JP5946334B2 - Polycarbonate resin composition - Google Patents

Description

  The present invention relates to a polycarbonate resin composition, and more particularly, to a polycarbonate resin composition having excellent chemical resistance and high surface hardness.

  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 the production of molded parts, especially for home appliances, electronic devices, and liquid crystal display device components (housings), etc., making use of their beautiful appearance to obtain products with high commercial value. .

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 likely to be scratched, and it is desired to have excellent scratch resistance. In addition, since the polycarbonate resin is inferior in chemical resistance, it cannot be used in applications requiring chemical resistance in many cases.
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, anti-plasticizer such as terphenyl compound, polycaprolactone, etc. (Patent Document 3) has been proposed, but the surface hardness is improved to some extent and the transparency is good, but the impact resistance is not sufficient There wasn't.
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, this resin composition has a reduced transparency, and the hardness and chemical resistance are not always satisfactory.

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

  The present invention has been made in view of the above-described problems, and an object of the present invention is to provide a polycarbonate resin composition having excellent chemical resistance and high surface hardness.

The inventors of the present invention have a polycarbonate resin composition containing two types of polycarbonate resins and polyester resins each having a specific structural unit in a specific ratio, and having a phosphorus stabilizer, which has excellent chemical resistance and high surface hardness. And the present invention was completed.
That is, the present invention provides the following polycarbonate resin composition.

[1] A resin composition containing a polycarbonate resin (A), a thermoplastic polyester resin (B), and a phosphorus stabilizer (C),
The ratio of the content of the polycarbonate resin (A) and the thermoplastic polyester resin (B) is 90/10 to 60/40 in mass ratio of (A) / (B),
The polycarbonate resin (A) contains a polycarbonate resin component (A1) having a structural unit of the following general formula (1) and a polycarbonate resin component (A2) having a structural unit of the following general formula (2). The content of A1) is 55% by mass or more in a total of 100% by mass of the polycarbonate resin (A) and the thermoplastic polyester resin (B),
The content of the phosphorus stabilizer (C) is 0.001 to 1 part by mass with respect to 100 parts by mass in total of the polycarbonate resin (A) and the thermoplastic polyester fat (B). object.
(In general formula (1), X is
Or a single bond, and two R ^{1 s} may be the same or different and each represents an alkyl group having 1 to 4 carbon atoms or an optionally substituted aryl group having 1 to 20 carbon atoms, and two R ² are the same However, they may be different and each represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an aryl group having 1 to 20 carbon atoms which may be substituted, and R ³ and R ⁴ are a hydrogen atom, having 1 to 4 carbon atoms. An alkyl group or an optionally substituted aryl group having 1 to 20 carbon atoms is shown, and Z represents an optionally substituted carbocyclic ring having 4 to 12 carbon atoms. )
(X in the general formula (2) has the same meaning as the general formula (1).)

[2] The polycarbonate resin composition according to [1], further containing 2 parts by mass or more of the elastomer (D) with respect to 100 parts by mass in total of the polycarbonate resin (A) and the thermoplastic polyester fat (B).
[3] The polycarbonate resin composition according to the above [1] or [2], wherein the thermoplastic polyester fat (B) is a polybutylene terephthalate resin.
[4] The polycarbonate resin composition according to any one of [1] to [3], wherein the phosphorus stabilizer (C) is an organic phosphate compound.
[5] The polycarbonate resin composition according to the above [4], wherein the organic phosphate compound is monostearyl acid phosphate and / or distearyl acid phosphate.
[6] The polycarbonate resin composition according to any one of [1] to [5], wherein the polycarbonate resin component (A1) is a polycarbonate resin produced by an interfacial polymerization method.
[7] the general formula (1) R ¹ in a methyl group, R ² is hydrogen atom, the above-mentioned [1, characterized in that X in the general formula (1) and (2) is isopropylidene ] The polycarbonate resin composition in any one of [6].
[8] A molded product obtained by molding the polycarbonate resin composition according to any one of [1] to [7].
[9] The molding according to the above [8], wherein the molded product is a display device member, a display device cover, a protective device, a casing or cover of an electric / electronic device, a vehicle-mounted member, a single layer or a multilayer sheet. Goods.

According to the present invention, a polycarbonate resin composition having both high surface hardness and extremely high chemical resistance can be obtained.
The mechanism by which the chemical resistance of the polycarbonate resin composition of the present invention is dramatically improved is not clear, but the polycarbonate resin component (A1) is less compatible with the thermoplastic polyester resin (B), and therefore the It is considered that the polycarbonate resin composition has a very fine layer structure.

  The reason why the polycarbonate resin composition of the present invention exhibits high surface hardness is that the effect of improving the surface hardness of the polycarbonate resin component (A1) relative to the resin composition is remarkable, and the polycarbonate resin component (A1) is polycarbonate. It is presumed that this is because the tendency to be unevenly distributed on the surface portion of the molded body is stronger than that of the resin component (A2). This surface hardness improvement effect is obtained by using, as a raw material monomer, an aromatic dihydroxy compound 2,2-bis (3-methyl-4-hydroxyphenyl) propane as a polycarbonate resin component (A1). A resin (referred to as “C-PC”) was used and 2,2-bis (4-hydroxyphenyl) propane (that is, bisphenol A) was used as a raw material monomer as a polycarbonate resin component (A2). This is remarkable when the polycarbonate resin component (A2) (denoted as “A-PC”) is used.

<Summary of invention>
The polycarbonate resin composition of the present invention is a resin composition containing a polycarbonate resin (A), a thermoplastic polyester resin (B), and a phosphorus stabilizer (C),
The ratio of the content of the polycarbonate resin (A) and the thermoplastic polyester resin (B) is 90/10 to 60/40 in mass ratio of (A) / (B),
The polycarbonate resin (A) contains a polycarbonate resin component (A1) having a structural unit of the general formula (1) and a polycarbonate resin component (A2) having a structural unit of the general formula (2). The content of A1) is 55% by mass or more in a total of 100% by mass of the polycarbonate resin (A) and the thermoplastic polyester resin (B),
The content of the phosphorus stabilizer (C) is 0.001 to 1 part by mass with respect to 100 parts by mass in total of the polycarbonate resin (A) and the thermoplastic polyester resin (B).

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.

<Polycarbonate resin (A)>
The polycarbonate resin (A) used in the present invention is a polycarbonate resin component (A1) having a structural unit represented by the general formula (1) and a polycarbonate resin having a structural unit represented by the general formula (2). Contains component (A2). The polycarbonate resin (A) may be a mixture of the polycarbonate resin component (A1) and the polycarbonate resin component (A2), or may be a copolymerized polycarbonate resin obtained by copolymerizing the component (A1) and the component (A2). .
Hereinafter, the polycarbonate resin components (A1) and (A2) will be described.

<Polycarbonate resin component (A1)>
The polycarbonate resin component (A1) is a polycarbonate resin component having a structural unit represented by the following general formula (1).
(In general formula (1), X is
Or a single bond, and two R ^{1 s} may be the same or different and each represents an alkyl group having 1 to 4 carbon atoms or an optionally substituted aryl group having 1 to 20 carbon atoms, and two R ² are the same However, they may be different and each represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an aryl group having 1 to 20 carbon atoms which may be substituted, and R ³ and R ⁴ are a hydrogen atom, having 1 to 4 carbon atoms. An alkyl group or an optionally substituted aryl group having 1 to 20 carbon atoms is shown, and Z represents an optionally substituted carbocyclic ring having 4 to 12 carbon atoms. )

Examples of the alkyl group having 1 to 4 carbon atoms of R ¹ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Examples of the optionally substituted aryl group having 1 to 20 carbon atoms include a phenyl group, a benzyl group, a tolyl group, a 4-methylphenyl group, and a naphthyl group.

Examples of the alkyl group having 1 to 4 carbon atoms of R ² include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Examples of the optionally substituted aryl group having 1 to 20 carbon atoms include a phenyl group, a benzyl group, a tolyl group, a 4-methylphenyl group, and a naphthyl group.

Among these, R ¹ is preferably a methyl group, an ethyl group, an n-propyl group, or a 4-methylphenyl group, and particularly preferably a methyl group. R ² is preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or a 4-methylphenyl group, and particularly preferably a hydrogen atom.

In the general formula (1), X is
Or a single bond, R ³ and R ⁴ represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an optionally substituted aryl group having 1 to 20 carbon atoms, and Z represents an optionally substituted carbon number. 4 to 12 carbon rings are shown.

Examples of the alkyl group having 1 to 4 carbon atoms of R ³ and R ⁴ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Groups and the like. As a C1-C20 aryl group which may be substituted, a phenyl group, a benzyl group, a tolyl group, 4-methylphenyl group, a naphthyl group etc. are mentioned, for example.
Among these, R ³ and R ⁴ are preferably a methyl group, an ethyl group, an n-propyl group, and a 4-methylphenyl group, more preferably a methyl group, and in particular, both R ³ and R ⁴ are methyl groups. Preferably there is.

Z is bonded to the carbon to which two phenyl groups are bonded in the general formula (1) to form a substituted or unsubstituted divalent carbocycle. Examples of the divalent carbocycle include a cycloalkylidene group such as a cyclopentylidene group, a cyclohexylidene group, a cycloheptylidene group, a cyclododecylidene group, an adamantylidene group (preferably a carbon number of 5 To 12).
Examples of the substituted ones include those having these methyl substituents and ethyl substituents. Among these, a cyclohexylidene group, a methyl-substituted cyclohexylidene group, and a cyclododecylidene group are preferable, and a cyclohexylidene group is particularly preferable.

The structural unit represented by the general formula (1) is preferably a structural unit represented by the following general formula (3).
Here, in the general formula (3), two R ^{1 s} may be the same or different and each represents an alkyl group having 1 to 4 carbon atoms and an optionally substituted aryl group having 1 to 20 carbon atoms. ² may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an optionally substituted aryl group having 1 to 20 carbon atoms, and R ³ and R ⁴ are a hydrogen atom, 1 to carbon atoms. 4 alkyl group and an optionally substituted aryl group having 1 to 20 carbon atoms. )

In general formula (3), R ¹ is preferably a methyl group, an ethyl group, an n-propyl group, or a 4-methylphenyl group, and particularly preferably a methyl group. R ² is preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or a 4-methylphenyl group, and particularly preferably a hydrogen atom.
R ³ and R ⁴ are preferably a methyl group, an ethyl group, an n-propyl group, or a 4-methylphenyl group, more preferably a methyl group, and in particular, both R ³ and R ⁴ are methyl groups. Is preferred.

Preferable specific examples of the polycarbonate resin component (A1) used in the present invention include the following polycarbonate resins i) to iv).
i) having a 2,2-bis (3-methyl-4-hydroxyphenyl) propane structural unit, that is, having a structural unit in which R ¹ is a methyl group, R ² is a hydrogen atom, and X is an isopropylidene group,
ii) 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane structural unit, that is, having a structural unit in which R ¹ is a methyl group, R ² is a methyl group, and X is an isopropylidene group,
iii) 2,2-bis (3-methyl-4-hydroxyphenyl) cyclohexane structural unit, that is, having a structural unit in which R ¹ is a methyl group, R ² is a hydrogen atom, and X is a cyclohexylidene group,
iv) 2,2-bis (3-methyl-4-hydroxyphenyl) cyclododecane structural unit, that is, a structural unit in which R ¹ is a methyl group, R ² is a hydrogen atom, and X is a cyclododecylidene group.
Among these, the polycarbonate resin (component) is more preferably i), ii) or iii), more preferably i) or iii), particularly i).

  These polycarbonate resin components (A1) are 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2, respectively. -Bis (3-methyl-4-hydroxyphenyl) cyclohexane and 2,2-bis (3-methyl-4-hydroxyphenyl) cyclododecane can be used as dihydroxy compounds.

  The polycarbonate resin component (A1) may have a carbonate structural unit other than the structural unit of the general formula (1), and may have a structural unit derived from another dihydroxy compound as described later. The copolymerization amount of structural units other than the structural 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 having the polycarbonate resin component (A1) is preferably 20,000 to 35,000. When the viscosity average molecular weight is within this range, a molded product having good moldability and high mechanical strength can be easily obtained. When the viscosity average molecular weight is less than 20,000, impact resistance is lowered, and cracking or chipping occurs when the product is produced. In the case of exceeding 35,000, the fluidity tends to be lowered, and it is difficult to produce a thin molded product, particularly a thin molded product having a thickness of 2 mm or less. The lower limit of the molecular weight is more preferably 22,000, still more preferably 23,000, particularly preferably 24,000, and the upper limit is more preferably 33,000, still more preferably 32,000, particularly preferably 30,000. It is.
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 .

  As the polycarbonate resin having the polycarbonate resin component (A1), one or a mixture of two or more may be used.

<Polycarbonate resin component (A2)>
The polycarbonate resin component (A2) used in the present invention is a polycarbonate resin component having a structural unit represented by the following general formula (2).
(X in the general formula (2) has the same meaning as the general formula (1).)

A preferable 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 component (A2) 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 copolymerization amount of structural units other than the structural 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, 10 mol% or less, and most preferably 5 mol% or less.

Examples of other dihydroxy compounds 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, 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- (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) cyclopent Tan, 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, etc. Can be mentioned.

The viscosity average molecular weight (Mv) of the polycarbonate resin having the polycarbonate resin component (A2) used in the present invention is preferably 16,000 to 28,000. When the viscosity average molecular weight is within this range, a molded product having good moldability and high mechanical strength is easily obtained. When the viscosity average molecular weight is less than 16,000, impact resistance is remarkably reduced, There is a high possibility that defects such as chipping will occur, and if it exceeds 28,000, the fluidity will decrease, and it will be difficult to produce a thin molded product. The lower limit of the molecular weight of the polycarbonate resin having the polycarbonate resin component (A2) is more preferably 17,000, still more preferably 18,000, and the upper limit thereof is more preferably 27,000.
The definition of the viscosity average molecular weight (Mv) is as described above.

<Method for Producing Polycarbonate Resin Components (A1) and (A2)>
The method for producing the polycarbonate resin having the polycarbonate resin component (A1) or (A2) or the copolymer polycarbonate resin having the component (A1) or (A2) used in the present invention is not particularly limited, and any 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.
Hereinafter, a particularly preferable one of these methods will be specifically described.

-Interfacial polymerization method 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 the dihydroxy compound and a carbonate precursor (preferably phosgene) are reacted. Thereafter, interfacial polymerization is carried out in the presence of a polymerization catalyst to obtain a polycarbonate resin. 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 bisphenol 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).

  The polycarbonate resin component (A1) is preferably a polycarbonate resin produced by an interfacial polymerization method. As described above, the chemical resistance of the polycarbonate resin composition of the present invention is drastically improved because the polycarbonate resin component (A1) is less compatible with the thermoplastic polyester resin (B), and therefore the present invention. This is probably because the polycarbonate resin composition (A1) produced by the interfacial polymerization method does not exhibit this compatible tendency. .

-Melt transesterification method In the melt transesterification 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 transesterification 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 transesterification 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 transesterification method, a catalyst deactivator may be used as necessary. As the catalyst deactivator, a compound that neutralizes the transesterification catalyst can be arbitrarily used. 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.

<Ratio of polycarbonate resin components (A1) and (A2)>
The ratio of the polycarbonate resin component (A1) and the polycarbonate resin component (A2) used in the present invention is, by mass ratio, polycarbonate resin component (A1) / polycarbonate resin component (A2) = 95/5 to 50/50. Is preferred. When the mass ratio of the polycarbonate resin component (A1) is less than 50, the surface hardness is lowered, and when the product is commercialized, the surface is easily scratched. When the mass ratio exceeds 95, the impact resistance is lowered. It becomes easy to cause troubles such as cracks and chipping. A preferable mass ratio is polycarbonate resin component (A1) / polycarbonate resin component (A2) = 95/5 to 60/40.
In addition, content of a polycarbonate resin component (A1) needs to be 55 mass% or more in the total 100 mass% of polycarbonate resin (A) and a thermoplastic polyester resin (B). If the content of the polycarbonate resin component (A1) is less than 55% by mass, the surface hardness is lowered and the surface is easily damaged when manufactured.

Moreover, in this invention, it is preferable that 10 mass% or more is a flaky powder in the total 100 mass% of a polycarbonate resin component (A1) and a polycarbonate resin component (A2). The content ratio of the flaky powder is preferably 15% by mass or more, more preferably 20% by mass or more. By including the flaky powder at such a ratio, it is possible to prevent classification of the phosphorus-based stabilizer and other additive components blended as necessary during the production of the polycarbonate resin composition, It tends to be easy to obtain a molded article that suppresses the aggregation of additives and the like and is excellent in flame retardancy, impact resistance, and 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 during winding of the polycarbonate resin, the winding speed, and the discharge amount of the extruder.

<Thermoplastic polyester resin (B)>
The thermoplastic polyester resin (B) used in the present invention is obtained by a condensation reaction mainly comprising a dicarboxylic acid component comprising a dicarboxylic acid or a reactive derivative thereof and a diol component comprising a diol or an ester derivative thereof. The resulting polymer or copolymer.

  Production of the thermoplastic polyester resin (B) according to the present invention is carried out by reacting a dicarboxylic acid component and a diol component while heating in the presence of a polycondensation catalyst containing titanium, germanium, antimony or the like according to a conventional method. The by-product water or lower alcohol is discharged out of the system. Here, it is possible to take either a batch type polymerization method or a continuous type polymerization method, and it is also possible to increase the degree of polymerization by solid phase polymerization.

  The dicarboxylic acids may be either aromatic dicarboxylic acids or aliphatic dicarboxylic acids, but aromatic dicarboxylic acids are preferred from the viewpoints of heat resistance and dimensional stability. Examples of aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, and 4,4′-biphenyl ether. Dicarboxylic acid, 4,4′-biphenylmethane dicarboxylic acid, 4,4′-biphenylsulfone dicarboxylic acid, 4,4′-biphenylisopropylidenedicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4′-dicarboxylic acid Acid, 2,5-anthracene dicarboxylic acid, 2,6-anthracene dicarboxylic acid, 4,4′-p-ter-phenylenedicarboxylic acid, 2,5-pyridinedicarboxylic acid, etc., and these substituted products (for example, Alkyl group-substituted products such as 5-methylisophthalic acid) and reactive derivatives (eg dimethyl terephthalate) Le, alkyl ester derivatives such as diethyl terephthalate) and the like can also be used.

  Of these, terephthalic acid, 2,6-naphthalenedicarboxylic acid and their alkyl ester derivatives are more preferred, and terephthalic acid and its alkyl ester derivatives are particularly preferred. These aromatic dicarboxylic acids may be used alone or in combination of two or more, and together with the aromatic dicarboxylic acid, an aliphatic dicarboxylic acid such as adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, One or more alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid may be used in combination.

  Examples of the diols include ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propanediol, triethylene glycol, 1,4-butanediol, Aliphatic diols such as neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, decamethylene glycol, 2,2-dimethyl-1,3-propanediol 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, cyclohexanediol, trans- or cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol; Alicyclic diols such as p-xylene diol, bisphenol A, tetrabromobisphenol A, tetrabromobisphenol A bis (2-hydroxyethyl ether) ) Aromatic such as geo - can be exemplified Le, and the like, it can also be used these substituents.

  Of these, ethylene glycol, 1,3-propanediol, 1,4-butanediol and 1,4-cyclohexanedimethanol are more preferable from the viewpoint of heat resistance, dimensional stability, etc. 4-butanediol is particularly preferred. These may be used alone or in combination of two or more. Further, as the diol component, one or more kinds of long chain diols having a molecular weight of 400 to 6,000, that is, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol, etc. May be copolymerized in combination with the above diols.

  Moreover, the thermoplastic polyester resin (B) according to the present invention can be branched by introducing a small amount of a branching agent. Although there is no restriction | limiting in the kind of branching agent, Trifunctional monomers, such as trimellitic acid, trimesic acid, trimellitic acid, pyromerotic acid, a trimethylol ethane, a trimethylol propane, a pentaerythritol, are mentioned.

  Preferable specific examples of the thermoplastic polyester resin (B) used in the present invention include polyethylene terephthalate resin (PET), polypropylene terephthalate resin (PPT), polybutylene terephthalate resin (PBT), polyhexylene terephthalate resin, polyethylene naphthalate resin. (PEN), polybutylene naphthalate resin (PBN), poly (1,4-cyclohexanedimethylene terephthalate) resin (PCT), polycyclohexylcyclohexylate (PCC), and the like. Among these, polyethylene terephthalate resin (PET), polypropylene terephthalate resin (PPT), and polybutylene terephthalate resin (PBT) are preferable from the viewpoint of fluidity and impact resistance. It is preferable to contain 10% by mass or more.

  Specific examples of other thermoplastic polyester resins (B) include, for example, polypivalolactone resins obtained by ring-opening polymerization of lactones, poly (ε-caprolactone) resins, and liquid crystal polymers that form liquid crystals in the molten state (Thermotropic). Liquid Crystal Polymer (TLCP). Specific examples of commercially available liquid crystal polyester resins include Xyday from Nippon Petrochemical Co., Ltd., Sumika Super LCP from Sumitomo Chemical Co., Ltd., VECTRA from Ticona, and Rod Run from Unitika.

  The polybutylene terephthalate resin particularly preferably used in the present invention is composed of terephthalic acid as a main component as a dicarboxylic acid component and 1,4-butanediol as a main component as a diol component, and a saturated polyester obtained by a condensation reaction thereof. It is a polymer or copolymer, and is a thermoplastic polyester resin containing a butylene terephthalate unit as a repeating unit, preferably 70 mol% or more, more preferably 80 mol% or more.

The intrinsic viscosity of the thermoplastic polyester resin (B) used in the present invention may be appropriately selected and determined, but is usually 0.4 to 2 dl / g, preferably 0.5 to 1.5 dl / g. Preferably it is 0.6-1.3 dl / g. It is preferable for the intrinsic viscosity to be 0.4 dl / g or more because mechanical properties and residence heat stability in the resin composition of the present invention tend to be improved. Conversely, it is preferable that the intrinsic viscosity be 2 dl / g or less because the fluidity of the resin composition tends to be improved.
The intrinsic viscosity is a value measured at 30 ° C. using a mixed solvent of phenol / tetrachloroethane (mass ratio 1/1).

The terminal carboxyl group concentration of the thermoplastic polyester resin (B) is usually 3 to 60 μeq / g, preferably 5 to 50 μeq / g, more preferably 7 to 40 μeq / g. When the terminal carboxyl group is 60 μeq / g or less, the mechanical properties of the resin composition tend to be improved. Conversely, when the terminal carboxyl group concentration is 3 μeq / g or more, the residence heat stability of the resin composition is stabilized. It tends to improve the properties, which is preferable.
The terminal carboxyl group concentration of the thermoplastic polyester resin (B) is determined by dissolving 0.5 g of resin in 25 ml of benzyl alcohol and titrating with 0.01 mol / l benzyl alcohol solution of sodium hydroxide. be able to.

  Furthermore, as the thermoplastic polyester resin (B), not only a virgin raw material but also a thermoplastic polyester resin regenerated from a used product, a so-called material recycled thermoplastic polyester resin can be used. Used products include containers, films, sheets, fibers, non-conforming products, sprues, runners, etc., and pulverized products obtained from them or pellets obtained by melting them can also be used. .

<Ratio of polycarbonate resin (A) and thermoplastic polyester resin (B)>
The ratio of the content of the polycarbonate resin (A) and the thermoplastic polyester resin (B) used in the present invention is a mass ratio, and the polycarbonate resin (A) / thermoplastic polyester resin (B) = 90 / 10-60 / 40. It is. When the mass ratio of the polycarbonate resin (A) is less than 60, the surface hardness is lowered, and when the product is commercialized, the surface is easily damaged, and when it exceeds 90, the chemical resistance is lowered. The content ratio of the polycarbonate resin (A) and the thermoplastic polyester resin (B) is preferably polycarbonate resin (A) / thermoplastic polyester resin (B) = 85/15 to 65/35.
And content of a polycarbonate resin component (A1) needs to be 55 mass% or more in a total of 100 mass% of polycarbonate resin (A) and a thermoplastic polyester resin (B). When the content of the polycarbonate resin component (A1) is less than 55% by mass, the surface hardness is lowered and the surface is easily damaged when manufactured. The content of the polycarbonate resin component (A1) is preferably 60% by mass or more in a total of 100% by mass of the polycarbonate resin (A) and the thermoplastic polyester resin (B).

<Phosphorus stabilizer (C)>
Examples of the phosphorus stabilizer (C) used in the present invention include phosphorous acid, phosphorous acid metal salt, phosphoric acid, phosphoric acid metal salt, phosphonite compound, phosphite compound, phosphate compound, and metal salt thereof. Of these, organic phosphate compounds and their metal salts, organic phosphite compounds or organic phosphonite compounds are preferred.

The organic phosphate compound is preferably the following general formula:
(R ¹ O) _3-n P (═O) OH _n
(In the formula, R ¹ is an alkyl group or an aryl group, and may be the same or different. N represents an integer of 0 to 2.)
It is a compound represented by these. More preferably, R ¹ is a long-chain alkyl acid phosphate compound having 8 to 30 carbon atoms. Specific examples of the alkyl group having 8 to 30 carbon atoms include octyl group, 2-ethylhexyl group, isooctyl group, nonyl group, isononyl group, decyl group, isodecyl group, dodecyl group, tridecyl group, isotridecyl group, tetradecyl group, A hexadecyl group, an octadecyl group, an eicosyl group, a triacontyl group, etc. are mentioned.

Examples of the long-chain alkyl acid phosphate include octyl acid phosphate, 2-ethylhexyl acid phosphate, decyl acid phosphate, lauryl acid phosphate, stearyl acid phosphate, oleyl acid phosphate, behenyl acid phosphate, phenyl acid phosphate, nonyl phenyl cyclo acid phosphate Acid phosphate, Phenoxyethyl acid phosphate, Alkoxy polyethylene glycol acid phosphate, Bisphenol A acid phosphate, Dimethyl acid phosphate, Diethyl acid phosphate, Dipropyl acid phosphate, Diisopropyl acid phosphate, Dibutyl acid phosphate, Dioc Le acid phosphate, di-2-ethylhexyl acid phosphate, dioctyl acid phosphate, dilauryl acid phosphate, distearyl acid phosphate, diphenyl acid phosphate, and a bis-nonylphenyl acid phosphate, or the like.
Among these, stearyl acid phosphate is preferable, and monostearyl acid phosphate or distearyl acid phosphate is exemplified. This product is commercially available under the trade name “ADK STAB AX-71” from ADEKA.
As the metal of the metal salt of the organic phosphate compound, calcium, magnesium, aluminum, and zinc are preferable, and zinc is particularly preferable.

As the organic phosphite compound, preferably, the following general formula:
^{R 2 O-P (OR 3} ) (OR 4)
Wherein R ² , R ³ and R ⁴ are each a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and at least one of R ² , R ³ and R ⁴ One is an aryl group having 6 to 30 carbon atoms.)
The compound represented by these is mentioned.

  Examples of the organic phosphite compound include triphenyl phosphite, tris (nonylphenyl) phosphite, dilauryl hydrogen phosphite, triethyl phosphite, tridecyl phosphite, tris (2-ethylhexyl) phosphite, and tris (tridecyl). ) Phosphite, tristearyl phosphite, diphenyl monodecyl phosphite, monophenyl didecyl phosphite, diphenyl mono (tridecyl) phosphite, tetraphenyldipropylene glycol diphosphite, tetraphenyltetra (tridecyl) pentaerythritol tetraphosphite Hydrogenated bisphenol A phenol phosphite polymer, diphenyl hydrogen phosphite, 4,4′-butylidene-bis (3-methyl-6-t rt-butylphenyldi (tridecyl) phosphite), tetra (tridecyl) 4,4′-isopropylidenediphenyldiphosphite, bis (tridecyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, di Lauryl pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tris (4-tert-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, hydrogenated bisphenol A pentaerythritol phosphite Phytopolymer, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite Phosphite, 2,2'-methylenebis (4,6-di -tert- butylphenyl) octyl phosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite and the like.

The organic phosphonite compound is preferably the following general formula:
R ⁵ -P (OR ⁶ ) (OR ⁷ )
(Wherein R ⁵ , R ⁶ and R ⁷ are each a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and at least one of R ⁵ , R ⁶ and R ⁷ ) One is an aryl group having 6 to 30 carbon atoms.)
The compound represented by these is mentioned.

  Examples of the organic phosphonite compound include tetrakis (2,4-di-iso-propylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-n-butylphenyl) -4,4′-biphenyl. Range phosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylene diphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3'-biphenylene diphospho Knight, tetrakis (2,4-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite, tetrakis (2,6-di-iso-propylphenyl) -4,4'-biphenylenediphosphonite, Tetrakis (2,6-di-n-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2, -Di-tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,3'-biphenylenediphosphonite, and tetrakis (2,6- And di-tert-butylphenyl) -3,3′-biphenylenediphosphonite.

As for phosphorus stabilizer (C), 1 type may be contained and 2 or more types may be contained by arbitrary combinations and ratios.
As the phosphorus-based stabilizer (C), as described above, stearyl acid phosphate that exhibits excellent compatibility and dramatically improves elongation and thin-wall toughness in combination with the polycarbonate resin (A) is particularly preferable.

  Content of a phosphorus stabilizer (C) is 0.001-1 mass part with respect to a total of 100 mass parts of polycarbonate resin (A) and thermoplastic polyester fat (B). When the content of the phosphorus stabilizer (C) is less than 0.001 part by mass, it is difficult to expect improvement in the thermal stability and compatibility of the resin composition, and molecular weight reduction and hue deterioration during molding are likely to occur. When the amount exceeds 1 part by mass, the amount tends to be excessive, and silver generation and hue deterioration tend to occur more easily. The content of the phosphorus stabilizer (C) is more preferably 0.005 to 0.7 parts by mass, and still more preferably 0.01 to 0.5 parts by mass.

<Elastomer (D)>
The polycarbonate resin composition of the present invention preferably contains an elastomer (D).
As the elastomer (D), methyl methacrylate-butadiene-styrene copolymer (MBS resin), styrene-butadiene-styrene copolymer (SBS), copolymer hydrogenated by hydrogenation of SBS (SEBS) Called styrene-butadiene triblock copolymer and its hydrogenated product, called styrene-isoprene copolymer (SIS), and hydrogenated copolymer (SIPS) Styrene-isoprene triblock copolymer and its hydrogenated products, EPR, EPDM and other olefinic elastomers called TPO, polyester elastomers, silicone elastomers, acrylate elastomers, silicone rubbers and acrylate rubbers A vinyl monomer is graft-polymerized to a composite rubber composed of components. Composite rubber-based graft copolymer, and the like made.

  Of these, a graft copolymer obtained by graft copolymerizing a rubber component with a monomer component copolymerizable therewith is preferable. The production method of the graft copolymer may be any production method such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization, and the copolymerization method may be single-stage graft or multi-stage graft.

  The rubber component usually has a glass transition temperature of 0 ° C. or lower, preferably −20 ° C. or lower, more preferably −30 ° C. or lower. Specific examples of the rubber component include polybutadiene rubber, polyisoprene rubber, polybutyl acrylate and poly (2-ethylhexyl acrylate), polyalkyl acrylate rubber such as butyl acrylate / 2-ethyl hexyl acrylate copolymer, and polyorganosiloxane rubber. Silicone rubber, butadiene-acrylic composite rubber, IPN (Interpenetrating Polymer Network) type composite rubber composed of polyorganosiloxane rubber and polyalkylacrylate rubber, styrene-butadiene rubber, ethylene-propylene rubber, ethylene-butene rubber, ethylene-octene rubber, etc. And ethylene-α-olefin rubber, ethylene-acrylic rubber, fluororubber, and the like. These may be used alone or in admixture of two or more. Among these, in terms of mechanical properties and surface appearance, polybutadiene rubber, polyalkyl acrylate rubber, polyorganosiloxane rubber, IPN composite rubber composed of polyorganosiloxane rubber and polyalkyl acrylate rubber, and styrene-butadiene rubber are preferable. .

  Specific examples of the monomer component that can be graft copolymerized with the rubber component include aromatic vinyl compounds such as styrene, vinyl cyanide compounds such as acrylonitrile, (meth) acrylic acid ester compounds, (meth) acrylic acid compounds, and glycidyl. Epoxy group-containing (meth) acrylic acid ester compounds such as (meth) acrylate; maleimide compounds such as maleimide, N-methylmaleimide and N-phenylmaleimide; α, β-unsaturated carboxylic acids such as maleic acid, phthalic acid and itaconic acid Examples thereof include acid compounds and anhydrides thereof (eg maleic anhydride). These monomer components may be used alone or in combination of two or more. Among these, aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, and (meth) acrylic acid compounds are preferable from the viewpoint of mechanical properties and surface appearance, and (meth) acrylic acid esters are more preferable. A compound. Specific examples of the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, and the like. be able to.

  The graft copolymer obtained by copolymerizing the rubber component is preferably of the core / shell type graft copolymer type from the viewpoint of impact resistance and surface appearance. Among them, a layer containing at least one rubber component selected from the above-mentioned polybutadiene-containing rubber, polyalkyl acrylate-containing rubber, and polyorganosiloxane / polyalkyl acrylate-containing rubber is used as a core layer, and its surroundings. A core / shell type graft copolymer comprising a shell layer formed by (co) polymerizing (meth) acrylic acid ester or acrylonitrile / styrene is particularly preferable. The core / shell type graft copolymer preferably contains 40% by mass or more of a rubber component, and more preferably contains 60% by mass or more. Moreover, what contains 10 mass% or more of (meth) acrylic acid is preferable.

  Preferable specific examples of these core / shell type graft copolymers include methyl methacrylate-butadiene-styrene copolymer (MBS), methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (MABS), and methyl methacrylate-butadiene copolymer. Copolymer (MB), methyl methacrylate-acrylic rubber copolymer (MA), methyl methacrylate-acrylic rubber-styrene copolymer (MAS), methyl methacrylate-acrylic-butadiene rubber copolymer, methyl methacrylate-acrylic-butadiene rubber- Examples thereof include styrene copolymers and methyl methacrylate- (acryl / silicone IPN rubber) copolymers. Such a graft copolymer may be used individually by 1 type, or may use 2 or more types together.

  The preferable content of the elastomer (D) is 2 to 40 parts by mass with respect to 100 parts by mass in total of the polycarbonate resin (A) and the thermoplastic polyester fat (B). If the amount is less than 2 parts by mass, the impact resistance improvement effect by the elastomer becomes insufficient. If the amount exceeds 40 parts by mass, the hardness of the molded product obtained by molding the polycarbonate resin composition decreases, and the appearance defect and the heat resistance decrease. Prone to occur. The lower limit of the content is preferably 3 parts by mass or more, and the upper limit of the content is preferably 30 parts by mass or less, more preferably 20 parts by mass or less.

<Other additives>
The polycarbonate resin composition of the present invention may contain other various additives as necessary. Examples of additives include flame retardants, anti-dripping agents, ultraviolet absorbers, mold release agents, other stabilizers other than phosphorus stabilizers (C), colorants, antistatic agents, and the like, and glass fibers and glass. Examples of the filler include flakes, glass beads, carbon fibers, wollastonite, calcium silicate, and aluminum borate whiskers.

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

<Flame Retardant>
The polycarbonate resin composition of the present invention may contain a flame retardant, and examples of the flame retardant include a metal salt flame retardant, a phosphorus flame retardant, a silicone flame retardant, and a halogen flame retardant. Among these, metal salt flame retardants, phosphorus flame retardants, halogen flame retardants are preferred, metal salt flame retardants are more preferred, organometallic salt flame retardants are more preferred, and organic sulfonic acid metal salt flame retardants. Is particularly preferred.

  Among organic sulfonic acid metal salt flame retardants, fluorine-containing aliphatic sulfonic acid alkali metal salts such as potassium trifluoromethanesulfonate and potassium perfluorobutanesulfonate, potassium diphenylsulfone-3-sulfonate, and sodium benzenesulfonate , (Poly) sodium styrenesulfonate, potassium (poly) styrenesulfonate, sodium paratoluenesulfonate, potassium paratoluenesulfonate, cesium paratoluenesulfonate, (sodium (branched) sodium dodecylbenzenesulfonate, sodium trichlorobenzenesulfonate Aromatic sulfonic acid alkali metal salts such as can be preferably used.

  The content of the organic sulfonic acid metal salt flame retardant is preferably 0.01 to 1 part by mass, more preferably 0.03, relative to 100 parts by mass in total of the polycarbonate resin (A) and the thermoplastic polyester resin (B). -0.5 mass part, More preferably, it is 0.04-0.3 mass part, Most preferably, it is 0.06-0.2 mass part.

Examples of phosphorus flame retardants include red phosphorus, coated red phosphorus, polyphosphate compounds, phosphate ester compounds, and phosphazene compounds. Among these, phosphate ester compounds are preferable.
The phosphate ester compound may be a low molecule, an oligomer, or a polymer. Specific examples thereof include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl. Phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, diisopropylphenyl phosphate, tris (chloroethyl) phosphate, tris (dichloropropyl) phosphate, tris (chloropropyl) phosphate, bis (2,3- Dibromopropyl) -2,3-dichloropropyl phosphate, tris (2,3-dibromopropyl) phosphate, bis (chloropropyl) monooctyl Sulfate, bisphenol A bisphosphate, hydroquinone bisphosphate, resorcin bisphosphate, trioxybenzene triphosphate, etc., phenyl resorcin / polyphosphate, cresyl / resorcin / polyphosphate, phenyl / cresyl / resorcin / polyphosphate, xylyl / resorcin / poly Condensed phosphoric acid such as phosphate, phenyl-pt-butylphenyl / resorcin / polyphosphate, phenyl / isopropylphenyl / resorcin / polyphosphate, cresyl / xylyl / resorcin / polyphosphate, phenyl / isopropylphenyl / diisopropylphenyl / resorcin / polyphosphate Examples include esters. Among these, condensed phosphates are preferable from the viewpoint of thermal stability.

  The content of the phosphorus-based flame retardant is preferably 2 to 30 parts by mass, more preferably 4 to 25 parts by mass, and still more preferably, with respect to 100 parts by mass in total of the polycarbonate resin (A) and the thermoplastic polyester resin (B). 5 to 16 parts by mass.

  Examples of the silicone flame retardant include a silicone varnish, a silicone resin in which a substituent bonded to a silicon atom is an aromatic hydrocarbon group and an aliphatic hydrocarbon group having 2 or more carbon atoms, a main chain having a branched structure and containing A silicone compound having an aromatic group in the organic functional group, a silicone powder carrying a polydiorganosiloxane polymer which may have a functional group on the surface of silica powder, an organopolysiloxane-polycarbonate copolymer, etc. Can be mentioned.

  The content of the silicone flame retardant is preferably 2 to 30 parts by mass, more preferably 3 to 25 parts by mass, and still more preferably, with respect to 100 parts by mass in total of the polycarbonate resin (A) and the thermoplastic polyester resin (B). 4 to 20 parts by mass.

  As the halogen-based flame retardant, a brominated flame retardant is preferable. Specific examples of brominated flame retardants include, for example, brominated epoxy such as tetrabromobisphenol A, tribromophenol, brominated aromatic triazine, tetrabromobisphenol A epoxy oligomer, tetrabromobisphenol A epoxy polymer, and decabromodiphenyl oxide. Brominated benzyl (meth) acrylate such as tribromoallyl ether, pentabromobenzyl polyacrylate, brominated polyphenylene ether, brominated phenoxy resin, glycidyl brominated bisphenol A, tetrabromobisphenol A carbonate oligomer, tetrabromobisphenol A carbonate polymer Brominated polycarbonate such as ethylene bistetrabromophthalimide, brominated imide, decabromodiphenylethane, brominated poly Styrene, hexabromocyclododecane, and the like. Of these, brominated benzyl (meth) acrylate, brominated epoxy, brominated polystyrene and brominated imide are preferred from the viewpoint of good thermal stability, brominated benzyl (meth) acrylate, brominated polystyrene, brominated polycarbonate and Brominated imides are more preferred, with brominated polystyrene, brominated polycarbonates and brominated imides being even more preferred.

  The content of the halogen-based flame retardant is preferably 2 to 30 parts by mass, more preferably 10 to 28 parts by mass, and still more preferably with respect to 100 parts by mass in total of the polycarbonate resin (A) and the thermoplastic polyester resin (B). 15 to 25 parts by mass.

  The content of the flame retardant is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, with respect to 100 parts by mass in total of the polycarbonate resin (A) and the thermoplastic polyester resin (B). Moreover, Preferably it is 30 mass parts or less. When the content of the flame retardant is excessively small, the flame retardant effect tends to decrease. When the content of the flame retardant is excessively large, the mechanical strength of the resin molded product tends to decrease.

  The content of the flame retardant is usually 0.01 parts by mass or more, preferably 0.03 parts by mass or more, with respect to 100 parts by mass in total of the polycarbonate resin (A) and the thermoplastic polyester resin (B). Usually 30 parts by mass or less, preferably 20 parts by mass or less. If the flame retardant content is less than the lower limit of the range, the flame retardant improvement effect may be insufficient, and if the flame retardant content exceeds the upper limit of the range, the transparency In addition, mechanical properties and thermal properties may be degraded.

<Anti-dripping agent>
The polycarbonate resin composition of the present invention preferably contains an anti-drip agent.
As the anti-dripping agent, a fluoropolymer is preferable, and one kind of fluoropolymer may be used, or two or more kinds may be used in any combination and in any ratio.

  An example of the fluoropolymer is a fluoroolefin resin. The fluoroolefin resin is usually a polymer or copolymer containing a fluoroethylene structure. Specific examples include difluoroethylene resin, tetrafluoroethylene resin, tetrafluoroethylene / hexafluoropropylene copolymer resin, and the like. Of these, tetrafluoroethylene resin and the like are preferable. Examples of the fluoroethylene resin include a fluoroethylene resin having a fibril forming ability.

  Examples of the fluoroethylene resin having fibril-forming ability include “Teflon (registered trademark) 6J” manufactured by Mitsui DuPont Fluorochemicals, “Polyflon F201L”, “Polyflon F103”, “Polyflon FA500B” manufactured by Daikin Chemical Industries, Ltd. Can be mentioned. Further, as commercially available products of aqueous dispersions of fluoroethylene resins, for example, “Teflon (registered trademark) 30J” manufactured by Mitsui DuPont Fluorochemical Co., Ltd., “Teflon (registered trademark) 31-JR”, “Fluon D- manufactured by Daikin Chemical Industries Ltd.” 1 "etc. are mentioned. Furthermore, a fluoroethylene polymer having a multilayer structure obtained by polymerizing vinyl monomers can also be used. Examples of such a fluoroethylene polymer include polystyrene-fluoroethylene composites, polystyrene-acrylonitrile-fluoroethylene. Examples include composites, polymethyl methacrylate-fluoroethylene composites, polybutyl methacrylate-fluoroethylene composites, etc. Specific examples include “Metablene A-3800” manufactured by Mitsubishi Rayon Co., Ltd., “Blendex” manufactured by GE Specialty Chemical Co., Ltd. 449 "and the like. In addition, 1 type may contain the dripping inhibitor and 2 or more types may contain it by arbitrary combinations and a ratio.

The content of the dripping inhibitor is preferably 0.01 to 1 part by mass with respect to 100 parts by mass in total of the polycarbonate resin (A) and the thermoplastic polyester resin (B). Thus, by containing a dripping inhibitor, the melting characteristic of the resin composition can be improved, and specifically, the dripping preventing property at the time of combustion can be improved.
If the content of the anti-dripping agent is less than 0.01 parts by mass, the flame retardancy improving effect by the anti-drip agent tends to be insufficient, and if it exceeds 1 part by mass, the appearance of the molded article obtained by molding the resin composition Defects, mechanical strength, and transparency are likely to decrease. The lower limit of the content is more preferably 0.03 parts by mass, particularly preferably 0.05 parts by mass. The upper limit of the content is more preferably 0.8 parts by mass, particularly preferably 0.5 parts by mass.

<Ultraviolet absorber>
The polycarbonate resin composition of the present invention preferably contains an ultraviolet absorber. In particular, weather resistance tends to be more improved when used in combination with the phosphorus stabilizers described above.
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. Of these, benzotriazole-based UV absorbers, triazine-based UV absorbers, or malonic ester-based UV absorbers are more preferable.
In particular, it was confirmed that the weather resistance improving effect on the polycarbonate resin component (A1) was better than that of the polycarbonate resin component (A2) 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 with respect to 100 parts by mass in total of the polycarbonate resin (A) and the thermoplastic polyester resin (B). Moreover, it is preferably 1 part by mass or less, more preferably 0.6 part by mass or less, and further 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.

<Release agent>
The polycarbonate resin composition 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 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 100 parts by mass in total of the polycarbonate resin (A) and the thermoplastic polyester resin (B). Moreover, the 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 injection molding may occur.

The polycarbonate resin composition of the present invention may contain other stabilizers other than the phosphorus stabilizer (C).
As other stabilizers, phenol stabilizers and sulfur stabilizers are preferable.

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 other stabilizers is preferably 0.01 parts by mass or more, more preferably 0.02 parts by mass or more, with respect to 100 parts by mass in total of the polycarbonate resin (A) and the thermoplastic polyester resin (B). In addition, it is preferably 1 part by mass or less, more preferably 0.5 part by mass or less, and still more preferably 0.2 part by mass or less. When the stabilizer content is less than the lower limit of the above range, the effect of improving the molecular weight or transparency may not be obtained, and when the stabilizer content exceeds the upper limit of the above range, It tends to be unstable to heat and moisture.

<Pencil hardness>
Moreover, the polycarbonate resin composition of the present invention can preferably exhibit extremely high hardness of F or more in pencil hardness.
Here, the pencil hardness is measured according to JIS K5600-5-4. In the present invention, measurement is performed on a 100 × 100 × 2 mm test piece.
When the pencil hardness is lower than F, the surface hardness when the resin composition is used as a product is low, and the surface is easily damaged while the product is used. Among these, H or higher, particularly 2H or higher is preferable.

<Manufacture of polycarbonate resin composition>
When the polycarbonate resin composition of the present invention is produced, the polycarbonate resin components (A1) and (A2), the thermoplastic polyester resin (B), the phosphorus stabilizer (C), and an elastomer (D) blended as necessary. ) And the above-mentioned additives and the like are not particularly limited, and a wide variety of known polycarbonate resin composition production methods can be employed.
Specific examples include the polycarbonate resin components (A1) and (A2), the thermoplastic polyester resin (B) and the phosphorus stabilizer (C), the elastomer (D) blended as necessary, the above additives, and the like. Each component is mixed in advance using various mixers such as a tumbler and a Henschel mixer, and then melt-kneaded with a mixer such as a Banbury mixer, roll, brabender, single-screw kneading extruder, twin-screw kneading extruder, kneader or the like. A method is mentioned.

In addition, for example, without mixing each component in advance, or only a part of the components is mixed in advance, and fed to an extruder using a feeder and melt-kneaded to produce the polycarbonate resin composition of the present invention. You can also.
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. The polycarbonate resin composition of the present invention can also be produced.

<Polycarbonate resin molding>
A polycarbonate resin molded article is produced using the above-described polycarbonate resin composition of the present invention. The molding method of the polycarbonate resin molded body is not particularly limited, and examples thereof include a method of molding using a conventionally known molding machine such as an injection molding machine or an extrusion molding machine.
The polycarbonate resin molded body formed by molding the resin composition of the present invention is a molded body having excellent chemical resistance and high surface hardness.

  As described above, the polycarbonate resin composition of the present invention is excellent in chemical resistance, and a molded body having high surface hardness can be obtained. For example, a member for display device or a cover for display device, protective equipment, electrical and electronic equipment It is particularly suitable as a housing or a cover thereof, a vehicle-mounted member, a single layer or a multilayer sheet.

Examples of the display device member include constituent members of various display (display) devices (liquid crystal panels and touch panels), and examples of the display device cover include these various display devices, multifunctional mobile phones, smart phones, PDAs, and tablets. Examples thereof include a protective cover and a front panel of a type terminal, a personal computer, etc., and a cover of a display unit of a next-generation wattmeter, for example.
Examples of the transparent protector include a face cover (face guard) such as a helmet, a transparent shield, and the like.
As a casing of an electric / electronic device or its cover, for example, a TV, a radio cassette, a video camera, an audio player, a DVD player, a multi-function mobile phone, a smart phone, a PDA, a tablet terminal, a personal computer, a calculator, a copier, a printer, Examples include a casing or a cover of an electric / electronic device such as a facsimile.
In addition, examples of in-vehicle transparent members include glazing, resin windows, headlamp lenses, front (outside) members of car navigation systems (car audio, car AV, etc.), housings, etc., console boxes, center clusters, and meter clusters. Car interior parts such as front members are listed.
Furthermore, it is suitable for applications (liquid crystal display device members, transparent sheets, building materials, etc.) that require hardness, impact resistance, and transparency as single layer or multilayer sheets by single layer or multilayer extrusion.

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 component (A1)]
The following polycarbonate resin (CPC) was used as the polycarbonate resin component (A1).

[Production of polycarbonate resin (CPC) by the interfacial 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 (CPC) were as follows.
Pencil hardness: 2H
Viscosity average molecular weight (Mv): 28,000
Average particle size: 0.3mm

[Polycarbonate resin component (A2)]
The following polycarbonate resin (APC) was used as the polycarbonate resin component (A2).
[APC]:
Polycarbonate resin (pellet form) using bisphenol-A as a starting material and melt transesterification
Product name “NOVAREX M7027J” (registered trademark), manufactured by Mitsubishi Engineering Plastics
Pencil hardness: 2B
Viscosity average molecular weight (Mv): 27,000
Pellet length: 4mm
Pellet cross section: major axis 3mm, minor axis 2mm

[Thermoplastic polyester resin (B)]
Polybutylene terephthalate resin, trade name “Novaduran” (registered trademark) 5010L, manufactured by Mitsubishi Engineering Plastics Co., Ltd. (hereinafter abbreviated as “PBT”)

[Phosphorus stabilizer (C)]
(C-1) Mixture of monostearyl acid phosphate and distearyl acid phosphate manufactured by ADEKA, trade name “AX-71”
(C-2) Stearyl Acid Phosphate Zinc Salt, manufactured by Johoku Chemical Industry Co., Ltd., trade name “JP-518Zn”

[Elastomer (D)]
Butadiene / alkyl acrylate / alkyl methacrylate copolymer, manufactured by Rohm & Haas Co., Ltd., trade name "Paraloid EXL2603"

(Examples 1-5) (Comparative Examples 1-3)
Each component described above was blended and mixed at the composition (parts by mass) shown in Table 1, and kneaded at a barrel temperature of 270 ° C. with a twin-screw extruder (“TEX30XCT” manufactured by Nippon Steel Works) to produce a polycarbonate resin composition. After obtaining pellets and drying at 80 ° C. for 5 hours, various test pieces were prepared according to the following procedures and evaluated as follows.

The evaluation and measurement methods performed in the examples and comparative examples are as follows.
(I) Pencil hardness:
Using the injection molding machine (“SE100DU” manufactured by Sumitomo Heavy Industries, Ltd.), the polycarbonate resin composition pellets obtained by the above-described method are set to a cylinder set temperature of 260 to 280 ° C., a mold temperature of 80 ° C., and a screw rotation speed. Under the condition of 100 rpm, a plate having a thickness of 2 mm, a length of 100 mm and a width of 100 mm was injection molded. About the obtained plate, based on JISK5600-5-4, the pencil hardness was measured with a 1000-g load using the pencil hardness tester (made by Toyo Seiki Co., Ltd.).

(B) Chemical resistance:
Using the injection molding machine (“SE100DU” manufactured by Sumitomo Heavy Industries, Ltd.), the polycarbonate resin composition pellets obtained by the above-described method are set to a cylinder set temperature of 260 to 280 ° C., a mold temperature of 80 ° C., and a screw rotation speed. Under the condition of 100 rpm, a plate having a thickness of 2 mm, a length of 100 mm and a width of 100 mm was injection molded. The resulting plate is sprayed with a polishing agent “Armor All Protectant No. A-3” (import / sales source: Napolex Co., Ltd.) for car interior parts, treated at 60 ° C. for 24 hours, and then neutralized. It was washed with a detergent and the degree of surface roughness was confirmed after drying.
○: Almost no difference from that before the armor treatment was confirmed. ×: The surface was roughened due to the armor treatment, resulting in a wrinkled shape.

(C) Liquidity:
For the polycarbonate resin composition pellets obtained in the manner described above, using a high load-type flow tester, 280 ° C., the outflow amount Q value per unit time of the composition under the conditions of a load 160 kgf (Unit: × 10 ^-2 cc / sec) was measured to evaluate the fluidity. An orifice having a diameter of 1 mm and a length of 10 mm was used.

  From the results shown in Table 1, it can be seen that a polycarbonate resin composition satisfying all the specific requirements of the present invention is excellent in chemical resistance for the first time and has a high surface hardness.

  The polycarbonate resin composition of the present invention is excellent in chemical resistance and has a high surface hardness, so that it can be used as a molded product in various applications, in particular, a display device member or a display device cover, a casing of an electric or electronic device It is suitable for the cover, in-vehicle member, single layer or multilayer sheet, and has very high industrial applicability.

Claims (8)

A resin composition comprising a polycarbonate resin or a polycarbonate resin composition (A), a thermoplastic polyester resin (B) selected from the group consisting of a polyethylene terephthalate resin and a polybutylene terephthalate resin, and a phosphorus stabilizer (C). And
The ratio of the content of the polycarbonate resin or the polycarbonate resin composition (A) and the thermoplastic polyester resin (B) is 90/10 to 60/40 in mass ratio of (A) / (B),
The polycarbonate resin or the polycarbonate resin composition (A) contains a polycarbonate resin component (A1) having a structural unit of the following general formula (1) and a polycarbonate resin component (A2) having a structural unit of the following general formula (2). The content of the polycarbonate resin component (A1) is 55% by mass or more in a total of 100% by mass of the polycarbonate resin or the polycarbonate resin composition (A) and the thermoplastic polyester resin (B).
A phosphorus stabilizer (C) an organic phosphate compound, the content of that is, the total 100 parts by weight of a polycarbonate resin or polycarbonate resin composition (A) and the thermoplastic polyester fat (B), 0.05 ~ A polycarbonate resin composition characterized by being 1 part by mass.
(In general formula (1), X is
Or a single bond, and two R ^{1 s} may be the same or different and each represents an alkyl group having 1 to 4 carbon atoms or an optionally substituted aryl group having 1 to 20 carbon atoms, and two R ² are the same However, they may be different and each represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an aryl group having 1 to 20 carbon atoms which may be substituted, and R ³ and R ⁴ are a hydrogen atom, having 1 to 4 carbon atoms. An alkyl group or an optionally substituted aryl group having 1 to 20 carbon atoms is shown, and Z represents an optionally substituted carbocyclic ring having 4 to 12 carbon atoms. )
(X in the general formula (2) has the same meaning as the general formula (1).) Furthermore, the polycarbonate resin composition of Claim 1 which contains an elastomer (D) 2 mass parts or more with respect to a total of 100 mass parts of polycarbonate resin or a polycarbonate resin composition (A), and thermoplastic polyester fat (B). . The polycarbonate resin composition according to claim 1 or 2 thermoplastic polyester resins (B) is polybutylene terephthalate resin. The polycarbonate resin composition according to claim 3 , wherein the organic phosphate compound is monostearyl acid phosphate and / or distearyl acid phosphate. The polycarbonate resin composition according to any one of claims 1 to 4 , wherein the polycarbonate resin component (A1) is a polycarbonate resin produced by an interfacial polymerization method. Formula (1) in which R ¹ is a methyl group, R ² is a hydrogen atom, according to claim 1 to 5 in which X in the general formula (1) and (2), characterized in that isopropylidene The polycarbonate resin composition in any one. Molded article obtained by molding the polycarbonate resin composition according to any one of claims 1-6. Moldings, member for a display device, a display device for a cover, protective equipment, housing or cover of the electrical and electronic equipment, vehicle members, molded article according to claim 7 which is a single layer or a multilayer sheet.