JP2013216796A - Polycarbonate resin molded product - Google Patents

Abstract

【選択図】なしDisclosed is a polycarbonate resin molded article having high surface hardness, impact resistance, and excellent hue (transparency).
A molded article obtained by injection molding a polycarbonate resin composition containing a polycarbonate resin (A) of the formula (1) and a polycarbonate resin (B) of the formula (2).

[Selection figure] None

Description

  The present invention relates to a polycarbonate resin molded body, and more particularly, to a polycarbonate resin molded body having both high surface hardness and high impact resistance and excellent hue.

  Polycarbonate resin is tough and excellent in impact resistance and electrical characteristics, and the resulting molded product is also excellent in dimensional stability, so electrical and electronic equipment housings, automotive interior parts, or precision Widely used as a raw material resin for manufacturing molded parts. In particular, in a member (housing) of a home appliance, an electronic device, a liquid crystal display device, etc., a product having a high commercial value can be obtained by utilizing its beautiful appearance.

However, since the surface hardness of polycarbonate resin is lower than that of glass, it is inferior in scratch resistance, and when it is wiped with a cloth or handled roughly, the surface is easily scratched, and it is desired to have scratch resistance.
Conventionally, in order to improve the scratch resistance, various coatings have been applied to the surface of the polycarbonate resin molded product. However, in the processing such as coating, since processing costs and labor are required, It is desired to impart scratch resistance to the polycarbonate resin molded article itself by improving the composition of the polycarbonate resin composition.

Conventionally, as techniques for increasing the hardness of the polycarbonate resin composition itself, polycarbonate resin blended with silicone oil (Patent Document 1), silicone compound or other slidable filler blended (Patent Document 2), biphenyl A compound containing an antiplasticizer such as a compound, a terphenyl compound, or polycaprolactone (Patent Document 3) has been proposed. However, although the surface hardness is improved to some extent, the impact resistance is not sufficient.
Patent Document 4 proposes a method of improving impact resistance by blending an acrylic elastomer and a polyester resin with an aromatic polycarbonate resin. However, although this resin composition has improved hardness and chemical resistance to some extent, transparency is lowered and both hardness and impact resistance are not satisfactory.

JP 2004-210889 A JP 2007-51233 A JP 2007-326938 A Japanese Examined Patent Publication No. 62-37671

In recent years, new products have appeared one after another in the fields of various display (display) devices, electrical and electronic devices, in-vehicle devices, etc. The required specifications for surface hardness, impact resistance, and hue are becoming increasingly sophisticated. However, until now, no actual high-level polycarbonate resin material having both high surface hardness and high impact resistance and excellent hue has been proposed.
An object of the present invention is to provide a polycarbonate resin molded article having both high surface hardness, high impact resistance, and all excellent hues.

The inventors of the present invention used a combination of two types of polycarbonate resins having specific repeating units, and at that time, polycarbonate resins produced by different polymerization methods were selected, and molded products obtained by injection molding. Was found to have high impact resistance and good hue (transparency) while exhibiting high surface hardness, and completed the present invention.
That is, this invention provides the following polycarbonate resin moldings.

（一般式（１）中、Ｒ^１はメチル基、Ｒ^２は水素原子またはメチル基を示し、Ｘは、

を示し、Ｒ^３及びＲ^４は水素原子またはメチル基を示し、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示す。）

（一般式（２）中、Ｘは前記一般式（１）におけるＸと同義である。） [1] A molded product obtained by injection molding a polycarbonate resin composition (A) having a repeating unit of the following general formula (1) and a polycarbonate resin composition (B) having a repeating unit of the following general formula (2) There,
The polycarbonate resin (A) and the polycarbonate resin (B) are produced by different polymerization methods, and the viscosity average molecular weight (Mv) of the polycarbonate resin (A) is in the range of 18,000 to 30,000. A polycarbonate resin molded article characterized in that the surface hardness (measured in accordance with JIS K5600) measured with a multipurpose test piece injection molded in accordance with K7152 is F or more in pencil hardness.

(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 represent a hydrogen atom or a methyl group, and Z represents a group that forms an alicyclic hydrocarbon which may combine with C to have a substituent having 6 to 12 carbon atoms. . )

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

[2] The polycarbonate resin molded article according to the above [1], wherein one of the production methods of the polycarbonate resin (A) and the polycarbonate resin (B) is an interfacial polymerization method and the other is a melt polymerization method.
[3] Polycarbonate resin (A)
i) a polycarbonate resin in which R ¹ in the general formula (1) is a methyl group, R ² is a hydrogen atom, and X is an isopropylidene group;
ii) a polycarbonate resin in which R ¹ in the general formula (1) is a methyl group, R ² is a methyl group, and X is an isopropylidene group, or iii) R ¹ in the general formula (1) is a methyl group, R ^A polycarbonate resin in which ² is a hydrogen atom and X is a cyclohexylidene group;
The polycarbonate resin molded article according to the above [1] or [2], which is selected from:
[4] The above [1] to [3], wherein the polycarbonate resin (A) is a polycarbonate resin in which R ¹ in the general formula (1) is a methyl group, R ² is a hydrogen atom, and X is an isopropylidene group. A polycarbonate resin molded article according to any one of the above.
[5] The polycarbonate resin molded article according to any one of [1] to [4], wherein the polycarbonate resin (B) is a polycarbonate resin in which X in the general formula (2) is an isopropylidene group.
[6] The content of the polycarbonate resin (A) and the polycarbonate resin (B) is 5 to 45 parts by mass of the polycarbonate resin (A) and the polycarbonate resin (B) based on a total of 100 parts by mass of (A) and (B). Is a polycarbonate resin molded article according to any one of [1] to [5] above, which is 95 to 55 parts by mass.

[7] Further, at least one stabilizer selected from the group consisting of phosphorus-based, phenol-based and sulfur-based stabilizers is added in an amount of 0. 0 relative to 100 parts by mass in total of the polycarbonate resins (A) and (B). The polycarbonate resin molded article according to any one of the above [1] to [6], which contains 01 to 1 part by mass.
[8] Any of [1] to [7] above, further containing 0.05 to 1 part by mass of a fatty acid ester as a release agent with respect to a total of 100 parts by mass of the polycarbonate resins (A) and (B). A molded product of the polycarbonate resin.
[9] The polycarbonate resin molded article according to the above [8], wherein the release agent is at least one selected from the group consisting of pentaerythritol tetrastearate, stearic acid stearate, and stearic acid monoglyceride.
[10] Further, at least one ultraviolet absorber selected from the group consisting of benzotriazole-based, triazine-based, and malonic ester-based ultraviolet absorbers is added in a total of 100 parts by mass of the polycarbonate resins (A) and (B). The polycarbonate resin molded product according to any one of [1] to [9], which is contained in an amount of 0.05 to 1 part by mass.
[11] The polycarbonate resin molded body according to any one of [1] to [10], wherein the molded body is an audio panel, a windshield member, or a protector.

According to the present invention, there is provided a polycarbonate resin molded article having both high surface hardness, high impact resistance and excellent color tone (transparency).
The reason why the polycarbonate resin molded body of the present invention exhibits such an effect is not certain, but when two types of polycarbonate resins are mixed, if the polymerization method is the same, both are compatible and the molded body Tends to have a uniform composition from the core to the surface layer. For example, the combination of the melt polymerization methods is probably the most familiar and probably compatible with the terminal hydroxyl group, and the composition of the core part and the surface layer part hardly change.
The polycarbonate resin (A) having the repeating unit of the general formula (1) used in the present invention is originally high in hardness. In the present invention, the repeating unit of the general formula (2) having a different polymerization method is used. When combined with the polycarbonate resin (B), the polycarbonate resin (A) having poor compatibility is likely to be unevenly distributed on the surface layer of the molded article, and the hardness is high. In this case, the polycarbonate resin (A) has a low molecular weight. The compatibility is increased and the hardness is difficult to be obtained, and the strength is also lowered. If the molecular weight is too high, it is difficult to extrude into the surface layer of the molded body and the fluidity is also lowered, so the viscosity average molecular weight is in the range of 18,000 to 30,000 By doing so, it is considered to have all of high surface hardness, high impact resistance, and excellent color tone (transparency).
Usually, in a system with poor compatibility, it is not good because it does not become transparent, or so-called “delamination” or surface peeling easily occurs. Excellent operational effects.

（一般式（１）中、Ｒ^１はメチル基、Ｒ^２は水素原子またはメチル基を示し、Ｘは、

を示し、Ｒ^３及びＲ^４は水素原子またはメチル基を示し、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示す。）

（一般式（２）中、Ｘは前記一般式（１）におけるＸと同義である。） <Outline of the invention>
The polycarbonate resin molded article of the present invention comprises a polycarbonate resin composition containing a polycarbonate resin (A) having a repeating unit of the following general formula (1) and a polycarbonate resin (B) having a repeating unit of the following general formula (2). An injection molded article,
The polycarbonate resin (A) and the polycarbonate resin (B) are produced by different polymerization methods, and the viscosity average molecular weight (Mv) of the polycarbonate resin (A) is in the range of 18,000 to 30,000. The surface hardness (measured in accordance with JIS K5600) measured with a multipurpose test piece injection-molded in accordance with K7152 is a pencil hardness of F or more.

(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 represent a hydrogen atom or a methyl group, and Z represents a group that forms an alicyclic hydrocarbon which may combine with C to have a substituent having 6 to 12 carbon atoms. . )

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

Hereinafter, the contents of the present invention will be described in detail.
The constituent elements described below may be explained based on typical embodiments and specific examples of the present invention. However, the present invention is construed to be limited to such embodiments and specific examples. It is not something.
Further, in the present specification, “to” is used in the sense of including the numerical values described before and after the lower limit and the upper limit unless otherwise specified.

（一般式（１）中、Ｒ^１はメチル基、Ｒ^２は水素原子またはメチル基を示し、Ｘは、

を示し、Ｒ^３及びＲ^４は水素原子またはメチル基を示し、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示す。） <Polycarbonate resin (A)>
The polycarbonate resin (A) used in the present invention is a polycarbonate resin having a repeating unit represented by the following general formula (1).

(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 represent a hydrogen atom or a methyl group, and Z represents a group that forms an alicyclic hydrocarbon which may combine with C to have a substituent having 6 to 12 carbon atoms. . )

In the general formula (1), R ¹ is a methyl group and R ² is a hydrogen atom or a methyl group, but R ² is particularly preferably a hydrogen atom.

である場合、Ｒ^３及びＲ^４の両方がメチル基であるイソプロピリデン基であることが好ましく、また、Ｘが、

のとき、Ｚは、上記式（１）中の２個のフェニル基と結合する炭素Ｃと結合して、炭素数６〜１２の二価の脂環式炭化水素基を形成するが、二価の脂環式炭化水素基としては、例えば、シキロヘキシリデン基、シクロヘプチリデン基、シクロドデシリデン基、アダマンチリデン基、シクロドデシリデン基等のシクロアルキリデン基が挙げられる。置換されたものとしては、これらのメチル置換基、エチル置換基を有するもの等が挙げられる。これらの中でも、シクロヘキシリデン基、シキロヘキシリデン基のメチル置換体（好ましくは３，３，５−トリメチル置換体）、シクロドデシリデン基が好ましい。 X is

Is preferably an isopropylidene group in which both R ³ and R ⁴ are methyl groups, and X is

In this case, 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 alicyclic 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.

Preferable specific examples of the polycarbonate resin (A) used in the present invention include the following polycarbonate resins i) to iv).
i) having a repeating unit derived from 2,2-bis (3-methyl-4-hydroxyphenyl) propane, that is, a repeating unit in which R ¹ is a methyl group, R ² is a hydrogen atom, and X is an isopropylidene group What you have,
ii) having a repeating unit derived from 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, that is, a repeating unit in which R ¹ is a methyl group, R ² is a methyl group, and X is an isopropylidene group thing,
iii) a repeating unit derived from 2,2-bis (3-methyl-4-hydroxyphenyl) cyclohexane, that is, having a repeating unit in which R ¹ is a methyl group, R ² is a hydrogen atom, and X is a cyclohexylidene group ,
iv) A repeating unit derived from 2,2-bis (3-methyl-4-hydroxyphenyl) cyclododecane, that is, a repeating unit in which R ¹ is a methyl group, R ² is a hydrogen atom, and X is a cyclododecylidene group. What you have.
Among these, the polycarbonate resin is more preferably i), ii) or iii), more preferably i) or iii), particularly i).

  These polycarbonate resins (A) are respectively 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2- Bis (3-methyl-4-hydroxyphenyl) cyclohexane and 2,2-bis (3-methyl-4-hydroxyphenyl) cyclododecane can be used as dihydroxy compounds.

  The polycarbonate resin (A) may have a carbonate repeating unit other than the repeating unit of the general formula (1). For example, the repeating unit of the general formula (2) (that is, a repeating unit derived from, for example, bisphenol-A). Or you may have a repeating unit derived from the other dihydroxy compound as mentioned later. The copolymerization amount of the repeating unit other than the repeating unit of the general formula (1) is usually 60 mol% or less, preferably 55 mol% or less, preferably 50 mol% or less, more preferably 40 mol% or less, and further 30 The mol% or less, particularly 20 mol% or less, 10 mol% or less, and most preferably 5 mol% or less.

The viscosity average molecular weight (Mv) of the polycarbonate resin (A) used in the present invention needs to be 18,000 to 30,000. When the viscosity average molecular weight is less than 18,000, the compatibility with the polycarbonate resin (B) is improved and the hardness is hardly obtained, and the strength is lowered. When the viscosity average molecular weight exceeds 30,000, the polycarbonate resin (A) Is difficult to extrude to the surface layer of the molded body, and the fluidity is also lowered, so that the moldability is deteriorated. In particular, it is difficult to produce a thin molded product having a thickness of, for example, 2 mm or less. Also, the hue tends to deteriorate.
The lower limit of the preferred molecular weight of the polycarbonate resin (A) is 19,000, more preferably 20,000, still more preferably 21,000, and the upper limit is preferably 29,000, more preferably 28,500.
Here, the viscosity average molecular weight (Mv) 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. Formula: means a value calculated from the formula η = 1.23 × 10 ⁻⁴ M ^0.83 .

  The polycarbonate resin (A) may be used singly or in combination of two or more, and may be adjusted to the above viscosity average molecular weight by mixing two or more types of polycarbonate resins having different viscosity average molecular weights. Moreover, you may mix and use the polycarbonate resin whose viscosity average molecular weight is outside said suitable range as needed.

（一般式（２）のＸは、前記一般式（１）と同義である。） <Polycarbonate resin (B)>
The polycarbonate resin (B) used in the present invention is a polycarbonate resin having a repeating unit represented by the following general formula (2).

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

を示すが、Ｘが、

である場合、Ｒ^３及びＲ^４の両方がメチル基であるイソプロピリデン基であることが好ましく、また、Ｘが、

のとき、Ｚは、上記式（２）中の２個のフェニル基と結合する炭素Ｃと結合して、炭素数６〜１２の二価の脂環式炭化水素基を形成するが、二価の脂環式炭化水素基としては、例えば、シキロヘキシリデン基、シクロヘプチリデン基、シクロドデシリデン基、アダマンチリデン基、シクロドデシリデン基等のシクロアルキリデン基が挙げられる。置換されたものとしては、これらのメチル置換基、エチル置換基を有するもの等が挙げられる。これらの中でも、シクロヘキシリデン基、シキロヘキシリデン基のメチル置換体（好ましくは３，３，５−トリメチル置換体）、シクロドデシリデン基が好ましい。 In general formula (2), X has the same meaning as in general formula (1),

Where X is

Is preferably an isopropylidene group in which both R ³ and R ⁴ are methyl groups, and X is

In this case, Z is bonded to carbon C bonded to the two phenyl groups in the above formula (2) to form a bivalent alicyclic hydrocarbon group having 6 to 12 carbon atoms. Examples of the alicyclic 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.

  A particularly preferred specific example of the polycarbonate structural unit represented by the general formula (2) is 2,2-bis (4-hydroxyphenyl) propane, that is, a carbonate structural unit derived from bisphenol-A.

  The polycarbonate resin (B) may have a carbonate structural unit other than the structural unit of the general formula (2), and may have a carbonate structural unit derived from another dihydroxy compound. The amount of the unit other than the repeating unit of the general formula (2) is usually preferably less than 50 mol%, more preferably 40 mol% or less, further 30 mol% or less, particularly 20 mol% or less, and 10 mol%. In the following, 5 mol% or less is most preferable.

The viscosity average molecular weight (Mv) of the polycarbonate resin (B) used in the present invention is preferably 16,000 to 40,000. If Mv is too high, the melt viscosity of the resin composition becomes high and molding becomes difficult. On the other hand, molding may be difficult even if Mv is too low.
The viscosity average molecular weight of the polycarbonate resin (B) is more preferably 30,000 or less, still more preferably 28,000 or less, and the lower limit is more preferably 18,000 or more, and further preferably 20,000 or more. is there.
The definition of the viscosity average molecular weight (Mv) is as described above.
The polycarbonate resin (B) may be adjusted to a viscosity average molecular weight within the above range by mixing two or more kinds of polycarbonate resins having different viscosity average molecular weights. Moreover, you may mix and use the polycarbonate resin whose viscosity average molecular weight is outside said suitable range as needed.

  A particularly preferred specific example of the polycarbonate repeating unit represented by the general formula (2) is 2,2-bis (4-hydroxyphenyl) propane, that is, a carbonate repeating unit derived from bisphenol-A.

The polycarbonate resin (B) may have a carbonate repeating unit other than the repeating unit of the general formula (2), and examples of the other dihydroxy compound include the following aromatic dihydroxy compounds.
2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 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) -1-phenylethane, bis (4-hydroxyphenyl) phenylmethane, 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane, 1,1- Bis (4-hydroxy-3,5-dimethylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3- (1-methylethyl) phenyl) cyclohexane, 1,1-bis (4-hydroxy-3-tert) -Butylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3- (1-methylpropyl) phenyl) cyclohexane, 1,1-bis (4-hydroxy-3-cyclohexylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3-phenylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3) Methylphenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3- (1-methylethyl) Phenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3-tert-butylphenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3- (1-methylpropyl) phenyl ) -1-phenylethane, 1,1-bis (4-hydroxy-3-cyclohexylphenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3-phenylphenyl) -1-phenylethane, , 1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclooctane, 4,4 ′-(1,3-phenylenediene) Sopropylidene) 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 and the like.

<Method for Producing Polycarbonate Resins (A) and (B)>
The method for producing each of the polycarbonate resins (A) and (B) used in the present invention is not limited, but the polycarbonate resin (A) and the polycarbonate resin (B) are produced by different polymerization methods. . Examples of the polymerization method include interfacial polymerization method, melt polymerization method, pyridine method, ring-opening polymerization method of cyclic carbonate compound, solid-phase transesterification method of prepolymer, and the like. The polymerization method is adopted.
Hereinafter, a particularly preferable one among these polymerization methods will be specifically described.

Interfacial polymerization method First, the case where the polycarbonate resin (A) or (B) is produced by the interfacial polymerization method will be described.
In the interfacial polymerization method, in the presence of an organic solvent inert to the reaction and an alkaline aqueous solution, the pH is usually kept at 9 or more, and each dihydroxy compound and a carbonate precursor (preferably phosgene) are reacted, followed by polymerization. A polycarbonate resin is obtained by performing interfacial polymerization in the presence of a catalyst. In the reaction system, a molecular weight adjusting agent (terminal terminator) may be present if necessary, and an antioxidant may be present for the purpose of preventing oxidation of the dihydroxy compound.

  Examples of the organic solvent inert to the reaction include chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, monochlorobenzene and dichlorobenzene; aromatic hydrocarbons such as benzene, toluene and xylene; It is done. In addition, 1 type may be used for an organic solvent and it may use 2 or more types together by arbitrary combinations and a ratio.

Examples of the alkali compound contained in the alkaline aqueous solution include alkali metal compounds and alkaline earth metal compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and sodium hydrogen carbonate. Among them, sodium hydroxide and Potassium hydroxide is preferred. In addition, an alkali compound may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.
Although there is no restriction | limiting in the density | concentration of the alkali compound in alkaline aqueous solution, Usually, in order to control pH in the alkaline aqueous solution of reaction to 10-12, it is used at 5-10 mass%. For example, when phosgene is blown, the molar ratio of the dihydroxy compound and the alkali compound is usually 1: 1.9 or more in order to control the pH of the aqueous phase to be 10 to 12, preferably 10 to 11. In particular, it is preferably set to 1: 2.0 or more, usually 1: 3.2 or less, and more preferably 1: 2.5 or less.

  Examples of the polymerization catalyst include aliphatic tertiary amines such as trimethylamine, triethylamine, tributylamine, tripropylamine, and trihexylamine; alicyclic rings such as N, N′-dimethylcyclohexylamine and N, N′-diethylcyclohexylamine. Tertiary amines; aromatic tertiary amines such as N, N′-dimethylaniline and N, N′-diethylaniline; quaternary ammonium salts such as trimethylbenzylammonium chloride, tetramethylammonium chloride and triethylbenzylammonium chloride Pyridine; guanine; guanidine salt; and the like. In addition, 1 type may be used for a polymerization catalyst and it may use 2 or more types together by arbitrary combinations and a ratio.

Examples of the molecular weight regulator include aromatic phenols having a monovalent phenolic hydroxyl group; aliphatic alcohols such as methanol and butanol; mercaptans; phthalimides, and the like. Among them, aromatic phenols are preferable.
Specific examples of such aromatic phenols include alkyl groups such as m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, p-tert-butylphenol, and p-long chain alkyl-substituted phenol. Examples thereof include substituted phenols; vinyl group-containing phenols such as isopropanyl phenol; epoxy group-containing phenols; carboxyl group-containing phenols such as o-oxinebenzoic acid and 2-methyl-6-hydroxyphenylacetic acid; In addition, a molecular weight regulator may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

  The usage-amount of a molecular weight regulator is 0.5 mol or more normally with respect to 100 mol of dihydroxy compounds, Preferably it is 1 mol or more, and is 50 mol or less normally, Preferably it is 30 mol or less. By making the usage-amount of a molecular weight modifier into this range, the thermal stability and hydrolysis resistance of polycarbonate resin can be improved.

In the reaction, the order of mixing the reaction substrate, reaction medium, catalyst, additive and the like is arbitrary as long as a desired polycarbonate resin is obtained, and an appropriate order may be arbitrarily set. For example, when phosgene is used as the carbonate precursor, the molecular weight regulator can be mixed at any time as long as it is between the reaction (phosgenation) of the dihydroxy compound and phosgene and the start of the polymerization reaction.
In addition, reaction temperature is 0-40 degreeC normally, and reaction time is normally several minutes (for example, 10 minutes)-several hours (for example, 6 hours).

-Melt polymerization method Next, the case where polycarbonate resin (A) or (B) is manufactured by a melt polymerization method is demonstrated. In the melt polymerization method, for example, a transesterification reaction between a carbonic acid diester and a dihydroxy compound is performed.

The dihydroxy compound is as described above.
On the other hand, examples of the carbonic acid diester include dialkyl carbonate compounds such as dimethyl carbonate, diethyl carbonate, and di-tert-butyl carbonate; diphenyl carbonate; substituted diphenyl carbonate such as ditolyl carbonate, and the like. Of these, diphenyl carbonate and substituted diphenyl carbonate are preferable, and diphenyl carbonate is particularly preferable. In addition, 1 type may be used for carbonic acid diester, and it may use 2 or more types together by arbitrary combinations and a ratio.

  The ratio of the dihydroxy compound and the carbonic acid diester is arbitrary as long as the desired polycarbonate resin can be obtained, but it is preferable to use an equimolar amount or more of the carbonic acid diester with respect to 1 mol of the dihydroxy compound. It is more preferable. The upper limit is usually 1.30 mol or less. By setting it as such a range, the amount of terminal hydroxyl groups can be adjusted to a suitable range.

  In the polycarbonate resin, the amount of terminal hydroxyl groups tends to have a great influence on thermal stability, hydrolysis stability, color tone, and the like. For this reason, you may adjust the amount of terminal hydroxyl groups as needed by a well-known arbitrary method. In the transesterification reaction, a polycarbonate resin in which the terminal hydroxyl group amount is adjusted can be usually obtained by adjusting the mixing ratio of the carbonic acid diester and the dihydroxy compound, the degree of vacuum during the transesterification reaction, and the like. In addition, the molecular weight of the polycarbonate resin usually obtained can also be adjusted by this operation.

When adjusting the amount of terminal hydroxyl groups by adjusting the mixing ratio of the carbonic acid diester and the dihydroxy compound, the mixing ratio is as described above.
Further, as a more aggressive adjustment method, there may be mentioned a method in which a terminal terminator is mixed separately during the reaction. Examples of the terminal terminator at this time include monohydric phenols, monovalent carboxylic acids, carbonic acid diesters, and the like. In addition, 1 type may be used for a terminal terminator and it may use 2 or more types together by arbitrary combinations and a ratio.

  When producing a polycarbonate resin by the melt polymerization method, a transesterification catalyst is usually used. Any transesterification catalyst can be used. Among these, it is preferable to use an alkali metal compound and / or an alkaline earth metal compound. In addition, auxiliary compounds such as basic boron compounds, basic phosphorus compounds, basic ammonium compounds, and amine compounds may be used in combination. In addition, 1 type may be used for a transesterification catalyst and it may use 2 or more types together by arbitrary combinations and a ratio.

  In the melt polymerization method, the reaction temperature is usually 100 to 320 ° C. The pressure during the reaction is usually a reduced pressure condition of 2 mmHg or less. As a specific operation, a melt polycondensation reaction may be performed under the conditions in this range while removing by-products such as hydroxy compounds.

  The melt polycondensation reaction can be performed by either a batch method or a continuous method. In the case of a batch system, the order of mixing the reaction substrate, reaction medium, catalyst, additive, etc. is arbitrary as long as the desired polycarbonate resin is obtained, and an appropriate order may be set arbitrarily. However, in view of the stability of the polycarbonate resin and the polycarbonate resin composition, the melt polycondensation reaction is preferably carried out continuously.

In the melt polymerization method, a catalyst deactivator may be used as necessary. As a catalyst deactivator, the compound which neutralizes a transesterification catalyst can be used arbitrarily. Examples thereof include sulfur-containing acidic compounds and derivatives thereof. In addition, a catalyst deactivator may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.
The amount of the catalyst deactivator used is usually 0.5 equivalents or more, preferably 1 equivalent or more, and usually 10 equivalents or less, relative to the alkali metal or alkaline earth metal contained in the transesterification catalyst. Preferably it is 5 equivalents or less. Furthermore, it is 1 mass ppm or more normally with respect to polycarbonate resin, and is 100 mass ppm or less normally, Preferably it is 20 mass ppm or less.

<Different polymerization methods>
The polycarbonate resin (A) and the polycarbonate resin (B) must be produced by different polymerization methods. The combination of the polymerization methods is i) a polycarbonate resin (A) obtained by a melt polymerization method, a polycarbonate resin ( A method in which B) is carried out by an interfacial polymerization method, or a method in which ii) a polycarbonate resin (A) is carried out by an interfacial polymerization method and a polycarbonate resin (B) is carried out by a melt polymerization method, is preferred. The former is i). Since the polycarbonate resin (A) is inferior in polymerization reactivity compared to the polycarbonate resin (B) because of its steric hindrance, it is desirable to produce it by a melt polymerization method with higher reactivity.

<Ratio of polycarbonate resin (A) and (B)>
The mixing ratio of the polycarbonate resin (A) and the polycarbonate resin (B) used in the present invention is 5 to 45 parts by mass of the polycarbonate resin (A) based on a total of 100 parts by mass of the polycarbonate resin (A) and the polycarbonate resin (B). The polycarbonate resin (B) is preferably 95 to 55 parts by mass. When the amount of the polycarbonate resin (A) is less than 5 parts by mass, the surface hardness is reduced and the surface of the molded body is easily damaged, and when it exceeds 45 parts by mass, the impact resistance is easily reduced. There is a tendency that defects such as chipping occur or the hue deteriorates.
A preferable mixing ratio is 10 to 40 parts by mass of the polycarbonate resin (A) and 90 to 60 parts by mass of the polycarbonate resin (B) on the basis of a total of 100 parts by mass of (A) and (B).

Moreover, in this invention, it is preferable that 10 mass parts or more are flake-form powders in a total of 100 mass parts of polycarbonate resin (A) and polycarbonate resin (B). The content ratio of the flaky powder is preferably 15 parts by mass or more, more preferably 20 parts by mass or more. By including the flaky powder at such a ratio, it is possible to prevent classification of other additive components blended as necessary at the time of producing the polycarbonate resin composition, generation of unmelted materials, aggregation of additives, etc. , And it tends to be easy to obtain a molded product excellent in impact resistance and hue (transparency). The average particle size of the flaky powder is preferably 2 mm or less, and more preferably 1.5 mm or less.
The polycarbonate resin other than the flaky powder is preferably a pellet. The pellet length is preferably 1 to 5 mm, more preferably 2 to 4 mm. When the cross section is elliptical, the major axis is 2 to 3.5 mm, the minor axis is 1 to 2.5 mm, and the diameter is when the section is circular. The thing of 2-3 mm is preferable. The length and cross-sectional shape of the pellet can be adjusted by the number of rotations of the strand cutter blade, the winding speed, and the discharge amount of the extruder during the production of the polycarbonate resin.

<Other additives>
Various other additives can also be blended in the polycarbonate resin molded article of the present invention as necessary. Examples of additives include stabilizers, mold release agents, ultraviolet absorbers, flame retardants, colorants, antistatic agents, thermoplastic elastomers, glass fibers, glass flakes, glass beads, carbon fibers, wollastonite, calcium silicate. And inorganic fillers such as aluminum borate whiskers.

  In addition, resin components other than the polycarbonate resins (A) and (B), for example, polyamide, polyethylene, polypropylene, polyester, polyphenylene ether, polystyrene, polyphenylene sulfide, polysulfone, polyether, as long as the effects of the present invention are not impaired. One or two or more of sulfone, ABS resin, SAN resin, liquid crystal polymer and the like can be added and mixed, but the effect of the present invention by using the polycarbonate resin (A) and the polycarbonate resin (B) in combination is used. In order to obtain effectively, when using these other resin components, it is preferable to set it as 10 mass% or less with respect to the sum total of polycarbonate resin (A) and polycarbonate resin (B), especially 5 mass% or less.

<Stabilizer>
The polycarbonate resin molded article of the present invention preferably contains a stabilizer in order to prevent a decrease in molecular weight or deterioration of transparency during molding or the like.
As the stabilizer, a phosphorus stabilizer, a phenol stabilizer, and a sulfur stabilizer are preferable.
Examples of the phosphorus stabilizer include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof. Specifically, triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, mono Butyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylene bis (4,6- G-t rt-butylphenyl) octyl phosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tributyl phosphate, Triethyl phosphate, trimethyl phosphate, triphenyl phosphate, diphenyl monoorthoxenyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, 4,4′-biphenylenediphosphosphinic acid tetrakis (2,4-di-tert-butylphenyl), Examples thereof include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate.

Examples of the phenol-based 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), pentaerythritol tetrakis (3- (3,5-di-neopentyl-4-hydroxyphenyl) And hindered phenol stabilizers such as propionate).
Among these, pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) ) Propionate is preferred. These two hindered phenolic antioxidants are commercially available from BASF under the names “Irganox 1010” and “Irganox 1076”.

As the sulfur stabilizer, tetrakis [methylene-3- (dodecylthio) propionate] methane, bis [2-methyl-4- {3-n-alkyl (C ₁₂ or C ₁₄ ) thiopropionyloxy} -5-t- Butylphenyl] sulfide, di-tridecyl-thio-di-propionate, di-stearyl-thio-di-propionate, di-lauryl-thio-di-propionate and the like, which may be used alone or in combination Two or more kinds can be used in combination.

  The content of the stabilizer is preferably 0.01 parts by mass or more, more preferably 0.02 parts by mass or more with respect to a total of 100 parts by mass of the polycarbonate resins (A) and (B). Part or less, more preferably 0.5 part by weight or less, and still more preferably 0.2 part by weight or less. When the stabilizer content is less than or equal to the lower limit of the above range, the effect of improving molecular weight reduction or transparency deterioration may not be obtained, and when the stabilizer content exceeds the upper limit of the above range, the reverse It tends to be unstable to heat and moisture.

<Release agent>
The polycarbonate resin molded article of the present invention preferably contains a release agent.
Examples of the release agent include aliphatic carboxylic acids, fatty acid esters composed 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. A fatty acid ester composed of an aliphatic carboxylic acid and an alcohol is more preferable.

  Examples of the aliphatic carboxylic acid constituting the fatty acid ester 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, melicic acid, montanic acid, tetrariacontanoic acid. , Adipic acid, azelaic acid and the like.

  As alcohol which comprises fatty acid ester, a saturated or unsaturated monohydric alcohol, a saturated or unsaturated polyhydric alcohol, etc. can be mentioned. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these alcohols, monovalent or polyvalent saturated alcohols having 30 or less carbon atoms are preferable, and aliphatic saturated monohydric alcohols or polyhydric alcohols having 30 or less carbon atoms are more preferable. Here, aliphatic includes alicyclic compounds. Specific examples of these alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol. Etc.

  Specific examples of fatty acid esters composed of aliphatic carboxylic acids and alcohols include beeswax (mixture based on myristyl palmitate), stearic acid stearate, behenic acid behenate, behenic acid stearate, palmitic acid monoglyceride, stearic acid Examples include monoglyceride, stearic acid diglyceride, stearic acid triglyceride, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate. Among these, it is more preferable to use at least one mold release agent selected from the group consisting of pentaerythritol tetrastearate, stearic acid stearate, and stearic acid monoglyceride.

  The content of the release agent is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, with respect to a total of 100 parts by mass of the polycarbonate resins (A) and (B). An upper limit becomes like this. Preferably it is 1 mass part or less, More preferably, it is 0.6 mass part or less, More preferably, it is 0.4 mass part or less. When the content of the release agent is less than the lower limit of the range, the effect of releasability may not be sufficient, and when the content of the release agent exceeds the upper limit of the range, hydrolysis resistance And mold contamination during molding may occur.

<Ultraviolet absorber>
The polycarbonate resin molded article of the present invention preferably contains an ultraviolet absorber. In particular, when used in combination with the above-mentioned phosphorus stabilizer and / or phenol stabilizer, the weather resistance tends to be more improved.
Examples of the ultraviolet absorber include organic ultraviolet absorbers such as benzotriazole compounds, benzophenone compounds, salicylate compounds, cyanoacrylate compounds, triazine compounds, oxanilide compounds, malonic ester compounds, hindered amine compounds, and the like. Among these, at least one UV absorber selected from the group consisting of benzotriazole-based UV absorbers, triazine-based UV absorbers, and malonic ester-based UV absorbers is more preferable.
In particular, it was confirmed that the weather resistance improvement effect on the polycarbonate resin (A) was better than that of the polycarbonate resin (B), and the change in color tone was smaller.

  Specific examples of the benzotriazole ultraviolet absorber include, for example, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis (α, α -Dimethylbenzyl) phenyl] -benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butyl-phenyl) -benzotriazole, 2- (2'-hydroxy-3'-tert-butyl) -5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butyl-phenyl) -5-chlorobenzotriazole), 2- (2'- Hydroxy-3 ′, 5′-di-tert-amyl) -benzotriazole, 2- (2′-hydroxy-5′-tert-octylphenyl) benzotria Sol, 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol], among others, 2- (2 '-Hydroxy-5'-tert-octylphenyl) benzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) Phenol] is preferred, and 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole is particularly preferred.

  Specific examples of the triazine-based UV absorber include 2,4-diphenyl-6- (2-hydroxy-4-methoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy -4-ethoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-propoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6 (2-hydroxy-4-butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-hexyloxyphenyl) -1,3,5-triazine, 2,4 -Diphenyl-6- (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-dodecyloxyphenyl) 1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-benzyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4) -Butoxyethoxyphenyl) -1,3,5-triazine and the like.

  Specific examples of the malonic acid ester ultraviolet absorber include 2- (alkylidene) malonic acid esters, particularly 2- (1-arylalkylidene) malonic acid esters, and such malonic acid ester ultraviolet absorbers. Specific examples include “PR-25” manufactured by Clariant Japan, “B-CAP” manufactured by BASF, and the like.

  The content of the ultraviolet absorber is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, and preferably 100 parts by mass with respect to the total of 100 parts by mass of the polycarbonate resins (A) and (B). Is 1 part by mass or less, more preferably 0.6 part by mass or less, and still more preferably 0.4 part by mass or less. If the content of the ultraviolet absorber is less than the lower limit of the range, the effect of improving the weather resistance may be insufficient, and if the content of the ultraviolet absorber exceeds the upper limit of the range, the mold Debogit etc. may occur and cause mold contamination.

  There are no particular limitations on the method of mixing the polycarbonate resin and additives added as necessary. In the present invention, for example, a method of kneading a solid state polycarbonate resin such as pellets or powder and other additives after kneading with an extruder or the like, a method of mixing a molten polycarbonate resin and other additives, etc. And a method of adding an additive or the like during the polymerization reaction of the raw material monomer in the melt polymerization method or the interfacial polymerization method or at the end of the polymerization reaction.

<Pencil hardness>
The polycarbonate resin molding of the present invention preferably has a surface hardness (measured in accordance with JIS K5600) measured on a multipurpose test piece injection-molded in accordance with JIS K7152 that is F or higher in pencil hardness. The pencil hardness is more preferably H or higher. The molded body of the present invention is characterized by having such a high hardness.
When the pencil hardness is HB or less, the surface of the resin molded body tends to be damaged. Moreover, the pencil hardness of a molded object is 3H or less normally.

  Since the polycarbonate resin molded body of the present invention has the above-described characteristics, it is particularly suitable for, for example, audio panels such as car audio panels; windshield members such as motorcycles; protective equipment such as goggles, helmets, and security shields. It is.

<Manufacture of polycarbonate resin composition>
When the polycarbonate resin composition is produced, the method for mixing the polycarbonate resins (A) and (B) and the above-described additives blended as necessary is not particularly limited, and a known method for producing a polycarbonate resin composition is used. Can be widely adopted.
Specific examples include polycarbonate resins (A) and (B), and components such as the above-mentioned additives blended as necessary, after premixing them using various mixers such as a tumbler or Henschel mixer, and then Banbury. Examples thereof include a melt kneading method using a mixer such as a mixer, a roll, a Brabender, a single screw kneading extruder, a twin screw kneading extruder, or a kneader.

Further, for example, it is possible to produce a polycarbonate resin composition without mixing each component in advance or by mixing only a part of the components in advance and supplying the mixture to an extruder using a feeder and melt-kneading. .
Also, for example, by mixing a part of the components in advance and supplying the resulting mixture to an extruder and melt-kneading it as a master batch, this master batch is again mixed with the remaining components and melt-kneaded. A polycarbonate resin composition can also be produced.

<Polycarbonate resin molding>
The polycarbonate resin molded body of the present invention is produced using the polycarbonate resin composition described above. The polycarbonate resin molded body is molded by an injection molding method. For example, the polycarbonate resin molded body is injection molded using a conventionally known injection molding machine such as an injection molding machine, an ultra-high speed injection molding machine, or an injection compression molding machine.
The polycarbonate resin molded body formed by molding the resin composition of the present invention is a molded body having both high surface hardness and high impact resistance and excellent hue (transparency).

As described above, the polycarbonate resin molded body of the present invention is an injection-molded product having high surface hardness, impact resistance, and excellent hue (transparency), and therefore, a display device member, for example, various displays (displays). As a component member of a device (liquid crystal panel, touch panel, etc.) or a cover for a display device, for example, it can be suitably used as a face cover (face guard) such as a helmet, a transparent shield, a windshield member such as a motorcycle, a transparent protective device, etc. .
In particular, it is suitable for (car) audio panels, windshield members, and protective equipment.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not construed as being limited to the following examples.
In the following description, “parts” means “parts by mass” based on mass standards unless otherwise specified.

Each component used in the examples and comparative examples is as follows.
[Polycarbonate resin (A)]
The following polycarbonate resins (C-PC-1) to (C-PC-5) were used as the polycarbonate resin. Among these, (C-PC-4) and (C-PC-5) are polycarbonate resins that do not satisfy the viscosity average molecular weight defined by the polycarbonate resin (A) of the present invention.

(1) Production of polycarbonate resin (C-PC-1) by melt polymerization:
2,2-bis (3-methyl-4-hydroxyphenyl) propane (hereinafter referred to as “BPC”) 26.14 mol (6.70 kg) and diphenyl carbonate 26.66 mol (5.71 kg) The reactor was placed in a SUS reactor (with an internal volume of 40 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 liquid in the reactor is stirred, and cesium carbonate (Cs ₂ CO ₃ ) is added to the reaction liquid in a molten state as a transesterification catalyst so as to be 1.5 × 10 ⁻⁶ mol per 1 mol of BPC. 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 280 ° C. over 60 minutes and the pressure was reduced to 3 Torr to distill phenol corresponding to almost the entire distillation theoretical amount. Next, the pressure in the reactor was kept below 1 Torr under the same temperature, and the reaction was further continued for 80 minutes to complete the polycondensation reaction. At this time, the stirring rotation speed of the stirrer was 38 rotations / minute, and the reaction liquid temperature just before the completion of the reaction was 290 ° C.
Next, the reaction solution in a molten state is fed into a twin screw extruder, and 4 equivalents of butyl p-toluenesulfonate to cesium carbonate is supplied from the first supply port of the twin screw extruder. After that, the reaction solution was extruded in a strand shape through a die of a twin screw extruder, and cut with a cutter to obtain polycarbonate resin pellets.

The physical properties of the obtained polycarbonate resin (C-PC-1) were as follows.
Pencil hardness: 2H
Viscosity average molecular weight (Mv): 28,000
Pellet length: 4mm
Pellet cross section: major axis 3mm, minor axis 2mm

(2) Production of polycarbonate resin (C-PC-2) by melt polymerization:
26.14 mol (6.70 kg) of BPC and 26.66 mol (5.71 kg) of diphenyl carbonate were placed in a SUS reactor (with an internal volume of 40 liters) equipped with a stirrer and a distillation condensing device. Was replaced with nitrogen gas, and the temperature was raised to 220 ° C. over 30 minutes in a nitrogen gas atmosphere.
Next, the reaction liquid in the reactor is stirred, and cesium carbonate (Cs ₂ CO ₃ ) is added to the reaction liquid in a molten state as a transesterification catalyst so as to be 1.5 × 10 ⁻⁶ mol per 1 mol of BPC. 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 280 ° C. over 60 minutes and the pressure was reduced to 3 Torr to distill phenol corresponding to almost the entire distillation theoretical amount. Next, the pressure in the reactor was kept below 1 Torr under the same temperature, and the reaction was further continued for 80 minutes to complete the polycondensation reaction. At this time, the stirring rotation speed of the stirrer was 38 rotations / minute, and the reaction liquid temperature just before the completion of the reaction was 265 ° C.
Next, the reaction solution in a molten state is fed into a twin screw extruder, and 4 equivalents of butyl p-toluenesulfonate to cesium carbonate is supplied from the first supply port of the twin screw extruder. After that, the reaction solution was extruded in a strand shape through a die of a twin screw extruder, and cut with a cutter to obtain polycarbonate resin pellets.

The physical properties of the obtained polycarbonate resin (C-PC-2) were as follows.
Pencil hardness: 2H
Viscosity average molecular weight (Mv): 22,000
Pellet length: 4mm
Pellet cross section: major axis 3mm, minor axis 2mm

(3) Production of polycarbonate resin (C-PC-3) by interfacial polymerization method:
BPC 13.80 kg / h, sodium hydroxide (NaOH) 5.8 kg / h and water 93.5 kg / h were dissolved at 35 ° C. in the presence of hydrosulfite 0.017 kg / h and then cooled to 25 ° C. The aqueous phase and the organic phase of 61.9 kg / h of methylene chloride cooled to 5 ° C. are supplied to a fluororesin pipe having an inner diameter of 6 mm and an outer diameter of 8 mm, respectively, and fluorine having an inner diameter of 6 mm and a length of 34 m is connected thereto. In a resin pipe reactor, it was brought into contact with 7.2 kg / hour of liquefied phosgene cooled to 0 ° C. separately introduced here.

The raw material is subjected to phosgenation and oligomerization reaction while flowing through phosgene and a pipe reactor at a linear velocity of 1.7 m / second for 20 seconds. At this time, the reaction temperature reached a tower top temperature of 60 ° C. in an adiabatic system. The temperature of the reaction product was adjusted by external cooling to 35 ° C. before entering the next oligomerization tank.
In the oligomerization, triethylamine 5 g / hour (0.9 × 10 ⁻³ mole relative to 1 mole of BPC) was used as a catalyst, and pt-butylphenol 0.153 kg / hour was used as a molecular weight regulator. Introduced.

In this way, the oligomerized emulsion obtained from the pipe reactor is further guided to a reaction vessel equipped with a stirrer having an internal volume of 50 liters and stirred at 30 ° C. in a nitrogen gas (N ₂ ) atmosphere to be oligomerized. Thus, the unreacted sodium salt of BPC (BPC-Na) present in the aqueous phase was consumed, and then the aqueous phase and the oil phase were allowed to stand and separate to obtain an oligomeric methylene chloride solution.
Of the oligomer methylene chloride solution, 23 kg was charged into a 70 liter Faudler-bladed reaction tank, and 10 kg of methylene chloride for dilution was added thereto. Further, 2.2 kg of 25% by weight aqueous sodium hydroxide solution and 6 kg of water were added. And 2.2 g of triethylamine (1.1 × 10 ⁻³ mol relative to 1 mol of BPC) were added, and the mixture was stirred at 30 ° C. in a nitrogen gas atmosphere and subjected to a polycondensation reaction for 60 minutes to obtain a polycarbonate resin.

Next, 30 kg of methylene chloride and 7 kg of water were added, and after stirring for 20 minutes, stirring was stopped and the aqueous phase and the organic phase were separated. To the separated organic phase, 20 kg of 0.1N hydrochloric acid was added and stirred for 15 minutes to extract triethylamine and a small amount of remaining alkali component, and then stirring was stopped to separate the aqueous phase and the organic phase.
Further, 20 kg of pure water was added to the separated organic phase, and the mixture was stirred for 15 minutes, and then the stirring was stopped to separate the aqueous phase and the organic phase. This operation was repeated (three times) until no chlorine ions were detected in the extracted waste water. The obtained purified organic phase was pulverized by feeding into 40 ° C. warm water and dried to obtain a flaky powder of polycarbonate resin.

The physical properties of the obtained polycarbonate resin (C-PC-3) were as follows.
Pencil hardness 2H
Viscosity average molecular weight (Mv) 30,000

(4) Production of polycarbonate resin (C-PC-4) by melt polymerization:
26.14 mol (6.70 kg) of BPC and 26.66 mol (5.71 kg) of diphenyl carbonate were placed in a SUS reactor (with an internal volume of 40 liters) equipped with a stirrer and a distillation condensing device. Was replaced with nitrogen gas, and the temperature was raised to 220 ° C. over 30 minutes in a nitrogen gas atmosphere.
Next, the reaction liquid in the reactor is stirred, and cesium carbonate (Cs ₂ CO ₃ ) is added to the reaction liquid in a molten state as a transesterification catalyst so as to be 1.5 × 10 ⁻⁶ mol per 1 mol of BPC. 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 280 ° C. over 60 minutes and the pressure was reduced to 3 Torr to distill phenol corresponding to almost the entire distillation theoretical amount. Next, the pressure in the reactor was kept below 1 Torr under the same temperature, and the reaction was further continued for 80 minutes to complete the polycondensation reaction. At this time, the stirring rotation speed of the stirrer was 38 rotations / minute, and the reaction liquid temperature just before the completion of the reaction was 260 ° C.
Next, the reaction solution in a molten state is fed into a twin screw extruder, and 4 equivalents of butyl p-toluenesulfonate to cesium carbonate is supplied from the first supply port of the twin screw extruder. After that, the reaction solution was extruded in a strand shape through a die of a twin screw extruder, and cut with a cutter to obtain polycarbonate resin pellets.

The physical properties of the obtained polycarbonate resin (C-PC-4) were as follows.
Pencil hardness: 2H
Viscosity average molecular weight (Mv): 17,000
Pellet length: 4mm
Pellet cross section: major axis 3mm, minor axis 2mm

(5) Production of polycarbonate resin (C-PC-5) by melt polymerization:
26.14 mol (6.70 kg) of BPC and 26.66 mol (5.71 kg) of diphenyl carbonate were placed in a SUS reactor (with an internal volume of 40 liters) equipped with a stirrer and a distillation condensing device. Was replaced with nitrogen gas, and the temperature was raised to 220 ° C. over 30 minutes in a nitrogen gas atmosphere.
Next, the reaction liquid in the reactor is stirred, and cesium carbonate (Cs ₂ CO ₃ ) is added to the reaction liquid in a molten state as a transesterification catalyst so as to be 1.5 × 10 ⁻⁶ mol per 1 mol of BPC. 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 280 ° C. over 60 minutes and the pressure was reduced to 3 Torr to distill phenol corresponding to almost the entire distillation theoretical amount. Next, the pressure in the reactor was kept below 1 Torr under the same temperature, and the reaction was further continued for 80 minutes to complete the polycondensation reaction. At this time, the stirring rotation speed of the stirrer was 38 rotations / minute, and the reaction liquid temperature just before the completion of the reaction was 303 ° C.
Next, the reaction solution in a molten state is fed into a twin screw extruder, and 4 equivalents of butyl p-toluenesulfonate to cesium carbonate is supplied from the first supply port of the twin screw extruder. After that, the reaction solution was extruded in a strand shape through a die of a twin screw extruder, and cut with a cutter to obtain polycarbonate resin pellets.

The physical properties of the obtained polycarbonate resin (C-PC-5) were as follows.
Pencil hardness: 2H
Viscosity average molecular weight (Mv): 33,000
Pellet length: 4mm
Pellet cross section: major axis 3mm, minor axis 2mm

[Polycarbonate resin (B)]
The following polycarbonate resins (A-PC-1) to (A-PC-2) were used as the polycarbonate resin (B).
(1) A-PC-1:
Polycarbonate resin (flaked powder) by the interfacial polymerization method using bisphenol-A as a starting material, average particle size 0.3 mm
Product name “NOVAREX (registered trademark) 7022J” manufactured by Mitsubishi Engineering Plastics Co., Ltd.
Pencil hardness 2B
Viscosity average molecular weight (Mv) 22,000
(2) A-PC-2:
Polycarbonate resin (pellet form) by melt polymerization using bisphenol-A as a starting material, pellet length: 5 mm, pellet cross section: major axis 3 mm, minor axis 2 mm
Product name “NOVAREX (registered trademark) M7025J” manufactured by Mitsubishi Engineering Plastics Co., Ltd.
Pencil hardness 2B
Viscosity average molecular weight (Mv) 23,000

(Examples 1-5) (Comparative Examples 1-6)
Each polycarbonate resin described above was blended and mixed in the proportions shown in Table 1 below (all expressed in parts by mass) and kneaded at a barrel temperature of 280 ° C. with a twin-screw extruder (“TEX30XCT” manufactured by Nippon Steel Works, Ltd.) After producing a polycarbonate resin composition and obtaining pellets and drying at 120 ° C. for 5 hours, various test pieces were prepared according to the following procedures, and the following evaluations were performed.

The evaluation and measurement methods performed in the examples and comparative examples are as follows.
(B) Pencil hardness of molded product Using the obtained polycarbonate resin composition pellets, in accordance with JIS K7152, using an injection molding machine (“J55AD” manufactured by Nippon Steel Co., Ltd.), barrel temperature of 280 ° C., gold The surface hardness of the injection-molded multipurpose test piece under the condition of a mold temperature of 80 ° C. is 1,000 g load using a pencil hardness tester (manufactured by Toyo Seiki Co., Ltd.) in accordance with JIS K5600-5-4. It was calculated | required as pencil hardness measured by.

(B) Surface impact strength Using the obtained polycarbonate resin composition pellets, using an injection molding machine (“J55AD” manufactured by Nippon Steel Co., Ltd.) under conditions of a barrel temperature of 280 ° C. and a mold temperature of 80 ° C. A 100 × 100 × 2 mm test piece was injection molded. About the obtained test piece, according to ASTM D2794, using a "DuPont impact strength measuring machine" manufactured by Toyo Seiki Seisakusyo Co., Ltd., a test was conducted 10 times with a crack as a fracture, and a 50% fracture energy was obtained. At that time, the radius of the hitting core was 1/16 inch, the weight was 133 g, and the temperature was 25 ° C. “NB” indicates that it was not destroyed.

(C) Molded product hue Using the obtained polycarbonate resin composition pellets, an injection molding machine (“J55AD” manufactured by Nippon Steel Works, Ltd.) was used for injection under conditions of a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C. Molding was performed to form a hue evaluation plate (100 × 50 × 3 mm). The hue of the obtained plate was visually evaluated.
○: Hue is good △: Yellowish and the hue is not so good The above evaluation results are shown in the following table.

  From the results shown in Table 1, it can be seen that a polycarbonate resin molded body that satisfies all the specific requirements of the present invention has both high surface hardness and high impact resistance, and is excellent in hue and transparency.

  The polycarbonate resin molded body of the present invention has both high surface hardness and high impact resistance and is excellent in hue (transparency). For example, a display device member, display device cover, windshield member, transparent protection It can be used as a molded body in various applications such as tools, and has very high industrial applicability.

Claims (11)

A molded article obtained by injection-molding a polycarbonate resin composition containing a polycarbonate resin (A) having a repeating unit of the following general formula (1) and a polycarbonate resin (B) having a repeating unit of the following general formula (2),
The polycarbonate resin (A) and the polycarbonate resin (B) are produced by different polymerization methods, and the viscosity average molecular weight (Mv) of the polycarbonate resin (A) is in the range of 18,000 to 30,000. A polycarbonate resin molded article characterized in that the surface hardness (measured in accordance with JIS K5600) measured with a multipurpose test piece injection molded in accordance with K7152 is F or more in pencil hardness.

(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 represent a hydrogen atom or a methyl group, and Z represents a group that forms an alicyclic hydrocarbon which may combine with C to have a substituent having 6 to 12 carbon atoms. . )

(In the general formula (2), X has the same meaning as X in the general formula (1).)   The polycarbonate resin molded product according to claim 1, wherein one of the production methods of the polycarbonate resin (A) and the polycarbonate resin (B) is an interfacial polymerization method and the other is a melt polymerization method. Polycarbonate resin (A)
i) a polycarbonate resin in which R ¹ in the general formula (1) is a methyl group, R ² is a hydrogen atom, and X is an isopropylidene group;
ii) a polycarbonate resin in which R ¹ in the general formula (1) is a methyl group, R ² is a methyl group, and X is an isopropylidene group, or iii) R ¹ in the general formula (1) is a methyl group, R ^A polycarbonate resin in which ² is a hydrogen atom and X is a cyclohexylidene group;
The polycarbonate resin molded product according to claim 1 or 2 selected from. The polycarbonate resin (A) is a polycarbonate resin in which R ¹ in the general formula (1) is a methyl group, R ² is a hydrogen atom, and X is an isopropylidene group. Polycarbonate resin molding.   The polycarbonate resin molded article according to any one of claims 1 to 4, wherein the polycarbonate resin (B) is a polycarbonate resin in which X in the general formula (2) is an isopropylidene group.   The content of the polycarbonate resin (A) and the polycarbonate resin (B) is based on a total of 100 parts by mass of (A) and (B), and 5 to 45 parts by mass of the polycarbonate resin (A) and 95 to 95% of the polycarbonate resin (B). It is 55 mass parts, The polycarbonate resin molding in any one of Claims 1-5.   Furthermore, at least one stabilizer selected from the group consisting of phosphorus-based, phenol-based and sulfur-based stabilizers is 0.01 to 1 with respect to 100 parts by mass in total of the polycarbonate resins (A) and (B). The polycarbonate resin molded product according to any one of claims 1 to 6, which is contained in parts by mass.   Furthermore, the polycarbonate resin in any one of Claims 1-7 which contains 0.05-1 mass part with respect to a total of 100 mass parts of the said polycarbonate resin (A) and (B) fatty acid ester as a mold release agent. Molded body.   The polycarbonate resin molded article according to claim 8, wherein the release agent is at least one selected from the group consisting of pentaerythritol tetrastearate, stearic acid stearate, and stearic acid monoglyceride.   Further, at least one ultraviolet absorber selected from the group consisting of benzotriazole-based, triazine-based, and malonic ester-based ultraviolet absorbers is used with respect to a total of 100 parts by mass of the polycarbonate resins (A) and (B). The polycarbonate resin molded product according to any one of claims 1 to 9, containing 0.05 to 1 part by mass.   The polycarbonate resin molded body according to any one of claims 1 to 10, wherein the molded body is an audio panel, a windshield member, or a protector.