JP2019156942A - Polycarbonate resin composition and molding - Google Patents

Abstract

To provide a polycarbonate resin composition generally excellent in surface hardness, transparency and heat resistance, and a molding molded from the polycarbonate resin composition.SOLUTION: A polycarbonate resin composition has (1) a polycarbonate resin containing a structural unit represented by formula (1) of 50 mol% or more, and (2) a polycarbonate resin with a glass transition temperature of 160°C or more, a mass ratio between the (1) polycarbonate resin and (2) polycarbonate resin being 10-90:90-10 (where, the total of them is 100 pts.mass), the (2) polycarbonate resin having a viscosity average molecular weight of 1,000-18,000; Ris a methyl group, Ris a hydrogen atom or a methyl group.SELECTED DRAWING: None

Description

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

  Polycarbonate resin is excellent in strength and electrical characteristics, and the resulting molded product is also excellent in dimensional stability, etc., so it can be used for electrical and electronic equipment casings, automotive interior parts, or precision molded parts. It is widely used as a raw material resin for manufacturing, and in particular, for home appliances, electronic devices, liquid crystal display display devices, etc., a product with high commercial value can be obtained by utilizing 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）と同義である。） For example, Patent Document 1 includes a polycarbonate resin (A) having a structural unit of the following general formula (1) and 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 at a mass ratio of (A) / (B) at a ratio of 80/20 to 20/80, and according to ASTM D2794 A polycarbonate resin composition characterized by having a measured DuPont impact strength at 25 ° C. of 10 J or more and a pencil hardness measured according to JIS K5600 of 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 represents

R ³ and R ⁴ each represent a hydrogen atom or a methyl group, and Z represents a group that forms an alicyclic hydrocarbon which may be bonded to C and have a substituent having 6 to 12 carbon atoms. . )

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

JP2013-0664045A

However, examination of the above Patent Document 1 revealed that it is not necessarily suitable for applications requiring heat resistance.
An object of the present invention is to solve the above-mentioned problems, and 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. The purpose is 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。 As a result of investigation by the present inventors based on the above problems, a polycarbonate resin having a high glass transition temperature and a relatively low viscosity average molecular weight is blended with the polycarbonate resin represented by the general formula (1). The inventors have found that a polycarbonate resin composition that is comprehensively excellent in surface hardness, transparency, and heat resistance can be obtained by adjusting the blending amounts thereof, and the present invention has been completed. Specifically, the above problem has been solved by the following means <1>, preferably <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 more, The mass ratio of the resin and (2) polycarbonate resin is 10 to 90:90 to 10 (however, the total is 100 parts by mass), and (2) the viscosity average molecular weight of the polycarbonate resin is 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 one of the following formulas,

R ³ and R ⁴ each independently represents a hydrogen atom or a methyl group, and Z is bonded to 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 R ² in the formula (1) is a hydrogen atom.
<3> The polycarbonate resin composition according to <1> or <2>, wherein the pencil hardness measured according to ISO 15184 of the (1) polycarbonate resin is H or more.
<4> The polycarbonate resin composition according to any one of <1> to <3>, wherein the glass transition temperature of the (2) polycarbonate resin is 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 are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 9 carbon atoms, an aryl group having 6 to 12 carbon atoms, 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 represents an integer of 0 to 4;
<6> A molded product obtained by molding the polycarbonate resin composition according to any one of <1> to <5>.

  According to the present invention, it is possible to provide a polycarbonate resin composition which is comprehensively excellent in surface hardness, transparency and 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 the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

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

Ｒ³およびＲ⁴は、それぞれ独立に、水素原子またはメチル基を表し、ＺはＣと結合して炭素数６〜１２の、置換基を有していてもよい脂環式炭化水素を形成する基を表す。 The polycarbonate resin composition of the present invention includes (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 more. The mass ratio of (1) polycarbonate resin to (2) polycarbonate resin is 10 to 90:90 to 10 (however, the total is 100 parts by mass), (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 one of the following formulas,

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

  By adopting the above configuration, a polycarbonate resin composition and a molded product having high surface hardness, relatively low transparency, and high heat resistance can be obtained. Particularly, (2) polycarbonate resin having a low viscosity average molecular weight. By using this, even in a two-component blend of (1) polycarbonate resin and (2) polycarbonate resin, there is a high technical significance in that the transparency can be lowered.

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 a structural unit represented by Formula (1)>
The polycarbonate resin composition of this invention contains the polycarbonate resin which contains 50 mol% or more of structural units represented by (1) 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 one of the following formulas,

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

Two R ² in the formula (1) may be the same or different from each other, preferably the same. R ² is preferably a hydrogen atom.

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

Specific examples of the preferred (1) polycarbonate resin include the following polycarbonate resins i) to iv).
i) One 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 ¹ is —C (CH ₃ ) Having a structural unit of 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 ¹ is —C (CH ₃ ). Having a structural unit that is _2-
iii) a structural unit composed of 2,2-bis (3-methyl-4-hydroxyphenyl) cyclohexane, that is, a structural unit in which R ¹ is a methyl group, R ² is a hydrogen atom, and X ¹ is a cyclohexylidene group. Having
iv) A structural unit composed of 2,2-bis (3-methyl-4-hydroxyphenyl) cyclododecane, that is, R ¹ is a methyl group, R ² is a hydrogen atom, and X ¹ is a cyclododecylidene group. Having structural units.
Of these, i), ii) and iii) are preferred, i) and iii) are more preferred, and i) is more preferred.

In this invention, (1) 50 mol% or more of structural units which comprise polycarbonate resin are contained. Preferably more than 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 a structural unit represented by Formula (1).
The (1) polycarbonate resin may contain only one type of structural unit represented by the formula (1), or may contain two or more types. When 2 or more types are included, the total amount is preferably within the above range.

The (1) polycarbonate resin may have a structural unit other than the structural unit represented by the formula (1). Examples of the dihydroxy compound constituting such other 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 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-methyl) Propyl) phenyl) cyclohexane, 1,1-bis (4-hydroxy-3-cyclohexylphenyl) cyclohexane, , 1,1-bis (4-hydroxy-3-phenylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3-methylphenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3, 5 -Dimethylphenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3- (1-methylethyl) phenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3-tert- Butylphenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3- (1-methylpropyl) phenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3-cyclohexylphenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3-phenylphenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) Clopentane, 1,1-bis (4-hydroxyphenyl) cyclooctane, 4,4 ′-(1,3-phenylenediisopropylidene) bisphenol, 4,4 ′-(1,4-phenylenediisopropylidene) bisphenol, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 4,4′-dihydroxybenzophenone, 4,4′-dihydroxyphenyl ether, 4,4 '-Dihydroxybiphenyl, 1,1-bis (4-hydroxyphenyl) -3,3-5-trimethylcyclohexane, 1,1-bis (4-hydroxy-6-methyl-3-tert-butylphenyl) butane.

The amount of copolymerization of other structural units other than the structural unit represented by formula (1) in the polycarbonate resin (1) is 50 mol% or less, preferably less than 50 mol%, more preferably 40 mol%. Hereinafter, it is more preferably 30 mol% or less, more preferably 20 mol% or less, still more preferably 10 mol% or less, and 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 the formula (1), or may contain two or more types. When 2 or more types are included, the total amount is preferably within the above range.

The viscosity average molecular weight (Mv) of the polycarbonate resin (1) is preferably a lower limit of 15,000 or more, more preferably 17,000 or more, and further preferably more than 18,000, More preferably, it is 19,000 or more, and more preferably 20,000 or more. In addition, the upper limit value of Mv is preferably 35,000 or less, more preferably 30,000 or less, and further preferably 28,000 or less.
By setting the viscosity average molecular weight to the above lower limit or more, a molded product having improved heat resistance and moldability and high mechanical strength can be obtained. Moreover, by setting it as the said upper limit or less, the fluidity | liquidity of a molded article improves and a thin molded article etc. can be manufactured efficiently. Furthermore, by setting the viscosity average molecular weight (Mv) in the above range, it is possible to obtain a molded product having an excellent balance between high transparency and high hardness.
The viscosity average molecular weight (Mv) is measured according to the method described in Examples described later (hereinafter, the same applies to Mv).
The viscosity average molecular weight may be adjusted by blending two or more kinds of polycarbonate resins to be in the above range.

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

  The (1) polycarbonate resin preferably has a glass transition temperature of 110 ° C. or higher, more preferably 115 ° C. or higher, and still 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 Examples described later (hereinafter the same for the glass transition temperature).

  The method for producing the (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.

The polycarbonate resin composition of the present invention preferably contains the above (1) polycarbonate resin in the range of 10 to 90% by mass of the composition.
The polycarbonate resin composition of the present invention may contain only one kind of the above (1) polycarbonate resin, or may contain two or more kinds. When 2 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 includes (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. By including such a resin, heat resistance can be improved. 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 obtained molded product can be relatively lowered.

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 are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 9 carbon atoms, an aryl group having 6 to 12 carbon atoms, 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 represented.
n1, n2 and n3 each independently represents an integer of 0 to 4.

When R ^{5 to} R ⁸ have a carbon atom, these carbon atoms further include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, and iodine. It may have a substituent selected from atoms.
R ⁵ and R ⁷ are each independently 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. -17 aralkyl groups are preferred, alkyl groups having 1 to 9 carbon atoms are more preferred, alkyl groups having 1 to 3 carbon atoms are more preferred, and methyl groups are still more preferred. Moreover, the direction which does not have a substituent is preferable.
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. It 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, and a methyl group or phenyl group. And more preferably a methyl group. Moreover, when it has a substituent, a C1-C5 alkyl group is preferable, It is more preferable that it is a C1-C3 alkyl group, and it is more preferable that it is a methyl group. However, it is preferable not to have a substituent.
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. The alkyl group is preferably an alkyl group having 1 to 9 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and still more preferably a methyl group. Moreover, the direction which does not have a substituent is preferable.
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 (2) polycarbonate resin preferably contains 50 mol% or more of the structural unit represented by the formula (2), more preferably more than 50 mol%, still more preferably 60 mol% or more. 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 is the structural unit represented by the 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 2 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。 The 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 the above formula (2-1) are each independently synonymous with R ^{5 to} R ⁸ and n1, n2 and n3 in the formula (2), and preferred ranges are also the same. It is.

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

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

  Examples of the (2) polycarbonate resin include 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-hydroxy) Enyl) cyclohexane, 1,1-bis (4-hydroxydiphenyl) phenylmethane, 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3,5-dimethyl) Phenyl) 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-phenyl eta 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-bis (4-hydroxy-3-cyclohexylphenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3-phenylphenyl) -1-phenylethane, 1,1-bis (4-hydroxy) Phenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclooctane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4- Including structural units composed of compounds selected from hydroxy-3-methylphenyl) fluorene, 4,4′-dihydroxybiphenyl and 1,1-bis (4-hydroxyphenyl) -3,3-5-trimethylcyclohexane Polycarbonate resins are preferred, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3-methylphenyl) -1-phenylethane, 1,1-bis (4 More preferred is a polycarbonate resin containing a structural unit composed of a compound selected from -hydroxyphenyl) -1-diphenylmethane and 1,1-bis (4-hydroxy-3-methylphenyl) -1-diphenylmethane. 1,1-bis (4-hydroxyphenyl) -1-phenylethane A polycarbonate resin containing the structural unit to be formed is more preferable.

(2) The viscosity average molecular weight (Mv) of the polycarbonate resin 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. More preferably, it is more preferably 10,000 or more. Further, the upper limit value 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. Or less, more preferably 13,000 or less.
By setting the viscosity average molecular weight to the above lower limit or more, a molded product having improved heat resistance and moldability and high mechanical strength can be obtained. Moreover, by setting it as the said upper limit or less, the fluidity | liquidity of a molded article improves and a thin molded article etc. can be manufactured efficiently. Furthermore, by setting the viscosity average molecular weight (Mv) in the above range, it is possible to obtain a molded product having an excellent balance between high transparency and high hardness.
The viscosity average molecular weight may be adjusted by blending two or more kinds of polycarbonate resins to be in the above range.

  The (2) polycarbonate resin has a pencil hardness measured according to ISO 15184, for example, from 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, further preferably 168 ° C. or higher, and more preferably 170 ° C. or higher, 173 ° C. or higher, 175 ° C. As described above, it may be 180 ° C. or higher and 185 ° C. or higher. The upper limit of the glass transition temperature is not particularly defined, 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 above (2) polycarbonate resin in the range 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 (2) polycarbonate resin, or may contain two or more types. When 2 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 the above (1) polycarbonate resin and (2) polycarbonate resin is 10 to 90:90 to 10, preferably 13 to 85:87 to 15. 85:85 to 15 is more preferable, 20 to 80:80 to 20 is still more preferable, and 25 to 75:75 to 25 is even more preferable. However, the total of the above (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 occupies 60% by mass or more, more preferably 65% by mass or more, and further 70% by mass. % Or more, particularly 90% by 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 the structural unit represented by the formula (3) (hereinafter sometimes referred to as “(3) polycarbonate resin”).
Formula (3)

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

R ³ and R ⁴ each independently represents a hydrogen atom or a methyl group, and Z is bonded to C to form an alicyclic hydrocarbon having 6 to 12 carbon atoms, which may have a substituent. Represents a group.
X ² has the same meaning as X ¹ described in the above formula (1), 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 composed of bisphenol-A (carbonate structural unit).
In this invention, (3) polycarbonate resin contains the structural unit represented by the said Formula (3) exceeding 50 mol%. Preferably it is 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 (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 2 or more types are included, the total amount is preferably within the above range.

  The (3) polycarbonate resin may have a structural unit other than the structural unit represented by the formula (3). Examples of the dihydroxy compound constituting such other structural unit include structural units other than the structural unit represented by the formula (1) described in the above (1) polycarbonate resin (provided that, Excluding those corresponding to the structural unit represented by formula (3)).

The amount of copolymerization of other structural units other than the structural unit represented by the formula (3) in the polycarbonate resin (3) is less than 50 mol%, preferably 45 mol% or less, more preferably 40 mol%. Hereinafter, it is more preferably 30 mol% or less, more preferably 20 mol% or less, still more preferably 10 mol% or less, and still 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 the formula (3), or may contain two or more types. When 2 or more types are included, the total amount is preferably within the above range.

The viscosity average molecular weight (Mv) of the polycarbonate resin (3) is preferably a lower limit of 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. Further, the upper limit value of Mv is preferably 30,000 or less, more preferably 28,000 or less, and further preferably 26,000 or less.
By setting the viscosity average molecular weight to the above lower limit or more, a molded product with improved moldability and higher mechanical strength can be obtained. Moreover, by setting it as the said upper limit or less, the fluidity | liquidity of a molded article improves more and a thin molded article etc. can be manufactured more efficiently.
The viscosity average molecular weight may be adjusted by blending two or more kinds of polycarbonate resins to be in the above range.

  The (3) polycarbonate resin is exemplified by a pencil hardness measured according to ISO 15184 of 3B to B, and further exemplified by 2B.

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

  The method for producing the (3) 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 interfacial polymerization method is more preferable.

When the polycarbonate resin composition of the present invention includes the above (3) polycarbonate resin, 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 preferable. Moreover, it is preferable that the upper limit of the said content is 40 mass% or less, It is more preferable that it is 35 mass% or less, Furthermore, 30 mass% or less may be 10 mass% or less.
The polycarbonate resin composition of the present invention may contain only one kind of the above (3) polycarbonate resin, or may contain two or more kinds. When 2 or more types are included, the total amount is preferably within the above range.

  A preferred 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 a polycarbonate resin.

<Other ingredients>
The polycarbonate resin composition of the present invention may contain other components other than the above, if necessary, as long as desired physical properties are not significantly impaired. Examples of other components include thermoplastic resins other than the polycarbonate resin described above (for example, acrylic resin), various resin additives, and the like.
Examples of resin additives include mold release agents, stabilizers (thermal stabilizers, antioxidants, etc.), ultraviolet absorbers, antistatic agents, flame retardants, flame retardant aids, dyes and pigments, antifogging agents, lubricants, Antiblocking agents, fluidity improvers, plasticizers, dispersants, antibacterial agents and the like can be mentioned. In addition, 1 type may contain resin additive and 2 or more types may contain it by arbitrary combinations and ratios.

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 the following formula (X).
Formula (X)

In the 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 may have a substituent having 6 carbon atoms. It represents an aliphatic hydrocarbon group having 1 to 3 carbon atoms substituted with an aromatic hydrocarbon group having ˜20 or an optionally substituted aromatic hydrocarbon group having 6 to 17 carbon atoms.

As the acrylic resin used in the present invention, those described in WO2014 / 038500, WO2013 / 094898, JP2006-199774, and JP2010-116501 can be employed in addition to the above. The contents of which are incorporated herein.
When mix | blending an acrylic resin, it is preferable that the compounding quantity is the range of 1-10 mass% of the polycarbonate resin composition of this invention.

<< Releasing agent >>
Examples of the release agent 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, polysiloxane silicone oils, and the like.

  Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic monovalent, divalent or trivalent carboxylic acid. Here, the aliphatic carboxylic acid includes alicyclic carboxylic acid. Among these, preferable aliphatic carboxylic acids are monovalent or divalent carboxylic acids having 6 to 36 carbon atoms, and aliphatic saturated monovalent carboxylic acids having 6 to 36 carbon atoms are more preferable. Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, mellicic acid, tetrariacontanoic acid, montanic acid, adipine Examples include acids and azelaic acid.

  As aliphatic carboxylic acid in ester of aliphatic carboxylic acid and alcohol, the same thing as the said aliphatic carboxylic acid can be used, for example. On the other hand, examples of the alcohol 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, monovalent or polyvalent 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. In addition, an aliphatic includes an alicyclic compound 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. Is mentioned.

  In addition, said ester may contain aliphatic carboxylic acid and / or alcohol as an impurity. Moreover, although said ester may be a pure substance, it may be a mixture of a plurality of compounds. Furthermore, the aliphatic carboxylic acid and alcohol which combine to form one ester may be used alone or in combination of two or more in any combination and ratio.

  Specific examples of esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture based on myricyl palmitate), stearyl stearate (stearate stearate), behenyl behenate, stearyl behenate, glycerin mono Examples include palmitate, glycerol monostearate, glycerol distearate, glycerol tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate, etc. It is done.

  Examples of the aliphatic hydrocarbon 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 oligomer having 3 to 12 carbon atoms. Here, the aliphatic hydrocarbon includes alicyclic hydrocarbons. Further, 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 even a mixture of various constituent components 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 part by mass or more, preferably 100 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 mass part or more, and is 2 mass parts or less normally, Preferably it is 1 mass part or less, More preferably, it is 0.6 mass part or less. By making the content of the release agent not less than the lower limit of the above range, the effect of releasability is effectively exhibited, and by making the content not more than the upper limit of the above range, degradation of hydrolysis resistance and injection molding are achieved. It is possible to more effectively suppress mold contamination at the time. A molded article having excellent transparency can be obtained regardless of the content of the release agent, but hardness and heat resistance tend to be reduced by exceeding the upper limit of the above range.
The mold release agent may contain only 1 type and may contain 2 or more types. When 2 or more types are included, the total amount is preferably within the above range.

<< Stabilizer >>
Examples of the stabilizer include a heat stabilizer and an antioxidant.
Examples of the heat stabilizer include phosphorus stabilizers.
Any known phosphorous stabilizer can be used. Specific examples include phosphorus oxo acids such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, and polyphosphoric acid; acidic pyrophosphate metal salts such as acidic sodium pyrophosphate, acidic potassium pyrophosphate, and acidic calcium pyrophosphate; phosphoric acid Group 1 or Group 2B metal phosphates such as potassium, sodium phosphate, cesium phosphate and zinc phosphate; organic phosphate compounds, organic phosphite compounds, organic phosphonite compounds, etc. Particularly preferred.

Organic phosphite compounds include triphenyl phosphite, tris (monononylphenyl) phosphite, tris (monononyl / dinonyl phenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, monooctyl Diphenyl phosphite, dioctyl monophenyl phosphite, monodecyl diphenyl phosphite, didecyl monophenyl phosphite, tridecyl phosphite, trilauryl phosphite, tristearyl phosphite, 2,2-methylenebis (4,6-di- tert-butylphenyl) octyl phosphite and the like.
Specific examples of such organic phosphite compounds include, for example, “ADEKA STAB 1178”, “ADEKA STAB 2112”, “ADEKA STAB HP-10” manufactured by ADEKA, “JP-351” manufactured by Johoku Chemical Industry Co., Ltd., “ JP-360 ”,“ JP-3CP ”,“ Irgaphos 168 ”manufactured by BASF, and the like.

Examples of the antioxidant include hindered phenol stabilizers.
Specific examples of the hindered phenol stabilizer 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-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert -Butyl-4- (4,6-bis (octylthio) -1,3,5-triazin-2-ylamino) phenol, 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) Ethyl] -4,6-di -tert- pentylphenyl acrylate.

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

  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 with respect to 100 parts by mass in total of the polycarbonate resin component and other resin components blended as necessary. 0.005 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 making 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 descriptions in paragraphs 0059 to 0062 of JP-A-2006-216534 can be referred to, and the contents thereof are incorporated in the present specification.

<< Antistatic Agent >>
As the antistatic agent, the description in paragraphs 0063 to 0067 of JP-A-2006-216534 can be referred to, and the contents thereof are incorporated in the present specification.

<< Flame Retardant >>
As the flame retardant, the description in paragraphs 0068 to 0075 of JP-A-2006-216534 can be referred to, and the contents thereof are incorporated in the present specification.

<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, and 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 ideal lower limit of haze is 0%, but 0.1% or more, and even 0.3% 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 more, and can be F or more, H or more, 2H or more. The upper limit value of the pencil hardness is not particularly defined, but for example, 3H or less, and even 2H or less is a practically meaningful 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 of the polycarbonate resin composition of the present invention measured according to ISO 75-2 can be 103 ° C. or higher, and further 105 ° C. or higher, 108 ° C. or higher, 110 ° C. or higher, 113 ° C. or higher, It can also be set to 115 ° C. or higher and 120 ° C. or higher. The upper limit value of the deflection temperature under load is not particularly defined, but for example, it is at a practical level even at 140 ° C. or lower, or even 135 ° C. or lower.
The polycarbonate resin composition of the present invention preferably satisfies all of the above-mentioned haze, pencil hardness and deflection temperature under load.

<Production method of polycarbonate resin composition>
There is no limitation on the production method of the polycarbonate resin composition of the present invention, and a wide variety of production methods of known polycarbonate resin compositions can be adopted, and the above (1) polycarbonate resin and (2) polycarbonate resin, and blended as necessary. Other components are mixed in advance using various mixers such as a tumbler or Henschel mixer, and then melted in a mixer such as a Banbury mixer, roll, brabender, single-screw kneading extruder, twin-screw kneading extruder, kneader, etc. The method of kneading is mentioned.
The temperature for melt kneading is not particularly limited, but is usually in the range of 240 to 320 ° C.

<Molded product>
The polycarbonate resin composition (for example, pellets) described above is molded into various molded products by various molding methods.
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. For example, a film shape, a rod shape, a cylindrical shape, an annular shape, a circular shape, an elliptical shape, a polygonal shape , Irregular shape, hollow shape, frame shape, box shape, panel shape, button shape and the like.

The method for molding a molded product is not particularly limited, and a conventionally known molding method can be employed.For example, an injection molding method, an injection compression molding method, an extrusion molding method, a profile extrusion method, a transfer molding method, a hollow molding method, Gas assisted hollow molding method, blow molding method, extrusion blow molding, IMC (in-mold coating molding) molding method, rotational molding method, multilayer molding method, two-color molding method, insert molding method, sandwich molding method, foam molding method And a pressure molding method.
Among these, the molding is preferably performed by an injection molding method. For example, the 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 340 ° C, and more preferably 260 to 320 ° C. The injection speed during injection molding is preferably 10 to 1,000 mm / second, more preferably 10 to 500 mm / second.

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

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

1. Raw 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 reactor was placed in a SUS reactor (with an internal volume of 10 liters) equipped with a stirrer and a distillation condenser, and after the inside of the reactor was replaced with nitrogen gas, the temperature was raised to 220 ° C. over 30 minutes in a nitrogen gas atmosphere.
Next, the reaction solution in the reactor is stirred, and cesium carbonate (Cs ₂ CO ₃ ) is used as a transesterification reaction catalyst in the molten reaction solution so as to be 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, under the same temperature, the pressure in the reactor was reduced to 100 Torr over 40 minutes, and the reaction was further performed for 100 minutes to distill phenol.
Next, the temperature in the reactor was raised to 284 ° C. over 60 minutes and the pressure was reduced to 3 Torr, and phenol corresponding to almost the entire distillation amount was distilled. Next, the pressure in the reactor was kept below 1 Torr at the same temperature, and the reaction was further continued for 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 just before the completion of the reaction was 289 ° C., and the stirring power was 0.75 kW.
Next, the reaction solution in a molten state is fed into a twin screw extruder, and 4-fold molar amount of butyl p-toluenesulfonate is supplied from the first supply port of the twin screw extruder with respect to cesium carbonate, 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 a pellet of polycarbonate resin (1).

  The following measurement was 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 was determined by using methylene chloride as a solvent and obtaining an intrinsic viscosity (η) (unit: dL / g) at a temperature of 20 ° C. using an Ubbelohde viscometer. Calculated from the formula.
η = 1.23 × 10 ⁻⁴ Mv ^0.83

<Measurement of pencil hardness>
After the polycarbonate resin pellets were dried at 100 ° C. for 5 hours, an injection molding machine (“J55-60H” manufactured by Nippon Steel Works, Ltd.) was used. (2) Polycarbonate resin is a flat plate test 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 piece (90 mm × 50 mm × 2 mm thickness) was prepared. About this flat-plate-shaped test piece, based on ISO15184, the pencil hardness measured by the 750g load was calculated | required using the pencil hardness tester (made by Toyo Seiki Co., Ltd.).

<Measurement of glass transition temperature>
In accordance with JIS K7122, the glass transition temperature was measured by performing two cycles of temperature increase and decrease according to the following DSC measurement conditions. A differential scanning calorimeter (DSC, manufactured by Shimadzu Corporation, “DSC-60”) was used as a measuring apparatus.
Measurement start temperature: 25 ° C
Temperature increase rate: 10 ° C / min Achieving temperature: 300 ° C
Temperature drop rate: 5 ° C / min

2. Examples 1-8, Comparative Examples 1-3
<Manufacture 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) and uniformly mixed with a tumbler mixer, and then a twin-screw extruder (Nippon Steel Corporation). Using TEX30α), a cylinder set temperature of 300 ° C., a screw rotation speed of 180 rpm, and a discharge rate of 30 kg / hr, fed to the extruder from the barrel upstream of the extruder, and melt-kneaded to obtain a polycarbonate resin composition pellet. It was.

<Measurement of HAZE>
The polycarbonate resin composition pellets obtained above were dried at 100 ° C. for 5 hours, and then an injection molding machine (“J55-60H” manufactured by Nippon Steel Works, Ltd.) was used. A flat test piece having a thickness of 90 mm × 50 mm × 2 mm was injection molded under the conditions of ° C., screw rotation speed 100 rpm, injection speed 100 mm / second. About the obtained flat test piece, haze (unit:%) was measured with the Nippon Denshoku Industries Co., Ltd. NDH-2000 type | mold haze meter.

<Measurement of pencil hardness>
The polycarbonate resin composition pellets obtained above were dried at 100 ° C. for 5 hours, and then an injection molding machine (“J55-60H” manufactured by Nippon Steel Works, Ltd.) was used. A flat test piece having a thickness of 90 mm × 50 mm × 2 mm was injection molded under the conditions of ° C., screw rotation speed 100 rpm, injection speed 100 mm / second. About the obtained flat test piece, it measured by the method similar to the measurement of the pencil hardness of the polycarbonate resin of the said raw material.

<Measurement of heat resistance (deflection temperature under load, DTUL)>
The polycarbonate resin composition pellets obtained above were dried at 100 ° C. for 5 hours, and then used with an injection molding machine (“J55-60H” manufactured by Nippon Steel Co., Ltd.), cylinder setting temperature 300 ° C., mold temperature 80 ° C. Injection molding was performed under 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 a load of 1.80 MPa in accordance with ISO75-1 and ISO75-2. The unit is indicated in ° 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: All three of the following requirements are met.
B: Satisfies two requirements within each of the following criteria.
Standard a: Pencil hardness is 2H or higher, DTUL is 105 ° C. or higher, and haze is 5.0% or lower Standard b: Pencil hardness is H, DTUL is 113 ° C. or higher, and haze is 5.0% or lower Standard c: Pencil hardness is F DTUL is 118 ° C. or higher, haze is 5.0% or less C: Pencil hardness is HB or less, or DTUL is less than 105 ° C., or haze exceeds 85%

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

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

Claims (6)

(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 (1) polycarbonate resin to (2) polycarbonate resin is 10 to 90:90 to 10 (however, the total is 100 parts by mass), and (2) the viscosity average molecular weight of the polycarbonate resin is 1,000. A polycarbonate resin composition of ˜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 one of the following formulas,

R ³ and R ⁴ each independently represents a hydrogen atom or a methyl group, and Z is bonded to C to form an alicyclic hydrocarbon having 6 to 12 carbon atoms, which may have a substituent. Represents a group. The polycarbonate resin composition according to claim 1, wherein R ² in the formula (1) is a hydrogen atom. The polycarbonate resin composition according to claim 1 or 2, wherein the pencil hardness measured according to ISO 15184 of the (1) polycarbonate resin is H or more. The polycarbonate resin composition according to any one of claims 1 to 3, wherein the glass transition temperature of the (2) polycarbonate resin is 160 to 220 ° C. Said (2) polycarbonate resin is a polycarbonate resin composition of any one of Claims 1-4 which is a polycarbonate resin containing the structural unit represented by following formula (2);
Formula (2)

In formula (2), R ^{5 to} R ⁸ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 9 carbon atoms, an aryl group having 6 to 12 carbon atoms, 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 represents an integer of 0 to 4; The molded article formed by shape | molding the polycarbonate resin composition of any one of Claims 1-5.