JP7105583B2 - Polycarbonate resin composition and molded article - Google Patents

Description

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

Polycarbonate resins are excellent in strength and electrical properties, and the molded products obtained are excellent in dimensional stability, etc. Therefore, they are used in housings of electric and electronic equipment, interior parts for automobiles, and precision molded parts. It is widely used as a raw material resin for manufacturing, and in particular, it can be used to produce products with high commercial value, taking advantage of its beautiful appearance, such as parts for home appliances, electronic devices, and liquid crystal display devices.

（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）と同義である。） For example, in Patent Document 1, a polycarbonate resin (A) having a viscosity average molecular weight (Mv) of 20,000 to 35,000 having a structural unit of the following general formula (1) 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 at a mass ratio of (A) / (B) of 80/20 to 20/80, according to ASTM D2794 A polycarbonate resin composition is disclosed which has a measured DuPont impact strength of 10 J or more at 25° C. and a pencil hardness of F or more measured according to JIS K5600.

(In 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, Z represents a group that forms an optionally substituted alicyclic hydrocarbon having 6 to 12 carbon atoms in combination with C . )

(X in general formula (2) has the same meaning as in general formula (1).)

JP 2013-064045 A

However, when examining the above Patent Document 1, it was found that it is not necessarily suitable for applications where heat resistance is required.
An object of the present invention is to solve such problems, and to provide a polycarbonate resin composition that is comprehensively excellent in surface hardness, transparency and heat resistance, and a molded article molded from the polycarbonate resin composition. intended to provide

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＞前記式（１）におけるＲ²がいずれも水素原子である、＜１＞に記載のポリカーボネート樹脂組成物。
＜３＞前記（１）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＞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ガラス転移温度が１６０～２２０℃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（２）ポリカーボネート樹脂は、下記式（２）で表される構造単位を含むポリカーボネート樹脂である、＜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；
式（２）

式（２）中、Ｒ⁵～Ｒ⁸は、それぞれ独立に、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、炭素数１～９のアルキル基、炭素数６～１２のアリール基、炭素数１～５のアルコキシ基、炭素数２～５のアルケニル基または炭素数７～１７のアラルキル基を表す；ｎ１、ｎ２およびｎ３は、それぞれ独立に、０～４の整数を表す。
＜６＞＜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を成形してなる成形品。 Based on the above problems, as a result of investigation by the present inventor, a polycarbonate resin having a high glass transition temperature and a relatively small viscosity average molecular weight was blended with the polycarbonate resin represented by the general formula (1). , and found that a polycarbonate resin composition having overall excellent surface hardness, transparency and heat resistance can be obtained by adjusting the blending amounts thereof, thereby completing the present invention. Specifically, the above problems have been solved by the following means <1>, preferably by <2> to <6>.
<1> (1) a polycarbonate resin containing 50 mol% or more of a structural unit represented by the following formula (1), and (2) a polycarbonate resin having a glass transition temperature of 160°C or higher, and The mass ratio of the resin and (2) polycarbonate resin is 10 to 90:90 to 10 (the total is 100 parts by mass), and (2) the polycarbonate resin has a viscosity average molecular weight of 1,000 to 18,000. a polycarbonate resin composition;
formula (1)

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

R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group, and Z is combined with C to form an alicyclic hydrocarbon having 6 to 12 carbon atoms, which may have a substituent. represents a group.
<2> The polycarbonate resin composition according to <1>, wherein all R ² in the formula (1) are hydrogen atoms.
<3> The polycarbonate resin composition according to <1> or <2>, wherein the polycarbonate resin (1) has a pencil hardness of H or higher as measured according to ISO 15184.
<4> The polycarbonate resin composition according to any one of <1> to <3>, wherein the polycarbonate resin (2) has a glass transition temperature of 160 to 220°C.
<5> The polycarbonate resin composition according to any one of <1> to <4>, wherein the (2) polycarbonate resin is a polycarbonate resin containing a structural unit represented by the following formula (2);
formula (2)

In formula (2), R ⁵ to R ⁸ each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 9 carbon atoms, an aryl group having 6 to 12 carbon atoms, represents an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an aralkyl group having 7 to 17 carbon atoms;
<6> A molded article obtained by molding the polycarbonate resin composition according to any one of <1> to <5>.

INDUSTRIAL APPLICABILITY According to the present invention, it has become possible to provide a polycarbonate resin composition which is comprehensively excellent in surface hardness, transparency and heat resistance, and a molded article molded from the polycarbonate resin composition.

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

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

Ｒ³およびＲ⁴は、それぞれ独立に、水素原子またはメチル基を表し、ＺはＣと結合して炭素数６～１２の、置換基を有していてもよい脂環式炭化水素を形成する基を表す。 The polycarbonate resin composition of the present invention comprises (1) a polycarbonate resin containing 50 mol% or more of a structural unit represented by the following formula (1), and (2) a polycarbonate resin having a glass transition temperature of 160°C or higher. , the mass ratio of the (1) polycarbonate resin and (2) the polycarbonate resin is 10 to 90:90 to 10 (the total is 100 parts by mass), and (2) the viscosity average molecular weight of the polycarbonate resin is 1, 000 to 18,000.
formula (1)

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

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

With the above structure, a polycarbonate resin composition and a molded article having high surface hardness, relatively low transparency, and high heat resistance can be obtained. is highly technically significant in that the transparency can be lowered even in a blend of two components of (1) polycarbonate resin and (2) polycarbonate resin.

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。 <(1) Polycarbonate Resin Containing Structural Unit Represented by Formula (1)>
The polycarbonate resin composition of the present invention includes (1) a polycarbonate resin containing 50 mol % or more of the structural unit represented by formula (1).
formula (1)

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

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

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

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

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

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

Preferred specific examples of the polycarbonate resin (1) include the following polycarbonate resins i) to iv).
i) those having a structural unit composed of 2,2-bis(3-methyl-4-hydroxyphenyl)propane, i.e., R ¹ is a methyl group, R ² is a hydrogen atom, X ¹ is --C(CH ₃ ) ₂ having a structural unit that is -,
ii) a structural unit composed of 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, ie R ¹ is a methyl group, R ² is a methyl group and X ¹ is --C(CH ₃ ) ₂ having a structural unit that is -,
iii) a structural unit composed of 2,2-bis(3-methyl-4-hydroxyphenyl)cyclohexane, ie a structural unit in which R ¹ is a methyl group, R ² is a hydrogen atom and X ¹ is a cyclohexylidene group having
iv) a structural unit composed of 2,2-bis(3-methyl-4-hydroxyphenyl)cyclododecane, ie R ¹ is a methyl group, R ² is a hydrogen atom and X ¹ is a cyclododecylidene group Those with structural units.
Among these, the above i), ii) and iii) are preferred, the above i) and iii) are more preferred, and the above i) is even more preferred.

In the present invention, (1) 50 mol % or more of the structural units constituting the polycarbonate resin are contained. preferably greater than 50 mol%, more preferably 60 mol% or more, even more preferably 70 mol% or more, even more preferably 80 mol% or more, even more preferably 90 mol% or more, even more preferably 95 mol % or more are structural units represented by formula (1).
The (1) polycarbonate resin may contain only one type of structural unit represented by formula (1), or may contain two or more types thereof. When two or more types are included, the total amount is preferably within the above range.

The (1) polycarbonate resin may have structural units other than the structural unit represented by the formula (1). Examples of dihydroxy compounds constituting such other structural units 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 Pentane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3- (1-methylethyl)phenyl)propane, 2,2-bis(4-hydroxy-3-tert-butylphenyl)propane, 2,2-bis(4-hydroxy-3-(1-methylpropyl)phenyl)propane , 2,2-bis(4-hydroxy-3-cyclohexylphenyl)propane, 2,2-bis(4-hydroxy-3-phenylphenyl)propane, 1,1-bis(4-hydroxyphenyl)decane, 1, 1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,1-bis(4-hydroxydiphenyl)phenylmethane, 1,1-bis(4- hydroxy-3-methylphenyl)cyclohexane, 1,1-bis(4-hydroxy-3,5-dimethylphenyl)cyclohexane, 1,1-bis(4-hydroxy-3-(1-methylethyl)phenyl)cyclohexane, 1,1-bis(4-hydroxy-3-tert-butylphenyl)cyclohexane, 1,1-bis(4-hydroxy-3-(1-methylpropyl)phenyl)cyclohexane, 1,1-bis(4-hydroxy -3-cyclohexylphenyl)cyclohexane, 1,1-bis(4-hydroxy-3-phenylphenyl)cyclohexane, 1,1-bis(4-hydroxy-3-methylphenyl)-1-phenylethane, 1,1- Bis(4 - hydroxy-3,5-dimethylphenyl)-1-phenylethane, 1,1-bis(4-hydroxy-3-(1-methylethyl)phenyl)-1-phenylethane, 1,1-bis (4-hydroxy-3-tert-butylphenyl)-1-phenylethane, 1,1-bis(4-hydroxy-3-(1-methylpropyl)phenyl)-1-phenylethane, 1,1-bis( 4-hydroxy-3-cyclohexylphenyl)-1-phenylethane, 1,1-bis(4-hydroxy-3-phenylphenyl)-1-phenylethane, 1,1-bis(4-hydroxyphenyl ) cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclooctane, 4,4′-(1,3-phenylenediisopropylidene)bisphenol, 4,4′-(1,4-phenylenediisopropylidene) bisphenol, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxyphenyl ether, 4 ,4′-dihydroxybiphenyl, 1,1-bis(4-hydroxyphenyl)-3,3-5-trimethylcyclohexane, 1,1-bis(4-hydroxy-6-methyl-3-tert-butylphenyl)butane .

In the above (1) polycarbonate resin, the copolymerization amount of structural units other than the structural unit represented by formula (1) is 50 mol% or less, preferably less than 50 mol%, more preferably 40 mol%. Below, 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 (1) polycarbonate resin may contain only one type of structural unit other than the structural unit represented by formula (1), or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

The lower limit of the viscosity-average molecular weight (Mv) of the polycarbonate resin (1) is preferably 15,000 or more, more preferably 17,000 or more, and more preferably more than 18,000. It is more preferably 19,000 or more, and even more preferably 20,000 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 or more, heat resistance and moldability are improved, and a molded product having high mechanical strength can be obtained. Further, by setting the content to the above upper limit or less, the fluidity of the molded product is improved, and thin molded products can be efficiently produced. Furthermore, by setting the viscosity-average molecular weight (Mv) within the range described above, it is possible to obtain a molded article having an excellent balance between high transparency and high hardness.
The viscosity-average molecular weight (Mv) is measured according to the method described in the examples below (the same applies to Mv hereinafter).
The viscosity-average molecular weight may be adjusted within the above range by blending two or more polycarbonate resins.

The above (1) polycarbonate resin preferably has a pencil hardness of H or higher, more preferably 2H or higher, still more preferably 2H to 3H, even more preferably 2H, as measured according to ISO 15184. . The pencil hardness is measured according to the method described in the examples below (the same applies to the pencil hardness below).

The polycarbonate resin (1) preferably has a glass transition temperature of 110° C. or higher, more preferably 115° C. or higher, and even more preferably 118° C. or higher. Although the upper limit of the glass transition temperature is not particularly defined, it is, for example, 140° C. or lower, and further 13° C. or lower. The glass transition temperature is measured according to the method described in the examples below (the same applies to the glass transition temperature below).

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

The polycarbonate resin composition of the present invention preferably contains (1) the polycarbonate resin in an amount of 10 to 90% by mass of the composition.
The polycarbonate resin composition of the present invention may contain only one type of the above (1) polycarbonate resin, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

<(2) Polycarbonate resin having a glass transition temperature of 160°C or higher>
The polycarbonate resin composition of the present invention contains (2) a polycarbonate resin having a glass transition temperature of 160° C. or higher and a viscosity average molecular weight (Mv) of 1000 to 18,000. Heat resistance can be improved by containing such a resin. Furthermore, by using a polycarbonate resin having a relatively small Mv, the compatibility with the above (1) polycarbonate resin can be improved, and the haze of the resulting molded article can be made relatively low.

式（２）中、Ｒ⁵～Ｒ⁸は、それぞれ独立に、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、炭素数１～９のアルキル基、炭素数６～１２のアリール基、炭素数１～５のアルコキシ基、炭素数２～５のアルケニル基または炭素数７～１７のアラルキル基を表す。
ｎ１、ｎ２およびｎ３は、それぞれ独立に、０～４の整数を表す。 The (2) polycarbonate resin is preferably a polycarbonate resin containing a structural unit represented by the following formula (2).
formula (2)

In formula (2), R ⁵ to R ⁸ each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 9 carbon atoms, an aryl group having 6 to 12 carbon atoms, It represents an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an aralkyl group having 7 to 17 carbon atoms.
n1, n2 and n3 each independently represent an integer of 0 to 4;

When R ⁵ to R ⁸ have carbon atoms, these carbon atoms are further substituted by alkyl groups having 1 to 5 carbon atoms, alkoxy groups having 1 to 5 carbon atoms, fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. It may have a substituent selected from atoms.
R ⁵ and R ⁷ each independently represents an alkyl group having 1 to 9 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or 7 carbon atoms. An aralkyl group having up to 17 carbon atoms is preferable, an alkyl group having 1 to 9 carbon atoms is more preferable, an alkyl group having 1 to 3 carbon atoms is even more preferable, and a methyl group is even more preferable. Moreover, it is preferable not to have a substituent.
R ⁶ is an alkyl group having 1 to 9 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an aralkyl group having 7 to 17 carbon atoms. is preferably an alkyl group having 1 to 9 carbon atoms or an aryl group having 6 to 12 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms or a phenyl group, a methyl group or a phenyl group is more preferably a group, and even more preferably a methyl group. When it has a substituent, it is preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and even more preferably a methyl group. However, it is preferred to have no substituents.
R ⁸ is an alkyl group having 1 to 9 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an aralkyl group having 7 to 17 carbon atoms. is preferred, an alkyl group having 1 to 9 carbon atoms is more preferred, an alkyl group having 1 to 3 carbon atoms is even more preferred, and a methyl group is even more preferred. Moreover, it is preferable not to have a substituent.
n1 and n2 are each independently preferably 0 to 2, more preferably 0 or 1, and still more preferably 0.
n3 is preferably 0 to 2, more preferably 0 or 1, and still more preferably 0.
The above (2) polycarbonate resin preferably contains 50 mol% or more of the structural unit represented by formula (2), more preferably more than 50 mol%, and even more preferably 60 mol% or more. is 70 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, and even more preferably 95 mol% or more, of the structural unit represented by formula (2).
The (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 within the above range.

上記式（２－１）におけるＲ⁵～Ｒ⁸ならびにｎ１、ｎ２およびｎ３は、それぞれ独立に、式（２）におけるＲ⁵～Ｒ⁸ならびにｎ１、ｎ２およびｎ３と同義であり、好ましい範囲も同様である。 Formula (2) is preferably represented by the following formula (2-1).
Formula (2-1)

R ⁵ to R ⁸ and n1, n2 and n3 in formula (2-1) above are each independently synonymous with R ⁵ to R ⁸ and n1, n2 and n3 in formula (2), and the preferred ranges are also the same. is.

The (2) polycarbonate resin may have structural units 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) the polycarbonate resin described above (provided that excluding those corresponding to structural units represented by formula (2)).

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

As the polycarbonate resin (2), 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,1-bis(4-hydroxyphenyl)-1-diphenylmethane, 1,1-bis( 4-hydroxy-3-methylphenyl)-1-diphenylmethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,1-bis(4-hydroxy-3-methylphenyl)-1-phenyl ethane, 1,1-bis(4-hydroxyphenyl)-1-diphenylmethane, 1,1-bis(4-hydroxy-3-methylphenyl)-1-diphenylmethane, 2,2-bis(4-hydroxy-3, 5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3-phenylphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxydiphenyl)phenylmethane , 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane, 1,1-bis(4-hydroxy-3,5-dimethylphenyl)cyclohexane, 1,1-bis(4-hydroxy-3-( 1-methylethyl)phenyl)cyclohexane, 1,1-bis(4-hydroxy-3-tert-butylphenyl)cyclohexane, 1,1-bis(4-hydroxy-3-(1-methylpropyl)phenyl)cyclohexane, 1,1-bis(4-hydroxy-3-cyclohexylphenyl)cyclohexane, 1,1-bis(4-hydroxy-3-phenylphenyl)cyclohexane, 1,1-bis(4-hydroxy-3-methylphenyl)- 1-phenylethane, 1,1-bis(4-hydroxy-3,5-dimethylphenyl)-1-phenylethane, 1,1-bis(4-hydroxy-3-(1-methylethyl)phenyl)-1 -phenylethane, 1,1-bis(4-hydroxy-3-tert-butylphenyl)-1-phenylethane, 1,1-bis(4-hydroxy-3-(1-methylpropyl)phenyl)-1- Phenylethane, 1,1-bis(4-hydroxy-3-cyclohexylphenyl)-1-phenylethane, 1,1-bis(4-hydroxy-3-phenylphenyl)-1-phenylethane, 1,1-bis (4-hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclooctane, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4- Hydroxy-3-methylphenyl)fluorene, 4,4'-dihydroxybiphenyl and 1,1-bis(4-hydroxyphenyl)-3,3-5-trimethylcyclohexane comprising a structural unit composed of a compound selected from Polycarbonate resins are preferred, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,1-bis(4-hydroxy-3-methylphenyl)-1-phenylethane, 1,1-bis(4 -Hydroxyphenyl)-1-diphenylmethane and 1,1-bis(4-hydroxy-3-methylphenyl)-1-diphenylmethane containing a structural unit composed of a compound selected from 1,1-bis(4-hydroxy-3-methylphenyl)-1-diphenylmethane. , 1,1-bis(4-hydroxyphenyl)-1-phenylethane are more preferred.

The viscosity-average molecular weight (Mv) of the polycarbonate resin (2) has a lower limit of 1,000 or more, preferably 5,000 or more, more preferably 6,000 or more, and 8,000 or more. and more preferably 10,000 or more. In addition, the upper limit of Mv is 18,000 or less, preferably 17,000 or less, more preferably 16,000 or less, further preferably 15,000 or less, and 14,000 It is more preferably 13,000 or less, and even more preferably 13,000 or less.
By setting the viscosity-average molecular weight to the above lower limit or more, heat resistance and moldability are improved, and a molded product having high mechanical strength can be obtained. Further, by setting the content to the above upper limit or less, the fluidity of the molded product is improved, and thin molded products can be efficiently produced. Furthermore, by setting the viscosity-average molecular weight (Mv) within the range described above, it is possible to obtain a molded article having an excellent balance between high transparency and high hardness.
The viscosity-average molecular weight may be adjusted within the above range by blending two or more polycarbonate resins.

The (2) polycarbonate resin has a pencil hardness measured according to ISO 15184 of, for example, B to F, and may be HB or higher.

(2) The glass transition temperature of the polycarbonate resin is 160°C or higher, more preferably 165°C or higher, even more preferably 168°C or higher, further preferably 170°C or higher, 173°C or higher, and 175°C. The temperature may be 180° C. or higher, or 185° C. or higher. Although the upper limit of the glass transition temperature is not particularly defined, it is, for example, 220° C. or lower, more preferably 210° C. or lower.

The polycarbonate resin composition of the present invention preferably contains (2) the polycarbonate resin in an amount of 10 to 90% by mass of the composition.
The polycarbonate resin composition of the present invention may contain only one type of the polycarbonate resin (2) above, or may contain two or more types thereof. When two or more types are included, the total amount is preferably within the above range.

<Blend ratio of (1) polycarbonate resin and (2) polycarbonate resin>
In the polycarbonate resin composition of the present invention, the mass ratio of (1) polycarbonate resin and (2) polycarbonate resin is 10 to 90:90 to 10, preferably 13 to 85:87 to 15, and 15 to It is more preferably 85:85-15, even more preferably 20-80:80-20, and even more preferably 25-75:75-25. However, the total of (1) polycarbonate resin and (2) polycarbonate resin is 100 parts by mass. By setting it as such a range, the effect of this invention is exhibited more effectively.
In the polycarbonate resin composition of the present invention, the total amount of the above (1) polycarbonate resin and (2) polycarbonate resin preferably accounts for 60% by mass or more, more preferably 65% by mass or more, and further preferably 70% by mass. % or more, particularly 90 mass % or more.

式（３）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。
上記Ｘ²は、上記式（１）で説明したＸ¹と同義であり、好ましい範囲も同様である。 <Other polycarbonate resins>
The polycarbonate resin composition of the present invention may contain a polycarbonate resin other than the above (1) polycarbonate resin and (2) polycarbonate resin.
Examples of other polycarbonate resins include polycarbonate resins containing more than 50 mol % of structural units represented by formula (3) (hereinafter sometimes referred to as "(3) polycarbonate resins").
Formula (3)

In formula (3), X ² represents any of the following formulas,

R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group, and Z is combined with C to form an alicyclic hydrocarbon having 6 to 12 carbon atoms, which may have a substituent. represents a group.
X ² above has the same meaning as X ¹ explained in formula (1) above, and the preferred range is also the same.

A preferred specific example of the structural unit represented by the above formula (3) is 2,2-bis(4-hydroxyphenyl)propane, that is, a structural unit (carbonate structural unit) composed of bisphenol-A.
In the present invention, (3) the polycarbonate resin contains more than 50 mol % of the structural unit represented by the above formula (3). 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, even more preferably 95 mol% % or more is the structural unit represented by the formula (3).
The (3) polycarbonate resin may contain only one type of structural unit represented by the formula (3), or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

The (3) polycarbonate resin may have structural units other than the structural unit represented by the formula (3). 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) the polycarbonate resin described above (provided that excluding those corresponding to structural units represented by formula (3)).

In the above (3) polycarbonate resin, the copolymerization amount of structural units other than the structural unit represented by formula (3) is less than 50 mol%, preferably 45 mol% or less, more preferably 40 mol%. Below, more preferably 30 mol % or less, still more preferably 20 mol % or less, even more preferably 10 mol % or less, and even more preferably 5 mol % or less.
The (3) polycarbonate resin may contain only one type of structural unit other than the structural unit represented by formula (3), or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

The lower limit of the viscosity-average molecular weight (Mv) of the polycarbonate resin (3) is preferably 9,000 or more, more preferably 10,000 or more, and further preferably 12,000 or more. Particularly preferably, it may be 15,000 or more, and more preferably 20,000 or more. Also, the upper limit of Mv is preferably 30,000 or less, more preferably 28,000 or less, and even more preferably 26,000 or less.
By setting the viscosity-average molecular weight to the above lower limit or more, moldability is further improved and a molded article having higher mechanical strength can be obtained. Further, by setting the content to the above upper limit or less, the fluidity of the molded product is further improved, and thin molded products can be produced more efficiently.
The viscosity-average molecular weight may be adjusted within the above range by blending two or more polycarbonate resins.

The (3) polycarbonate resin has a pencil hardness of 3B to B, more preferably 2B, measured according to ISO 15184.

The polycarbonate resin (3) preferably has a glass transition temperature of 120° C. or higher, more preferably 125° C. or higher, even more preferably 130° C. or higher, and even more preferably 135° C. or higher. , 140° C. or higher. Although the upper limit of the glass transition temperature is not particularly defined, it is usually less than 160°C, further 155°C or less, and particularly 150°C or less.

The method for producing the (3) polycarbonate resin is not particularly limited, and any known method can be employed. Examples thereof include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid-phase transesterification method of a prepolymer. Among these, the interfacial polymerization method and the melt transesterification method are preferred, and the interfacial polymerization method is more preferred.

When the polycarbonate resin composition of the present invention contains the polycarbonate resin (3), the content thereof is 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, and 15% by mass or more. is more preferred. The upper limit of the content is preferably 40% by mass or less, more preferably 35% by mass or less, and may be 30% by mass or less and 10% by mass or less.
The polycarbonate resin composition of the present invention may contain only one type of the polycarbonate resin (3) above, or may contain two or more types thereof. When two or more types are included, the total amount is preferably within the above range.

A preferable embodiment of the polycarbonate resin composition of the present invention includes a form in which 90% by mass or more (preferably 95% by mass or more, more preferably 99% by mass or more) of the resin component is polycarbonate resin.

<Other ingredients>
The polycarbonate resin composition of the present invention may optionally contain other components than those mentioned above as long as the desired physical properties are not significantly impaired. Examples of other components include thermoplastic resins other than the polycarbonate resins described above (for example, acrylic resins, etc.), various resin additives, and the like.
Examples of resin additives include release agents, stabilizers (heat stabilizers, antioxidants, etc.), ultraviolet absorbers, antistatic agents, flame retardants, flame retardant aids, dyes and pigments, antifog agents, lubricants, Antiblocking agents, fluidity improvers, plasticizers, dispersants, antibacterial agents and the like. One resin additive may be contained, or two or more resin additives may be contained in any combination and ratio.

式（Ｘ）中、Ｒ⁶、Ｒ⁷およびＲ⁸は、それぞれ独立に、水素原子または炭素数１～２０の炭化水素基を表し、Ｒ⁹は置換基を有していてもよい炭素数６～２０の芳香族炭化水素基、または、置換基を有していてもよい炭素数６～１７の芳香族炭化水素基で置換された炭素数１～３の脂肪族炭化水素基を表す。 <<Acrylic Resin>>
The polycarbonate resin composition of the present invention may contain an acrylic resin as another thermoplastic resin. The acrylic resin is preferably an acrylic resin having a structural unit represented by formula (X) below.
Formula (X)

In formula (X), R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ⁹ is optionally substituted C 6 represents an aromatic hydrocarbon group of up to 20 or an aliphatic hydrocarbon group of 1 to 3 carbon atoms substituted with an optionally substituted aromatic hydrocarbon group of 6 to 17 carbon atoms.

In addition to the above, the acrylic resin used in the present invention can employ those described in WO2014/038500, WO2013/094898, JP-A-2006-199774, and JP-A-2010-116501. , the contents of which are incorporated herein.
When the acrylic resin is blended, the blending amount is preferably in the range of 1 to 10% by mass of the polycarbonate resin composition of the present invention.

<< Release agent >>
Examples of release agents include aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15,000, and polysiloxane silicone oils.

Aliphatic carboxylic acids include, for example, saturated or unsaturated aliphatic monovalent, divalent or trivalent carboxylic acids. Here, the aliphatic carboxylic acid also includes alicyclic carboxylic acid. Among these, preferred aliphatic carboxylic acids are monovalent or divalent carboxylic acids having 6 to 36 carbon atoms, more preferably aliphatic saturated monovalent carboxylic acids having 6 to 36 carbon atoms. Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, melissic acid, tetralyacontanoic acid, montanic acid, and adipine. acid, azelaic acid, and the like.

As the aliphatic carboxylic acid in the ester of aliphatic carboxylic acid and alcohol, for example, the same aliphatic carboxylic acid as mentioned above can be used. Alcohols, on the other hand, include, for example, saturated or unsaturated monohydric or polyhydric alcohols. These alcohols may have substituents such as fluorine atoms and aryl groups. Among these, monohydric or polyhydric saturated alcohols having 30 or less carbon atoms are preferable, and aliphatic saturated monohydric alcohols or saturated aliphatic polyhydric alcohols having 30 or less carbon atoms are more preferable. In addition, an alicyclic compound is also included with an aliphatic here.

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. are mentioned.

The above esters may contain aliphatic carboxylic acids and/or alcohols as impurities. Further, the above ester may be a pure substance, or may be a mixture of a plurality of compounds. Furthermore, the aliphatic carboxylic acids and alcohols that are combined to form one ester may be used alone, or two or more of them may be used in any combination and ratio.

Specific examples of esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture containing myricyl palmitate as a main component), stearyl stearate (stearate stearate), behenyl behenate, stearyl behenate, glycerin mono Palmitate, glycerin monostearate, glycerin distearate, glycerin tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate, etc. be done.

Examples of aliphatic hydrocarbons having a number average molecular weight of 200 to 15,000 include liquid paraffin, paraffin wax, microwax, polyethylene wax, Fischer-Tropsch wax, and α-olefin oligomers having 3 to 12 carbon atoms. In addition, an alicyclic hydrocarbon is also contained as an aliphatic hydrocarbon here. Also, these hydrocarbons may be partially oxidized.

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

The content of the release agent in the polycarbonate resin composition of the present invention is usually 0.001 parts by mass or more, preferably 100 parts by mass in total of the polycarbonate resin component and other resin components blended as necessary. It is 0.01 parts by mass or more, and usually 2 parts by mass or less, preferably 1 part by mass or less, more preferably 0.6 parts by mass or less. By setting the content of the mold release agent to the lower limit value or more of the above range, the effect of mold releasability is effectively exhibited, and by setting the content to the upper limit value of the above range or less, hydrolysis resistance is lowered and injection molding is prevented. It is possible to more effectively suppress mold contamination and the like. Molded articles with excellent transparency can be obtained regardless of the content of the release agent.
Only one release agent may be contained, or two or more release agents may be contained. When two or more types are included, the total amount is preferably within the above range.

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

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

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

Among them, pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate preferable. Specific examples of such hindered phenol stabilizers 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 polycarbonate resin composition of the present invention is usually 0.001 part by mass or more, preferably 0, per 100 parts by mass in total of the polycarbonate resin component and other resin components blended as necessary. 005 mass parts or more, more preferably 0.01 mass parts or more, and usually 1 mass part or less, preferably 0.5 mass parts or less, more preferably 0.3 mass parts or less. By setting the content of the stabilizer within the above range, the effect of adding the stabilizer is exhibited more effectively.

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

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

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

<Characteristics of Polycarbonate Resin Composition>
The polycarbonate resin composition of the present invention can achieve low haze. For example, the haze of a molded product obtained by molding the polycarbonate resin composition of the present invention to a thickness of 2 mm can be 85% or less, further, 30% or less, 10% or less, 5.0% or less, 3.0%. % or less, 2.0% or less, or 1.0% or less. The lower limit of the haze is ideally 0%, but 0.1% or more, and even 0.3% or more are practical levels.
The polycarbonate resin composition of the present invention can achieve high hardness. For example, the pencil hardness of the polycarbonate resin composition of the present invention measured according to ISO 15184 can be HB or higher, and can be F or higher, H or higher, or 2H or higher. Although the upper limit of the pencil hardness is not particularly defined, for example, 3H or less, or even 2H or less is a practically significant level. The pencil hardness increases in 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 polycarbonate resin composition of the present invention can have a deflection temperature under load measured according to ISO 75-2 of 103° C. or higher, and further, 105° C. or higher, 108° C. or higher, 110° C. or higher, 113° C. or higher, It can be 115° C. or higher, or 120° C. or higher. Although the upper limit of the deflection temperature under load is not particularly defined, for example, 140° C. or less, or even 135° C. or less is a practical level.
The polycarbonate resin composition of the present invention preferably satisfies all of the haze, pencil hardness and deflection temperature under load.

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

<Molded product>
The above-described polycarbonate resin composition (for example, pellets) is molded by various molding methods to obtain molded articles.
The shape of the molded product is not particularly limited and can be appropriately selected according to the use and purpose of the molded product. , odd-shaped products, hollow products, frame-shaped products, box-shaped products, panel-shaped products, button-shaped products, and the like.

The method for molding the molded article is not particularly limited, and conventionally known molding methods can be employed, such as injection molding, injection compression molding, extrusion molding, profile extrusion, transfer molding, blow molding, Gas-assisted blow molding method, blow molding method, extrusion blow molding method, IMC (in-mold coating molding) method, rotational molding method, multi-layer molding method, two-color molding method, insert molding method, sandwich molding method, foam molding method , pressure molding, and the like.
Among them, the 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, a super high speed injection molding machine, an injection compression molding machine. The cylinder setting temperature of the injection molding machine during injection molding is preferably 240 to 340°C, more preferably 260 to 320°C. The injection speed during injection molding is preferably 10 to 1,000 mm/sec, more preferably 10 to 500 mm/sec.

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

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

1. Raw materials <Production Example 1: Production of polycarbonate resin (1)>
2,2-bis(3-methyl-4-hydroxyphenyl)propane (hereinafter referred to as “BPC”) 26.14 mol (6.75 kg) and diphenyl carbonate 26.79 mol (5.74 kg), The mixture was placed in a SUS reactor (inner volume: 10 liters) equipped with a stirrer and a distillate condenser, and after the inside of the reactor was replaced with nitrogen gas, the temperature was raised to 220°C over 30 minutes under a nitrogen gas atmosphere.
Next, the reaction solution in the reactor is stirred, and cesium carbonate (Cs ₂ CO ₃ ) as a transesterification reaction catalyst is added to the molten reaction solution in an amount of 1.5×10 ⁻⁶ mol per 1 mol of BPC. In addition, the reaction solution was stirred and brewed at 220° C. for 30 minutes in a nitrogen gas atmosphere. Next, at the same temperature, the pressure inside the reactor was reduced to 100 Torr over 40 minutes, and the reaction was continued for 100 minutes to distill off phenol.
Next, the temperature in the reactor was raised to 284° C. over 60 minutes and the pressure was reduced to 3 Torr to distill almost the entire theoretical amount of phenol. Next, the pressure in the reactor was kept below 1 Torr at the same temperature, and the reaction was continued for an additional 60 minutes to complete the polycondensation reaction. At this time, the stirring rotation speed of the stirrer was 38 rpm, the temperature of the reaction liquid immediately before the reaction was completed was 289° C., and the stirring power was 0.75 kW.
Next, the reaction liquid in a molten state is fed into a twin-screw extruder, and butyl p-toluenesulfonate is fed from the first feed port of the twin-screw extruder in an amount four times the molar amount of cesium carbonate, After kneading with the reaction liquid, the reaction liquid was extruded through a die of a twin-screw extruder into strands and cut with a cutter to obtain pellets of polycarbonate resin (1).

The following measurements were performed on the polycarbonate resin as the raw material.

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

<Measurement of pencil hardness>
After drying the polycarbonate resin pellets at 100 ° C. for 5 hours, using an injection molding machine (“J55-60H” manufactured by Japan Steel Works, Ltd.), (1) polycarbonate resin and (3) polycarbonate resin are set at a cylinder temperature of 260. ℃, mold temperature 80 ℃, (2) Polycarbonate resin, cylinder set temperature 340 ℃, mold temperature 80 ℃, screw rotation speed 100 rpm, injection speed 100 mm / sec. Strips (90 mm x 50 mm x 2 mm thick) were made. For this flat test piece, the pencil hardness was determined according to ISO 15184 using a pencil hardness tester (manufactured by Toyo Seiki Co., Ltd.) with a load of 750 g.

<Measurement of glass transition temperature>
The glass transition temperature was measured in accordance with JIS K7122 by performing two cycles of heating and cooling under the following DSC measurement conditions. A differential scanning calorimeter (DSC, manufactured by Shimadzu Corporation, "DSC-60") was used as a measuring device.
Measurement start temperature: 25°C
Heating rate: 10°C/min Achieved temperature: 300°C
Temperature drop rate: 5°C/min

2. Examples 1-8, Comparative Examples 1-3
<Production of polycarbonate resin composition pellets>
Each component described in Table 1 above was blended in the proportions shown in Table 2 below (all expressed in parts by mass), mixed uniformly in a tumbler mixer, and then a twin-screw extruder (Nippon Steel Co., Ltd.) Using TEX30α manufactured by TEX30α), the mixture is fed into the extruder from the barrel upstream of the extruder at a cylinder setting temperature of 300° C., a screw rotation speed of 180 rpm, and a discharge rate of 30 kg/hr, and melt-kneaded to obtain polycarbonate resin composition pellets. rice field.

<Measurement of HAZE>
After drying the polycarbonate resin composition pellets obtained above at 100 ° C. for 5 hours, an injection molding machine (“J55-60H” manufactured by Japan Steel Works, Ltd.) was used to set the cylinder temperature to 300 ° C. and the mold temperature to 80. C., screw rotation speed of 100 rpm, and injection speed of 100 mm/sec. The haze (unit: %) of the obtained flat test piece was measured with an NDH-2000 type haze meter manufactured by Nippon Denshoku Industries Co., Ltd.

<Measurement of pencil hardness>
After drying the polycarbonate resin composition pellets obtained above at 100 ° C. for 5 hours, an injection molding machine (“J55-60H” manufactured by Japan Steel Works, Ltd.) was used to set the cylinder temperature to 300 ° C. and the mold temperature to 80. C., screw rotation speed of 100 rpm, and injection speed of 100 mm/sec. The resulting flat test piece was measured in the same manner as the measurement of the pencil hardness of the raw material polycarbonate resin.

<Measurement of heat resistance (deflection temperature under load, DTUL)>
After drying the polycarbonate resin composition pellets obtained above at 100 ° C. for 5 hours, an injection molding machine (“J55-60H” manufactured by Japan Steel Works, Ltd.) was used to set the cylinder temperature to 300 ° C. and the mold temperature to 80 ° C. , 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 a load of 1.80 MPa in accordance with ISO75-1 and ISO75-2. The unit is °C.

<Comprehensive evaluation>
Based on the results of haze, pencil hardness and heat resistance (DTUL), comprehensive evaluation was made according to the following criteria.
A: Meets all three of the requirements within each of the following criteria.
B: Satisfies two of the requirements within each of the following criteria.
Criteria a: pencil hardness of 2H or higher, DTUL of 105°C or higher, haze of 5.0% or lower Criteria b: pencil hardness of H, DTUL of 113°C or higher, haze of 5.0% or lower Criteria c: pencil hardness of F , DTUL of 118° C. or higher and haze of 5.0% or lower C: pencil hardness of HB or lower, DTUL of less than 105° C., or haze of more than 85%

As is clear from Table 2 above, the polycarbonate resin compositions of the present invention had excellent transparency, high pencil hardness, and excellent heat resistance (Examples 1 to 8).
(2) When the polycarbonate resin was not included, the heat resistance was inferior (Comparative Example 1). Moreover, even if a polycarbonate resin with high heat resistance was contained, when the viscosity average molecular weight (Mv) exceeded 18,000 (Comparative Example 2), the haze was increased. Furthermore, (1) when the polycarbonate resin was not contained (Comparative Example 3), the pencil hardness was low.

Since the polycarbonate resin composition of the present invention is a material that is comprehensively excellent in surface hardness, transparency and heat resistance, it can , lighting equipment and the like. Among these, in particular, it can be suitably used for electrical and electronic equipment, OA equipment, housings of information terminal equipment and home appliances, lighting equipment and vehicle parts (especially vehicle interior parts), smartphones and touch panels. Availability is very high.

Claims (5)

(1) a polycarbonate resin containing 50 mol% or more of a structural unit represented by the following formula (1);
(2) a polycarbonate resin having a glass transition temperature of 160° C. or higher,
The mass ratio of the (1) polycarbonate resin and (2) the polycarbonate resin is 10 to 90:90 to 10 (the total is 100 parts by mass), and (2) the viscosity average molecular weight of the polycarbonate resin (two or more When using a polycarbonate resin, the viscosity average molecular weight of the blend) is 1,000 to 14,000 ,
The polycarbonate resin composition , wherein the polycarbonate resin (2) is a polycarbonate resin containing a structural unit represented by the following formula (2) ;
formula (1)

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

R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group, and Z is combined with C to form an alicyclic hydrocarbon having 6 to 12 carbon atoms, which may have a substituent. representing a group ;
formula (2)

In formula (2), R ⁵ to R ⁸ each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 9 carbon atoms, an aryl group having 6 to 12 carbon atoms, represents an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an aralkyl group having 7 to 17 carbon atoms; 2. The polycarbonate resin composition according to claim 1, wherein all ^R2 in the formula (1) are hydrogen atoms. 3. The polycarbonate resin composition according to claim 1, wherein the (1) polycarbonate resin has a pencil hardness of H or more measured according to ISO 15184. The polycarbonate resin composition according to any one of claims 1 to 3, wherein the polycarbonate resin (2) has a glass transition temperature of 160 to 220°C. A molded article obtained by molding the polycarbonate resin composition according to any one of claims 1 to 4 .