol% or less.
The polycarbonate resin (2) may contain only one type of structural unit other than the structural unit represented by the formula (2), or may contain two or more types. When two or more types are included, the total amount is preferably in the above range.

The lower limit of the viscosity average molecular weight (Mv) of the polycarbonate resin (2) is preferably 15,000 or more, more preferably 17,000 or more, and further preferably 19,000 or more. The upper limit of Mv is preferably 35,000 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, heat resistance and moldability are improved, and a molded product having high mechanical strength can be easily obtained. Further, by setting the value to the above upper limit or less, the fluidity of the molded product is improved, and a thin-walled molded product or the like can be manufactured more efficiently. Further, by setting the viscosity average molecular weight (Mv) in the range, it is possible to obtain an excellent molded product with a balance between high transparency and high hardness.

The lower limit of the amount of terminal hydroxyl groups in the (2) polycarbonate resin is preferably 400 mass ppm or more, more preferably 500 mass ppm or more, further preferably 600 mass ppm or more, and 700 mass ppm or more. The above is more preferable. The upper limit of the amount of terminal hydroxyl groups is preferably 2000 mass ppm or less, more preferably 1800 mass ppm or less, and further preferably 1600 mass ppm or less.
By setting the amount of terminal hydroxyl groups in the above range, the initial hue at the time of molding tends to be further improved, and the retention heat stability tends to be further improved.

The above-mentioned (2) polycarbonate resin preferably has a pencil hardness of F or more, more preferably H or more, further preferably 2H to 3H, and even more preferably 2H, as measured according to ISO 15184. ..

The polycarbonate resin (2) has a glass transition temperature of 110 ° C. or higher, more preferably 115 ° C. or higher, and even more preferably 118 ° C. or higher. The upper limit of the glass transition temperature is not particularly determined, but is, for example, 130 ° C. or lower, and further 125 ° C. or lower.

The method for producing the above-mentioned (2) polycarbonate resin is not particularly limited, and any known method can be adopted. Examples thereof include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid phase transesterification method of a prepolymer. Among these, the interfacial polymerization method and the melt transesterification method are preferable.

The polycarbonate resin composition of the present invention preferably contains the above-mentioned (2) polycarbonate resin in the range of 10 to 85% by mass of the composition.
The polycarbonate resin composition of the present invention may contain only one type of the above-mentioned (2) polycarbonate resin, or may contain two or more types. When two or more types are included, the total amount is preferably in the above range.

<(3) Polyester resin with a glass transition temperature of 160 ° C or higher>
The polycarbonate resin composition of the present invention contains (3) a polyester resin having a glass transition temperature of 160 ° C. or higher. By including such a resin, the heat resistance of the obtained polycarbonate resin composition can be improved.
(3) The glass transition temperature of the polyester resin is 160 ° C. or higher, preferably 170 ° C. or higher, more preferably 180 ° C. or higher, and even more preferably 185 ° C. or higher. The upper limit of the glass transition temperature is not particularly determined, but is, for example, 220 ° C. or lower, and further 210 ° C. or lower.

The type of the above (3) thermoplastic resin is not particularly specified as long as the glass transition temperature satisfies the above range, but polyester resin, polycarbonate resin, polyether resin, polyamide resin, polyimide resin, polyester resin, polysulfone resin. , Polyether sulfone resin, polyether ether ketone resin, polyetherimide resin, polyamideimide resin and polyallylsulfone resin are preferable, polyester resin and polycarbonate resin are more preferable, and polyester resin is further preferable.

When the above (3) thermoplastic resin is a polyester resin, a preferred embodiment is composed of a structural unit derived from a dicarboxylic acid and a structural unit derived from a diol, and 70 mol% or more of the structural unit derived from the dicarboxylic acid is preferable. Is derived from 80 mol% or more, more preferably 90 mol% or more, further preferably 95 mol% or more, and 70 mol% or more of the structural unit derived from the diol, preferably 80 mol% or more. However, a polyester resin in which 90 mol% or more, more preferably 95 mol% or more is derived from bisphenol can be mentioned.

Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, and methyl. Telephthalic acid, 4,4'-biphenyldicarboxylic acid, 2,2'-biphenyldicarboxylic acid, 4,4'-biphenyletherdicarboxylic acid, 4,4'-diphenylmethanedicarboxylic acid, 4,4'-diphenylsulphondicarboxylic acid, Examples thereof include 4,4'-diphenylisopropyridenedicarboxylic acid, 1,2-bis (4-carboxyphenoxy) ethane, 5-sodium sulfoisophthalic acid, and terephthalic acid and isophthalic acid are preferable. The aromatic dicarboxylic acid may be one kind or two or more kinds.

Examples of the bisphenol include 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, and 2,2-bis (4-hydroxy). -3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxydiphenyl ether, 4,4'- Examples thereof include dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenylketone, 4,4'-dihydroxydiphenylmethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, and 2,2-bis (4-hydroxyphenyl) propane. Is preferable. The bisphenol may be one kind or two or more kinds.

When the polyester resin contains a structural unit derived from a dicarboxylic acid other than the structural unit derived from an aromatic dicarboxylic acid, a structural unit derived from an aliphatic dicarboxylic acid is exemplified. Examples of the aliphatic dicarboxylic acid include succinic acid, adipic acid, suberic acid, sebacic acid, dodecanedioic acid and the like.

When the polyester resin contains a structural unit derived from a diol other than the structural unit derived from bisphenol, a structural unit derived from an aliphatic diol is exemplified. Aliphatic diols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,7-heptanediol. , 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, neopentyl glycol, diethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol and the like.

式（３−１）において、ｎは正の整数であり、３〜１０００００が好ましい。
上記式（３−１）で表される構造単位を含むポリエステル樹脂は、上記式（３−１）で表される構造単位を全構造単位の８０モル％以上の割合で含むことが好ましく、９０モル％以上の割合で含むことがより好ましい。他の構造単位としては、上述したテレフタル酸およびイソフタル酸以外の芳香族ジカルボン酸、脂肪族ジカルボン酸、２，２−ビス（４−ヒドロキシフェニル）プロパン以外のジオールが例示される。 The polyester resin used in the present invention is more preferably a polyester resin containing a structural unit represented by the following formula (3-1).

In formula (3-1), n is a positive integer, preferably 3 to 100,000.
The polyester resin containing the structural unit represented by the above formula (3-1) preferably contains the structural unit represented by the above formula (3-1) in a proportion of 80 mol% or more of all the structural units, 90. It is more preferable to include it in a proportion of mol% or more. Examples of other structural units include aromatic dicarboxylic acids other than terephthalic acid and isophthalic acid, aliphatic dicarboxylic acids, and diols other than 2,2-bis (4-hydroxyphenyl) propane.

The intrinsic viscosity of the (3) polyester resin used in the present invention is preferably in the range of 0.3 to 1.5 dL / g, more preferably 0.4 to 1.0 dL / g, and 0.4 to 0. 7 dL / g is more preferable, and 0.45 to 0.6 dL / g is even more preferable. Inherent viscosity is measured according to the method described in Examples described below. (3) By setting the intrinsic viscosity of the thermoplastic resin to 0.3 dL / g or more, the mechanical properties and heat resistance tend to be further improved. Further, by setting the intrinsic viscosity to 1.5 dL / g or less, discoloration during melt processing and deterioration of fluidity can be effectively suppressed.

(3) The glass transition temperature of the polyester resin is 160 ° C. or higher, preferably 170 ° C. or higher, more preferably 180 ° C. or higher, and even more preferably 185 ° C. or higher. The upper limit of the glass transition temperature is not particularly determined, but is, for example, 220 ° C. or lower, and further 210 ° C. or lower.

The polycarbonate resin composition of the present invention preferably contains the polyester resin (3) in the range of 5 to 70% by mass of the composition.
The polycarbonate resin composition of the present invention may contain only one type of the polyester resin (3) described above, or may contain two or more types of the polyester resin. When two or more types are included, the total amount is preferably in the above range.

<(1) Polycarbonate resin ~ (3) Polyester resin blend ratio>
The polycarbonate resin composition of the present invention has a mass ratio of (1) polycarbonate resin, (2) polycarbonate resin and (3) polyester resin of 10 to 80: 10 to 85: 5 to 70, and 10 to 75:12. It is preferably ~ 83: 5 to 70, more preferably 10 to 70: 12 to 83: 5 to 70, further preferably 10 to 65: 15 to 83: 5 to 70, and 30 to 13 to It is even more preferably 60: 15-30: 10-10. However, the total of the above (1) polycarbonate resin to (3) polyester resin is 100 parts by mass. Within such a range, the effect of the present invention is more effectively exhibited.
The polycarbonate resin composition of the present invention has the mass ratio of (1) polycarbonate resin to (3) polyester resin, (1) polycarbonate resin / (3) polyester resin is 1.0 or more, and / or It is preferable that (2) polycarbonate resin / (3) polyester resin, which is the mass ratio of (2) polycarbonate resin and (3) polyester resin, is less than 1.0. Within such a range, the effect of the present invention is more effectively exhibited.
In the polycarbonate resin composition of the present invention, the total amount of the above (1) polycarbonate resin to (3) polyester resin preferably occupies 90% by mass or more, more preferably 95% by mass or more, and further 98% by mass. Percentage or more, particularly 99% by mass or more.

<Other ingredients>
The polycarbonate 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.
Examples of the resin additive include a mold release agent, a stabilizer (heat stabilizer, antioxidant, etc.), an ultraviolet absorber, an antistatic agent, a flame retardant, a flame retardant aid, a dye, a pigment, an antifogging agent, and a lubricant. , Antiblocking agents, fluidity improvers, plasticizers, dispersants, antibacterial agents and the like. In addition, 1 type may be contained in the resin additive, and 2 or more types may be contained in arbitrary combinations and ratios.

<< Release agent >>
Examples of the release agent include an aliphatic carboxylic acid, an ester of an aliphatic carboxylic acid and an alcohol, an aliphatic hydrocarbon compound having a number average molecular weight of 200 to 15,000, and a polysiloxane-based silicone oil.

Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic monovalent, divalent or trivalent carboxylic acids. Here, the aliphatic carboxylic acid also includes an alicyclic carboxylic acid. Among these, the preferred aliphatic carboxylic acid is a monovalent or divalent carboxylic acid having 6 to 36 carbon atoms, and an aliphatic saturated monovalent carboxylic acid having 6 to 36 carbon atoms is more preferable. Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, caproic acid, caproic acid, lauric acid, araquinic acid, behenic acid, lignoceric acid, cerotic acid, melissic acid, tetraliacontanic acid, montanic acid, and adipine. Examples include acid and azelaic acid.

As the aliphatic carboxylic acid in the ester of the aliphatic carboxylic acid and the alcohol, for example, the same one as the above-mentioned aliphatic carboxylic acid can be used. On the other hand, examples of alcohols include saturated or unsaturated monohydric or polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these, monohydric or polyhydric saturated alcohols having 30 or less carbon atoms are preferable, and aliphatic saturated monohydric alcohols or aliphatic saturated polyhydric alcohols having 30 or less carbon atoms are more preferable. Here, the aliphatic term also contains an alicyclic compound.

Specific examples of such alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol and the like. Can be mentioned.

The above ester may contain an aliphatic carboxylic acid and / or an alcohol as impurities. Further, the above ester may be a pure substance or a mixture of a plurality of compounds. Further, the aliphatic carboxylic acid and the alcohol which are combined to form one ester may be used alone or in any combination and ratio of two or more.

Specific examples of esters of aliphatic carboxylic acid and alcohol include beeswax (a mixture containing myricyl palmitate as a main component), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, and glycerin monosteer. Examples thereof include rate, glycerin distearate, glycerin tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate and the like.

Examples of the aliphatic hydrocarbon compound having a number average molecular weight of 200 to 15,000 include liquid paraffin, paraffin wax, microwax, polyethylene wax, fisher-tropus wax, α-olefin oligomer having 3 to 12 carbon atoms, and the like. .. Here, the aliphatic hydrocarbon compound also includes an alicyclic hydrocarbon. Moreover, these hydrocarbons may be partially oxidized.

Among these, paraffin wax, polyethylene wax or a partial oxide of polyethylene wax is preferable, and paraffin wax and polyethylene wax are more preferable.
The number average molecular weight of the aliphatic hydrocarbon is preferably 5,000 or less.
The aliphatic hydrocarbon may be a single substance, but a mixture of various constituents and molecular weights can be used as long as the main component is within the above range.

The content of the mold release agent in the polycarbonate resin composition of the present invention is usually 0.001 part by mass or more, preferably 0.001 part by mass or more, based on 100 parts by mass of the total of the polycarbonate resin component and other resin components blended as needed. It is 0.01 parts by mass or more, and is usually 2 parts by mass or less, preferably 1 part by mass or less, and more preferably 0.6 parts by mass or less. By setting the content of the release agent to be equal to or higher than the lower limit of the above range, the effect of mold release property is effectively exhibited, and by setting the content to be equal to or lower than the upper limit of the above range, the hydrolysis resistance is lowered and injection molding is performed. It is possible to more effectively suppress mold contamination at the time. A molded product with high transparency can be obtained regardless of the content of the release agent, but the hardness and heat resistance tend to decrease when the upper limit of the above range is exceeded.
The release agent may contain only one type, or may contain two or more types. When two or more types are included, the total amount is preferably in the above range.

<< 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 include phosphoric acid, phosphonic acid, phosphite, phosphinic acid, polyphosphoric acid and other phosphorus oxo acids; acidic sodium pyrophosphate, potassium pyrophosphate, acidic calcium pyrophosphate and other acidic pyrophosphate metal salts; phosphoric acid. Phosphates of Group 1 or Group 2B metals such as potassium, sodium phosphate, cesium phosphate, zinc phosphate; organic phosphate compounds, organic phosphite compounds, organic phosphonite compounds, etc. Especially preferable.

Examples of the organic phosphite compound include triphenyl phosphite, 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 "ADEKA STAB 1178", "ADEKA STAB 2112", "ADEKA STAB HP-10" manufactured by ADEKA, and "JP-351" and "JP-351" manufactured by Johoku Chemical Industry Co., Ltd. Examples thereof include "JP-360", "JP-3CP", and "Irgafos 168" manufactured by BASF Corporation.

Examples of the antioxidant include hindered phenol-based stabilizers.
Specific examples of hindered phenol-based stabilizers 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''-(mesitylen-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-Triazin-2-ylamino) phenol, 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate and the like. Be done.

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

The content of the stabilizer in the polycarbonate resin composition of the present invention is usually 0.001 part by mass or more, preferably 0, based on 100 parts by mass of the total of the polycarbonate resin component and other resin components blended as needed. It is .005 parts by mass or more, more preferably 0.01 parts by mass or more, and 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 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 polycarbonate resin composition>
The polycarbonate resin composition of the present invention can achieve a low haze. For example, the haze of a molded product obtained by molding the polycarbonate resin composition of the present invention into a thickness of 2 mm can be 10% or less, and further 7.0% or less, 5.0% or less, 3.0% or less, It can be 2.0% or less. The ideal lower limit of haze is 0%, but 0.3% or more, and even 0.5% or more is a practical level.
The polycarbonate resin composition of the present invention can achieve high hardness. For example, the pencil hardness measured according to ISO 15184 of the polycarbonate resin composition of the present invention can be HB or higher, and further can be F or higher. The upper limit of the pencil hardness is not particularly defined, but for example, 3H or less, further 2H or less, particularly H or less is a practical level. The pencil hardness increases in the order of 3B, 2B, B, HB, F, H, 2H, and 3H.
The polycarbonate resin composition of the present invention can achieve excellent heat resistance. For example, the deflection temperature under load measured according to ISO 75-2 of the polycarbonate resin composition of the present invention can be 115 ° C. or higher, and further 120 ° C. or higher, 124 ° C. or higher, 126 ° C. or higher. it can. The upper limit of the deflection temperature under load is not particularly defined, but for example, even at 140 ° C. or lower, and further at 135 ° C. or lower, it is at a practical level.
The polycarbonate resin composition of the present invention preferably satisfies all of the above haze, pencil hardness and deflection temperature under load.

<Manufacturing method of polycarbonate resin composition>
The method for producing the polycarbonate resin composition of the present invention is not limited, and a known method for producing the polycarbonate resin composition can be widely adopted, and the above-mentioned (1) polycarbonate resin to (3) polyester resin and, if necessary, blended. Other components are premixed using various mixers such as tumblers and henschel mixers, and then melted with mixers such as Banbury mixers, rolls, brabenders, single-screw kneading extruders, twin-screw kneading extruders, and kneaders. There is a method of kneading. In this case, the screw rotation speed, extrusion temperature, and extrusion resin temperature in the melt-kneading step are preferably in the same range as the screw rotation speed, extrusion temperature, and extrusion resin temperature in the first melt-kneading step described later.

In the polycarbonate resin composition of the present invention, (1) a polycarbonate resin and (3) a polyester resin are melt-kneaded (hereinafter, this step may be referred to as a "first melt-kneading step"), and further (2). ) It is preferable to add a polycarbonate resin and melt-knead (hereinafter, this step may be referred to as a "second melt-kneading step") to produce the product. By adopting such a method, a resin composition having more excellent transparency can be obtained.

The rotation speed of the screw in the first melt-kneading step is preferably 50 to 1000 rpm, more preferably 70 to 800 rpm, and even more preferably 100 to 500 rpm.
Further, the extrusion temperature in the first melt-kneading step is preferably 270 ° C. or higher, more preferably 280 ° C. or higher, further preferably 290 ° C. or higher, and further preferably 300 ° C. or higher. It is more preferably 310 ° C. or higher, and even more preferably 315 ° C. or higher. The upper limit of the extrusion temperature is preferably 350 ° C. or lower, more preferably 340 ° C. or lower, and even more preferably 330 ° C. or lower.
Here, the extrusion temperature means the set temperature of the barrel in the extruder.

The extruded resin temperature in the first melt-kneading step is preferably 280 ° C. or higher, more preferably 290 ° C. or higher, further preferably 300 ° C. or higher, and preferably 310 ° C. or higher. It is even more preferably 320 ° C. or higher, even more preferably 325 ° C. or higher. The upper limit of the extruded resin temperature is preferably 360 ° C. or lower, more preferably 350 ° C. or lower, and even more preferably 340 ° C. or lower.
Here, the extruded resin temperature means the temperature of the resin immediately before entering the die hole of the extruder, and is measured according to the method described in Examples described later.

The rotation speed of the screw in the second melt-kneading step is preferably 50 to 1000 rpm, more preferably 70 to 800 rpm, and even more preferably 100 to 500 rpm.
The extrusion temperature in the second melt-kneading step is preferably 230 ° C. or higher, more preferably 240 ° C. or higher, further preferably 245 ° C. or higher, and further preferably 250 ° C. or higher. Preferably, it is more preferably 255 ° C. or higher, further preferably 260 ° C. or higher, and may be 270 ° C. or higher. The upper limit of the extrusion temperature is preferably 350 ° C. or lower, more preferably 340 ° C. or lower, further preferably 330 ° C. or lower, 320 ° C. or lower, 310 ° C. or lower, 300 ° C. or lower, 290 ° C. or lower. It may be below ° C.

The extruded resin temperature in the second melt-kneading step is preferably 240 ° C. or higher, more preferably 250 ° C. or higher, further preferably 255 ° C. or higher, and more preferably 260 ° C. or higher. It is even more preferably 265 ° C. or higher, even more preferably 270 ° C. or higher, and may be 280 ° C. or higher and 290 ° C. or higher. The upper limit of the extruded resin temperature is preferably 360 ° C. or lower, more preferably 350 ° C. or lower, further preferably 340 ° C. or lower, and 330 ° C. or lower, 320 ° C. or lower, 310 ° C. or lower. There may be.

An embodiment of the above manufacturing method includes an embodiment in which (1) a polycarbonate resin and (3) a thermoplastic resin are melt-kneaded and pelletized, and then the pellets and (2) a polycarbonate resin are melt-kneaded. .. Once pelletized, the transparency of the obtained polycarbonate resin composition can be further enhanced.
On the other hand, it is not always essential that (1) the polycarbonate resin and (3) the thermoplastic resin are melt-kneaded and then pelletized. For example, after melt-kneading (1) a polycarbonate resin and (3) a thermoplastic resin, (2) a polycarbonate resin may be added and melt-kneaded as it is by side feed.

The difference in extrusion temperature between the first melt-kneading step and the second melt-kneading step in the above manufacturing method is preferably 0 to 70 ° C, more preferably 10 to 60 ° C, and 20 to 50 ° C. Is more preferable.
The difference in the extruded resin temperature between the first melt-kneading step and the second melt-kneading step in the above manufacturing method is preferably 0 to 70 ° C, more preferably 5 to 60 ° C, and 10 It is more preferably ~ 50 ° C.
In the above manufacturing method, the ratio of the melt-kneading time of the first melt-kneading step and the second melt-kneading step is preferably 10: 1 to 1:10, and preferably 5: 1 to 1: 5. More preferred.
The melt-kneading time refers to the time from feeding the raw material resin to the extruder to extrusion. However, (2) when the polycarbonate resin is side-fed, the first melt-kneading time refers to the time from feeding the raw material resin to the extruder to the side-feeding, and the second melt-kneading time is (2). 2) The time from side feeding of polycarbonate resin to extruding.
The production method may further include a step of pelletizing after the second melt-kneading step.

<Molded product>
The above-mentioned polycarbonate resin composition (for example, pellets) is molded by various molding methods to obtain a molded product.
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, plate-shaped, plate-shaped, rod-shaped, sheet-shaped, film-shaped, cylindrical, annular, etc. Examples thereof include a circular shape, an elliptical shape, a polygonal shape, a deformed product, a hollow product, a frame shape, a box shape, and a panel shape.

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-assisted hollow molding method, blow molding method, extrusion blow molding, IMC (in-mold coating molding) molding method, rotary molding method, multi-layer molding method, two-color molding method, insert molding method, sandwich molding method, foam molding method , Pressure molding method and the like.
Above all, molding is preferably performed by an injection molding method, and for example, injection molding is performed using a known injection molding machine such as an injection molding machine, an ultra-high speed injection molding machine, or an injection compression molding machine. The cylinder set temperature of the injection molding machine at the time of injection molding is preferably 240 to 380 ° C, more preferably 260 to 360 ° C. The injection speed during injection molding is preferably 10 to 1,000 mm / sec, more preferably 10 to 500 mm / sec.

The molded product of the present invention is obtained by molding the polycarbonate resin composition of the present invention. The molded product of the present invention is suitably used for parts such as electrical and electronic equipment, OA equipment, mobile information terminals, mechanical parts, home appliances, vehicle parts, various containers, lighting equipment, and the like. Among these, it is particularly preferably used for housings of electrical and electronic equipment, OA equipment, information terminal equipment and home appliances, lighting equipment and vehicle parts (particularly vehicle interior parts), and surface film such as smartphones and touch panels.

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 (1) -3>
Bisphenol A (BPA) (manufactured by Mitsubishi Chemical Corporation) 33.49 kg (about 147 mol) and diphenyl carbonate (DPC) (manufactured by Mitsubishi Chemical Corporation) 32.20 kg (about 150 mol) with an aqueous solution of cesium carbonate and cesium carbonate as a dihydroxy compound. The mixture was adjusted by adding 0.5 μmol per 1 mol. Next, the mixture was put into a first reactor having a content of 200 L equipped with a stirrer, a heat medium jacket, a vacuum pump, and a reflux condenser.
Next, the inside of the first reactor was depressurized to 1.33 kPa (10 Torr), and then the operation of restoring the pressure to atmospheric pressure with nitrogen was repeated 5 times to replace the inside of the first reactor with nitrogen. After the nitrogen substitution, the internal temperature of the first reactor was gradually raised through a heat medium having a temperature of 230 ° C. in a heat medium jacket to dissolve the mixture. Then, the stirrer was rotated at 55 rpm to control the temperature inside the heat medium jacket, and the internal temperature of the first reactor was maintained at 220 ° C. Then, while distilling off the phenol produced by the oligomerization reaction of BPA and DPC performed inside the first reactor, the pressure inside the first reactor was increased to 101.3 kPa (760 Torr) in absolute pressure over 40 minutes. The pressure was reduced from 1 to 13.3 kPa (100 Torr).
Subsequently, the transesterification reaction was carried out for 80 minutes while maintaining the pressure in the first reactor at 13.3 kPa and further distilling off phenol.
After that, the inside of the system is restored to 101.3 kPa with nitrogen in absolute pressure, boosted to 0.2 MPa with gauge pressure, and the oligomer in the first reactor is passed through a transfer pipe preheated to 200 ° C. or higher. Was pumped to the second reactor. The second reactor had an internal capacity of 200 L, was equipped with a stirrer, a heat medium jacket, a vacuum pump, and a reflux condenser, and controlled the internal pressure to atmospheric pressure and the internal temperature to 240 ° C.
Next, the oligomer pressure-fed into the second reactor is stirred at 16 rpm, the internal temperature is raised with a heat medium jacket, and the inside of the second reactor is passed through the second reactor at an absolute pressure of 101.3 kPa to 13.3 kPa over 40 minutes. The pressure was reduced to. Then, the temperature was continuously raised, and the internal pressure was reduced from 13.3 kPa to 399 Pa (3 Torr) in absolute pressure over another 40 minutes to remove the distilled phenol from the system. Further, the temperature was continuously raised, and after the absolute pressure in the second reactor reached 70 Pa (about 0.5 Torr), 70 Pa was maintained and the polycondensation reaction was carried out. The final internal temperature in the second reactor was 285 ° C. The polycondensation reaction was terminated when the stirrer of the second reactor became a predetermined stirring power.
Next, the inside of the second reactor is restored to an absolute pressure of 101.3 kPa with nitrogen, and the pressure is increased to 0.2 MPa with a gauge pressure, and the polycarbonate resin is extracted from the bottom of the second reactor in a strand shape to form a water tank. The polycarbonate resin (1) -3 was obtained by pelletizing using a rotary cutter while cooling with. The viscosity average molecular weight of the obtained polycarbonate resin (1) -3 was 20,000.

<Manufacturing Example 2: Production of Polycarbonate Resin (2)>
26.14 mol (6.75 kg) of 2,2-bis (3-methyl-4-hydroxyphenyl) propane (BPC) and 26.79 mol (5.74 kg) of diphenyl carbonate were added to a stirrer and distillate condensing device. The reactor was placed in a SUS reactor (internal volume of 10 liters), the inside of the reactor was replaced with nitrogen gas, and the temperature was raised to 220 ° C. over 30 minutes in a nitrogen gas atmosphere.
Next, the reaction solution in the reactor was stirred, and cesium carbonate (Cs ₂ CO ₃ ) as a transesterification reaction catalyst was added to the reaction solution in the 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 in 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 out phenol.
Next, the temperature inside the reactor was raised to 284 ° C. over 60 minutes and the pressure was reduced to 3 Torr to distill off phenol corresponding to almost the entire theoretical amount of distillation. Next, the pressure in the reactor was kept below 1 Torr at 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 the polycarbonate resin (2).

The following measurements were carried out on the thermoplastic resin ((1) polycarbonate resin, (2) polycarbonate resin and (3) polyester resin) which are the raw materials.

<Measurement of viscosity average molecular weight (Mv)>
For the viscosity average molecular weight (Mv) of the thermoplastic 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 an Ubbelohde viscometer. Calculated from the viscosity formula.
η = 1.23 × 10 ^-4 Mv ^0.83

<Measurement of pencil hardness>
After the thermoplastic resin pellets are dried at 100 ° C. for 5 hours, an injection molding machine (“J55-60H” manufactured by Japan Steel Works, Ltd.) is used to set the cylinder temperature for (1) polycarbonate resin and (2) polycarbonate resin. At 260 ° C. and a mold temperature of 80 ° C., (3) the polyester resin is flat under the conditions of a cylinder set temperature of 340 ° C., a mold temperature of 80 ° C., a screw rotation speed of 100 rpm and an injection speed of 100 mm / sec. A test piece (90 mm × 50 mm × 2 mm thickness) was prepared. With respect to this flat plate-shaped test piece, the pencil hardness measured under a load of 750 g was determined using a pencil hardness tester (manufactured by Toyo Seiki Co., Ltd.) in accordance with ISO 15184.

<Measurement of terminal hydroxyl group amount>
The unit of the amount of terminal hydroxyl groups is the mass of the amount of terminal hydroxyl groups expressed in ppm with respect to the mass of the polycarbonate resin. The measuring method was according to the colorimetric determination by the titanium tetrachloride / acetic acid method (the method described in Macromol. Chem. 88 215 (1965)). In Table 1 above, it is shown as "OH group amount". The total amount of terminal hydroxyl groups after mixing of the two types (1) polycarbonate resins was calculated as a mass average by the mixing ratio and is shown in Table 2.

<Measurement of intrinsic viscosity>
1.0 g of the sample was dissolved in 100 mL of 1,1,2,2-tetrachloroethane to prepare a solution having a temperature of 25 ° C. Inherent viscosity (unit: dL / g) using the obtained solution was measured using an Ubbelohde type viscosity tube based on ISO1624-1.

<Measurement of glass transition temperature>
The glass transition temperature of the thermoplastic resin was measured in accordance with JIS K7122 by performing two cycles of raising and lowering the temperature according to the following DSC measurement conditions. As a measuring device, a differential scanning calorimeter (DSC, manufactured by Shimadzu Corporation, "DSC-60") was used.
Measurement start temperature: 25 ° C
Temperature rise rate: 10 ° C / min Reach temperature: 300 ° C
Temperature drop rate: 5 ° C / min

2. Production of Polycarbonate Resin Composition Pellets Example 1, Comparative Example 1 and Comparative Example 2
The (1) polycarbonate resin, (3) polyester resin, stabilizer and mold release agent described in Table 1 above are blended in the proportions shown in Table 2 below (all indicated by parts by mass), and the tumbler mixer is used. After mixing uniformly, using a twin-screw extruder (TEX30α manufactured by Nippon Steel Co., Ltd.), the first extrusion temperature and the first extrusion resin temperature and rotation speed shown in Table 2 and the discharge amount are 30 kg / hr. From the barrel at the upstream part of the extruder, the mixture was fed to the extruder to obtain polycarbonate resin composition pellets. Further, the obtained polycarbonate resin composition pellets and (2) polycarbonate resin were blended in the proportions shown in Table 2 below, mixed uniformly with a tumbler mixer, and then the twin-screw extruder was operated again. The polycarbonate resin composition pellets were fed to the extruder from the barrel at the upstream portion of the extruder at the second extrusion temperature and the second extrusion resin temperature and the number of revolutions shown in Table 2 and at a discharge rate of 30 kg / hr. Obtained. The kneading time was adjusted so that the ratio of the melt-kneading time of the first melt-kneading step and the second melt-kneading step was 1: 1.
Here, the first extrusion temperature and the second extrusion temperature mean the set temperature of the barrel in the extruder, and the first extrusion resin temperature and the second extrusion resin temperature are the resin temperatures immediately before entering the die hole of the extruder. Means and was measured by inserting a thermocouple into the die. The unit of these temperatures is ° C. The rotation speed is the screw rotation speed, and is the same rotation speed for the first extrusion and the second extrusion.

<Measurement of HAZE>
After the polycarbonate resin composition pellets obtained above are dried at 100 ° C. for 5 hours, an injection molding machine (“J55-60H” manufactured by Japan Steel Works, Ltd.) is used to set a cylinder temperature of 300 ° C. and a mold temperature of 80. A flat plate-shaped test piece having a thickness of 90 mm × 50 mm × 2 mm was injection-molded under the conditions of ° C., screw rotation speed of 100 rpm, and injection speed of 100 mm / sec. 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.

<Measurement of pencil hardness>
After the polycarbonate resin composition pellets obtained above are dried at 100 ° C. for 5 hours, an injection molding machine (“J55-60H” manufactured by Japan Steel Works, Ltd.) is used to set a cylinder temperature of 300 ° C. and a mold temperature of 80. A flat plate-shaped test piece having a thickness of 90 mm × 50 mm × 2 mm was injection-molded under the conditions of ° C., screw rotation speed of 100 rpm, and injection speed of 100 mm / sec. The obtained flat plate-shaped test piece was measured by the same method as the measurement of the pencil hardness of the thermoplastic resin as the raw material.

<Measurement of heat resistance (deflection temperature under load, DTUL)>
The polycarbonate resin composition pellets obtained above are dried at 100 ° C. for 5 hours, and then used with an injection molding machine (“J55-60H” manufactured by Japan Steel Works, Ltd.) to set a cylinder temperature of 300 ° C. and a mold temperature of 80 ° C. , Injection molding was performed under the conditions of an injection time of 2 seconds and a molding cycle of 40 seconds, and an ISO multipurpose test piece (4 mm thick) was injection molded. The deflection temperature under load was measured under the condition of load 1.80 MPa according to ISO75-1 and ISO75-2. The unit is shown in ° C.

As is clear from Table 2 above, the polycarbonate resin composition of the present invention had a low haze, a high pencil hardness, and excellent heat resistance (Example 1).
On the other hand, (1) when a polycarbonate resin having a low amount of terminal hydroxyl groups is used (Comparative Example 1, Comparative Example 2). The haze has become much higher.

Since the polycarbonate resin composition of the present invention is a material having high surface hardness, high transparency, and excellent heat resistance, it is an electric / electronic device, an OA device, a mobile information terminal, a mechanical part, a home appliance, a vehicle, and the like. It is suitably used for parts, various containers, parts such as lighting equipment, and the like. Among these, in particular, it can be suitably used for housings of electrical and electronic equipment, OA equipment, information terminal equipment and home appliances, lighting equipment and vehicle parts (particularly vehicle interior parts), and surface film such as smartphones and touch panels, and is industrial. The above usability is very high.

Claims (7)

(1) A polycarbonate resin containing a structural unit represented by the following formula (1) in an amount of more than 50 mol%.
(2) A polycarbonate resin containing 50 mol% or more of the structural unit represented by the following formula (2), and
(3) Contains a polyester resin having a glass transition temperature of 160 ° C. or higher.
The amount of the terminal hydroxyl group of the (1) polycarbonate resin is 700 to 1600 mass ppm.
The weight ratio of the (1) polycarbonate resin, (2) polycarbonate resin and (3) polyester resin is 30 to 60: 15 to 30: 10 to 40 (however, the total is 100 parts by mass), and the polycarbonate resin composition. Stuff;

In equation (1), X ¹ represents one of the following equations.

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

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

R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group, and Z combines with C to form an alicyclic hydrocarbon having 6 to 12 carbon atoms and which may have a substituent. Represents a group. The polycarbonate resin composition according to claim 1, ^{wherein X 1} in the formula (1) is represented by the following formula;

In the above formula, R ³ and R ⁴ are methyl groups. The polycarbonate resin composition according to claim 1 or 2, wherein ^{R 2} in the formula (2) is a hydrogen atom. (2) The polycarbonate resin composition according to any one of claims 1 to 3, wherein the pencil hardness of the polycarbonate resin measured according to ISO 15184 is H or more. The polycarbonate resin composition according to any one of claims 1 to 4, wherein the glass transition temperature of the polyester resin (3) is 160 to 220 ° C. The haze of the molded product obtained by molding the polycarbonate resin composition to a thickness of 2 mm is 10% or less, the pencil hardness measured according to ISO 15184 is HB or more, and the deflection temperature under load measured according to ISO 75-2 is 115 ° C. or more. The polycarbonate resin composition according to any one of claims 1 to 5. A molded product obtained by molding the polycarbonate resin composition according to any one of claims 1 to 6.