JP2013112780A - Copolymerized polycarbonate resin composition and molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a copolymerized polycarbonate resin composition and a molded article excellent in fluidity and impact characteristics without decreasing surface hardness and chemical resistance.SOLUTION: The copolymerized polycarbonate resin composition comprises: 98 to 85 parts by weight of a copolymerized polycarbonate resin (A component), which contains a 2,2-bis(4-hydroxy-3-methylphenyl)propane component (component a-1) and a 2,2-bis(4-hydroxyphenyl)propane component (component a-2) as an aromatic dihydroxy component, wherein the proportion of the component a-1 is 40 to 90 mol% with respect to 100 mol of the whole aromatic dihydroxy compound, and which has a viscosity average molecular weight of 1.8×10to 3.2×10; and 2 to 15 parts by weight of a specified fluidity improving agent (B component); and blended in 100 parts by weight in total of the above A and B components, 1 to 10 parts by weight of an impact resistance improving agent (C component) and 0.05 to 0.5 parts by weight of a pentaerythritol ester (D component). The molded article is formed of the above resin composition.

Description

  The present invention reduces surface hardness and chemical resistance by blending a pentaerythritol ester with an aromatic polycarbonate resin composition containing a specific copolymer polycarbonate resin, a specific fluidity improver, and an impact improver. The present invention relates to a copolymer polycarbonate resin composition and a molded article having improved flowability and impact characteristics.

  Aromatic polycarbonate resins are widely used industrially because they have excellent mechanical and thermal properties. However, since the aromatic polycarbonate resin has a high melt viscosity, it has a drawback of poor flowability and poor moldability. The polycarbonate resin is a paint general test method described in JIS K5600-5-4-Part 5: Mechanical properties of coating film-Section 4: Pencil hardness measured in accordance with scratch hardness (pencil method) is 2B However, the surface is soft and easily damaged.

The present inventors for the first time have used aromatic 2-hydroxy components as 2,2-bis (4-hydroxy-3-methylphenyl) propane component (component a-1) and 2,2-bis (4-hydroxyphenyl) propane. Including the component (component a-2), the proportion of the component a-1 is 40 to 90 mol% with respect to 100 mol of the wholly aromatic hydroxy component, and the viscosity average molecular weight is 1.8 × 10 ^{4 to} 3.2. It has been found that the copolymer polycarbonate resin of × 10 ⁴ has excellent surface hardness, but the drawback of poor flowability and inferior moldability has not yet been solved.

  In recent years, molded products made of aromatic polycarbonate resins have become larger, thinner, more complicated in shape, more advanced in performance, and have a growing interest in environmental issues. Therefore, there is a need for a technique for improving the melt fluidity of the aromatic polycarbonate resin composition and improving the injection moldability without impairing the excellent properties of the resin composition.

  For example, as a method for improving the melt fluidity of an aromatic polycarbonate resin composition without impairing the properties of a molded article made of the aromatic polycarbonate resin composition, a method for reducing the molecular weight of the aromatic polycarbonate resin itself Is well known. Moreover, the resin composition which mix | blended specific styrene resin with the aromatic polycarbonate-type resin is proposed (for example, refer patent document 1, patent document 2). In addition, a resin composition in which a specific methacrylate resin is blended with an aromatic polycarbonate resin has been proposed (see, for example, Patent Document 3).

However, it is difficult to say that these resin compositions still have good fluidity and impact resistance, and further improvements are required.
On the other hand, as a method of improving fluidity and impact resistance, a polymer unit composed of (meth) acrylic acid ester having a specific structure represented by phenyl methacrylate as a fluidity improver for an aromatic polycarbonate resin and an aromatic vinyl A resin composition containing a copolymer composed of a polymer unit and an impact improver has been proposed (see, for example, Patent Document 4 and Patent Document 5).

However, in fields where impact resistance and fluidity are particularly required, such as automobile members, the characteristics are not sufficient, and further improvements have been required.
Therefore, a copolymerized polycarbonate resin composition and a molded product excellent in fluidity and impact properties without reducing surface hardness and chemical resistance have not been provided yet.

Japanese Patent Publication No.59-42024 JP-A-62-138514 JP-A 64-1749 International Publication No. 05/030819 Pamphlet JP 2006-257127 A

  An object of the present invention is to provide a copolymerized polycarbonate resin composition and a molded article excellent in fluidity and impact properties without reducing surface hardness and chemical resistance.

  As a result of intensive studies, the present inventors have formulated surface hardness and chemical resistance by adding pentaerythritol ester to a specific copolymer polycarbonate resin composition containing a specific fluidity improver and an impact improver. The inventors have determined that a copolymer polycarbonate resin composition and a molded article excellent in fluidity and impact characteristics can be obtained without lowering the viscosity and completed the present invention.

That is, the present invention is as follows.
1. The aromatic dihydroxy component comprises 2,2-bis (4-hydroxy-3-methylphenyl) propane component (component a-1) and 2,2-bis (4-hydroxyphenyl) propane component (component a-2). And a ratio of the component a-1 is 40 to 90 mol% with respect to 100 mol of the wholly aromatic dihydroxy component, and the viscosity average molecular weight is 1.8 × 10 ^{4 to} 3.2 × 10 ^4. With respect to a total of 100 parts by weight of 98 to 85 parts by weight of resin (component A) and 2 to 15 parts by weight of fluidity improver (component B), 1 to 10 parts by weight of impact improver (component C) and pentaerythritol ester ( D component) An aromatic polycarbonate resin composition containing 0.05 to 0.5 parts by weight, wherein the fluidity improver (component B) is represented by (i) the following general formula (1): (Meth) acrylic A unit comprising a unit formed from an acid ester monomer and / or a (meth) acrylic acid ester monomer (Ba) represented by formula (2) and an aromatic alkenyl compound monomer (Bb) as a main constituent unit The ratio of the monomer (Ba) and the monomer (Bb) in the B component is 80% by weight or more in 100% by weight of the B component, and the total of both in 100% by weight. The monomer (Ba) is 1 to 80% by weight and the monomer (Bb) is 20 to 99% by weight, and (ii) the chloroform-soluble component has a weight average molecular weight of 10,000 to 200,000. A copolymer polycarbonate resin composition.

（式中、Ｒ^１は水素原子またはメチル基、Ｒ^２は炭素環基自体であるか、または炭素環を結合した炭素鎖からなる炭化水素基を表す。）

（式中、Ｒ^３は水素原子またはメチル基、Ｒ^４は炭素環基自体であるか、または炭素環を結合した炭素鎖からなる炭化水素基を表し、ｎは１〜４の整数を表す。）

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents a carbocyclic group itself or a hydrocarbon group composed of a carbon chain bonded to a carbocyclic ring.)

(In the formula, R ³ represents a hydrogen atom or a methyl group, R ⁴ represents a carbocyclic group itself or a hydrocarbon group composed of a carbon chain bonded to a carbocyclic ring, and n represents an integer of 1 to 4. )

Hereinafter, the aromatic polycarbonate resin composition of the present invention may be simply referred to as a polycarbonate resin composition.
2. 2. The copolymer polycarbonate resin composition according to 1 above, wherein the impact improver (component C) comprises at least one rubber-modified resin selected from butadiene, acrylic and silicone, or a copolymer thereof. These rubber-modified resins or copolymers are remarkably excellent in impact resistance at low temperatures.
3. The copolymeric polycarbonate resin according to any one of 1 to 2 above, wherein the inorganic filler (E component) is contained in an amount of 0.1 parts by weight or more and 100 parts by weight or less with respect to 100 parts by weight of the total of the component A and the component B. Composition. According to the inorganic filler of such a blending amount, a copolymer polycarbonate resin composition having excellent mechanical properties such as rigidity and strength and dimensional stability that is difficult to cause sink due to post-shrinkage after taking out the mold during molding processing is provided. The
Typical examples of the inorganic filler (component E) include glass fiber, carbon fiber, glass flake, wollastonite, kaolin clay, mica, talc, and various whiskers (such as potassium titanate whisker and aluminum borate whisker). Is exemplified. Such an inorganic filler has good dispersibility in an aromatic polycarbonate resin and excellent thermal stability during melt-kneading, so a copolymer polycarbonate resin composition having an excellent balance of mechanical properties, dimensional stability, and thermal stability is obtained. provide. In particular, talc, mica and wollastonite are preferably used.
4). 4. The copolymer polycarbonate resin composition according to any one of 1 to 3, wherein the monomer (Ba) in the component B is phenyl methacrylate. Since the flow modifier (component B) having a structural unit formed from phenyl methacrylate is excellent in dispersibility and compatibility, it is a copolymer polycarbonate resin composition excellent in moldability and having a good appearance that is difficult to peel off in layers. It becomes.
5. 5. The copolymer polycarbonate resin composition according to any one of 1 to 4 above, wherein the monomer (Bb) in the component B is styrene. The flow modifier (component B) having a structural unit formed from styrene has a good balance of fluidity, dispersibility, and strength, and therefore has a good appearance with excellent molding processability. It becomes.
6). 6. Copolymer polycarbonate resin composition in any one of said 1-5 which contains 0.0001-1 weight part of heat stabilizer (F component) with respect to a total of 100 weight part of A component and B component.
7). A molded article obtained from the copolymer polycarbonate resin composition according to any one of 1 to 6 above.
8). 8. The molded article as described in 7 above, obtained by injection molding.
9. The molded article according to any one of 7 to 8, which is a member for an automobile.

  The copolymer polycarbonate resin composition and molded product of the present invention are obtained by blending a pentaerythritol ester with a copolymer polycarbonate resin composition containing a specific copolymer polycarbonate resin, a specific fluidity improver, and an impact improver. It was possible to have excellent fluidity and impact characteristics without deteriorating chemical resistance. Therefore, the industrial effect that it produces is exceptional.

Hereinafter, the present invention will be described in detail.
(I) Copolycarbonate resin (component A)
The copolymer polycarbonate resin (component A) used in the present invention is obtained by reacting a dihydric phenol and a carbonate precursor. Examples of the reaction method include an interfacial polycondensation method, a melt transesterification method, a solid phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound.

  The polycarbonate resin may be produced by any production method, and in the case of interfacial polycondensation, a terminal stopper of a monohydric phenol is usually used. The polycarbonate resin may be a branched polycarbonate obtained by polymerizing a trifunctional or higher polyfunctional component in addition to the dihydric phenol. Further, it may be a branched polycarbonate resin obtained by polymerizing polyfunctional phenols such as trifunctional phenols, and further, an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid, a polyorganosiloxane component, and a vinyl monomer are copolymerized. It may be a copolymerized polycarbonate.

  As a result of extensive investigations, the copolymeric polycarbonate resin of the present invention has a main aromatic dihydroxy component of 2,2-bis (4-hydroxy-3-methylphenyl) propane component (component a-1) and 2,2 -A bis (4-hydroxyphenyl) propane component (component a-2) is included, and the ratio of the component a-1 is 40 to 90 mol% with respect to 100 mol of the wholly aromatic dihydroxy component, and 50 to 80 mol%. Is preferred. When the ratio of the component a-1 is not less than the lower limit of the range, the scratch resistance is excellent, and when it is not more than the upper limit of the range, the impact resistance is excellent. The proportion of component a-1 may be achieved by mixing polycarbonate resins having different composition proportions. Moreover, although it is preferable that 90% or more of all the dihydroxy compound components are the component a-1 and the component a-2, hydroxyl compounds other than the component a-1 and the component a-2 are copolymerized to such an extent that performance is not impaired. be able to.

  In the reaction using, for example, phosgene as the carbonate precursor, the reaction is usually performed in the presence of an acid binder and a solvent. As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine is used. As the solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. In order to accelerate the reaction, a catalyst such as a tertiary amine or a quaternary ammonium salt can also be used. In that case, reaction temperature is 0-40 degreeC normally, and reaction time is several minutes-5 hours.

  For example, a transesterification reaction using a carbonic acid diester as a carbonate precursor is carried out by a method in which an aromatic dihydroxy component in a predetermined ratio is stirred with a carbonic acid diester while heating in an inert gas atmosphere to distill the resulting alcohol or phenol. Is called. The reaction temperature varies depending on the boiling point of the alcohol or phenol produced, but is usually in the range of 120 to 300 ° C. The reaction is completed while distilling off the alcohol or phenol produced under reduced pressure from the beginning. Moreover, in order to accelerate | stimulate reaction, the catalyst normally used for transesterification can also be used. Examples of the carbonic acid diester used in the transesterification include diphenyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. Of these, diphenyl carbonate is particularly preferred.

Monofunctional phenols usually used as a terminal terminator can be used. Particularly in the case of a reaction using phosgene as a carbonate precursor, monofunctional phenols are generally used as a terminator for controlling the molecular weight, and the resulting aromatic polycarbonate resin has a terminal monofunctional phenol. Since it is blocked by a group based on, it is superior in thermal stability as compared to those not. Specific examples of the monofunctional phenols include, for example, phenol, m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, 1-phenylphenol, 2-phenyl. Examples include phenol, p-tert-butylphenol, p-cumylphenol, isooctylphenol, and p-long chain alkylphenol.
In producing the polycarbonate resin, the above dihydric phenols can be used alone or in combination of two or more thereof, and a molecular weight regulator, a branching agent, a catalyst and the like can be used as necessary.

The molecular weight of the copolymer polycarbonate resin of the present invention is 1.8 × 10 ^{4 to} 3.2 × 10 ⁴ , preferably 1.9 × 10 ^{4 to} 3.0 × 10 ⁴ , expressed as a viscosity average molecular weight. more preferably from ^{2.0 × 10 4 ~2.6 × 10 4} . When the molecular weight is not less than the lower limit of the range, sufficient impact resistance is obtained, and when the molecular weight is not more than the upper limit of the range, the fluidity is good, which is preferable. Such molecular weight may be achieved by mixing polycarbonate resins having different molecular weights, but in such mixing, the molecular weight difference is preferably within 1.0 × 10 ⁴ .
The viscosity average molecular weight of the polycarbonate is first determined by using an Ostwald viscometer from a solution in which 0.7 g of polycarbonate is dissolved in 100 ml of methylene chloride at 20 ° C., with a specific viscosity (η _SP ) calculated by the following formula:
Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀
[T ₀ is methylene chloride falling seconds, t is sample solution falling seconds]
The viscosity average molecular weight M is calculated from the determined specific viscosity (η _SP ) by the following formula.
η _SP /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10 ⁻⁴ M ^0.83
c = 0.7

  Of 100 parts by weight of the resin composition comprising the specific copolymer polycarbonate resin (component A) and the specific fluidity improver (component B), which is the base of the copolymer polycarbonate resin composition of the present invention, the component A is 98. It is -85 weight part, Preferably it is 97-85 weight part, Most preferably, it is 96-90 weight part. When the component A is at least the lower limit, the mechanical properties such as impact resistance and heat resistance are excellent, and when it is not more than the upper limit, excellent fluidity is obtained.

(II) Fluidity improver (component B)
The flow modifier (component B) used in the present invention is (i) a (meth) acrylate monomer represented by the following general formula (1) and / or (meth) represented by the formula (2). It is a copolymer whose main constituent unit is a unit formed from an acrylate monomer (Ba) and an aromatic alkenyl compound monomer (Bb). (Ii) The weight-average molecular weight of the chloroform-soluble component is It is satisfied that it is 10,000 to 200,000.

（式中、Ｒ^１は水素原子またはメチル基、Ｒ^２は炭素環基自体であるか、または炭素環を結合した炭素鎖からなる炭化水素基を表す。）

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents a carbocyclic group itself or a hydrocarbon group composed of a carbon chain bonded to a carbocyclic ring.)

（式中、Ｒ^３は水素原子またはメチル基、Ｒ^４は炭素環基自体であるか、または炭素環を結合した炭素鎖からなる炭化水素基を表し、ｎは１〜４の整数を表す。）

(In the formula, R ³ represents a hydrogen atom or a methyl group, R ⁴ represents a carbocyclic group itself or a hydrocarbon group composed of a carbon chain bonded to a carbocyclic ring, and n represents an integer of 1 to 4. )

  In addition, it is preferable that all the monomer components are contained in the copolymer of a monomer (Ba) and a monomer (Bb) for the flow modifier used by this invention. However, in the production of a copolymer, it is unavoidable that a polymer consisting of not only a monomer but also a monomer is formed. In the present invention, the monomer (Ba) or the monomer (Bb) is used. A homopolymer may be included. This is because such a homopolymer has good compatibility with the copolymer and acts as a unit on the polycarbonate resin.

  In the flow modifier (component B) used in the present invention, the ratio of the monomer (Ba) and the monomer (Bb) is the sum of both components considering the balance between fluidity and mechanical properties. 80% by weight or more in 100% by weight, preferably 90% by weight or more, more preferably 95% by weight or more. Further, in the total of 100% by weight of both, the monomer (Ba) is preferably 1 to 80% by weight and The monomer (Bb) is 20 to 99% by weight, more preferably the monomer (Ba) is 3 to 50% by weight and the monomer (Bb) is 50 to 97% by weight. The monomer (Ba) is 5 to 30% by weight and the monomer (Bb) is 70 to 95% by weight, most preferably the monomer (Ba) is 5 to 20% by weight and the monomer (Bb) is 80 to 95% by weight.

When the monomer (Ba) is not less than the lower limit of the above range, improvement in delamination or compatibility with the flow reforming effect can be obtained. On the other hand, when the monomer (Ba) is less than or equal to the upper limit of the above range, excellent flow reforming effects and mechanical properties can be obtained.
Moreover, it is preferable that all the copolymer of a monomer (Ba) and a monomer (Bb) is a non-crosslinked copolymer. For example, when 10 ml of chloroform and 1 g of a flow modifier (component B) are stirred and mixed for 30 minutes, it is preferable that a crosslinked structure insoluble in chloroform is not observed. However, as long as the properties of excellent fluidity modification are not impaired, all of the copolymers need not be non-crosslinked, and some crosslinked structures insoluble in organic solvents such as chloroform and acetone exist. There is no particular problem.
The copolymer of the B component has a weight average molecular weight of 10,000 to 200,000 of the chloroform-soluble component excluding a part of the solvent-insoluble crosslinked structure. Such molecular weight keeps a good balance between formability and physical properties such as heat resistance and impact resistance.

  Such molecular weight is calculated by GPC (gel permeation chromatography) measurement under the following conditions. That is, GPC measurement was performed in a clean air environment at a temperature of 23 ° C. and a relative humidity of 50%, and two columns of ResiPore (length 300 mm, inner diameter 7.5 mm) manufactured by Polymer Laboratories were connected in series as a column, and chloroform as a mobile phase. Polymer Laboratories' Easy Cal PS-2 as a standard substance, and a photodiode array detector at a wavelength of 254 nm as a detector, chloroform as a developing solvent, and a solution of 10 mg of sample dissolved in 5 ml of chloroform, 100 μl is injected into the GPC measurement apparatus, and the measurement is performed under conditions of a column temperature of 40 ° C. and a flow rate of 1 ml / min.

  From the obtained results, the molecular weight is calculated from the peak in a range excluding the peak corresponding to the monomer and dimer which are difficult to be called a copolymer. Under the above conditions, since these peaks to be excluded are detected at a retention time of 20 minutes or later, the molecular weight is calculated from the peaks up to 20 minutes.

  In the weight average molecular weight of the flow modifier used in the present invention, a more preferable lower limit is 20,000, further preferably 30,000, and most preferably 40,000. Moreover, the upper limit with more preferable this weight average molecular weight is 150,000, More preferably, it is 140,000, Most preferably, it is 130,000. The soluble component in chloroform is mainly composed of a non-crosslinked copolymer composed of the monomer (Ba) and the monomer (Bb). A polymer of a monomer (Ba) or a monomer (Bb) may be included.

When the weight-average molecular weight of the soluble component is not less than the lower limit, various functions such as heat resistance and rigidity are not easily lowered. In addition, it is difficult to cause problems such as smoke generation, mist, mechanical stains, and poor appearance such as fish eyes during molding.
On the other hand, when the weight average molecular weight is not more than the upper limit, the melt viscosity of the flow modifier itself is not too high, so that a sufficient fluidity modifying effect can be obtained.
Moreover, in the flow modifier of the present invention, it is preferable to use one having a melt viscosity of 300 Pa · s or less.
The melt viscosity is a melt viscosity measured using a capillary rheometer under the conditions of nozzle D = 1 mm, L / D = 16, barrel temperature = 170 ° C., and shear rate = 3000 sec ⁻¹ .

  The copolymer of component B may be any of a random copolymer, a block copolymer, and a graft copolymer, or a mixture thereof. The random copolymer is more preferable in the present invention in that the refractive index of the copolymer is uniform even at a micro level and that it can be produced relatively easily. In the block copolymer, when the polymer unit of the monomer (Ba) is A and the polymer unit of the monomer (Bb) is B, AB type, ABA type, B Any block copolymer such as -A-B type and A-B-A-B type may be used. Furthermore, when the random copolymer unit of the monomer (Ba) and the monomer (Bb) is AB, it may be a block copolymer in which either A or B is substituted with AB. . Further, in the graft copolymer, a copolymer in which the polymer unit B is grafted to the polymer unit A, a copolymer in which the polymer unit A is grafted to the polymer unit B, and either A or B is AB. Any of the graft copolymers having a structure substituted by

  The method for producing the copolymer of component B is not particularly limited, and is represented by radical polymerization such as emulsion polymerization, suspension polymerization, solution polymerization, and bulk polymerization, various living anion polymerizations, and use of TEMPO. Living radical polymerization methods such as nitroxide-mediated radical polymerization, radical polymerization using reversible addition-fragmentation chain transfer agent (RAFT), and atom transfer radical polymerization (ATRP) can be used.

Hereinafter, as a preferred method for producing the flow modifier of the present invention, a method for synthesizing a copolymer by an emulsion radical polymerization method will be described.
Examples of the method for synthesizing a copolymer by the emulsion radical polymerization method include water, an emulsifier, a (meth) acrylic acid ester monomer represented by the above general formula (1) and / or a formula (2). Polymerized as necessary to (meth) acrylic acid ester monomer (Ba) and aromatic alkenyl compound monomer (Bb), and optionally other monomers, polymerization initiators, chain transfer agents, etc. A catalyst is added and polymerization is performed at a high temperature to synthesize a copolymer.

Examples of the emulsifier include nonionic emulsifiers, anionic emulsifiers, cationic emulsifiers, and zwitterionic emulsifiers.
Specific examples of the nonionic emulsifier include polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, dialkylphenoxy poly (ethyleneoxy) ethanol, polyvinyl alcohol, polyacrylic acid, and alkyl cellulose.

Specific examples of the anionic emulsifier include fatty acid salts, higher alcohol sulfates, liquid fatty oil sulfates, sulfates of aliphatic amines and aliphatic amides, fatty alcohol phosphates, dibasic fatty acid esters. Examples thereof include sulfone salts, fatty acid amide sulfonates, alkylaryl sulfonates, and naphthalene sulfonates of formalin condensates.
Specific examples of the cationic emulsifier include aliphatic amine salts, quaternary ammonium salts, and alkylpyridinium salts.
Specific examples of the zwitterionic emulsifier include alkylbetaines.

  The (meth) acrylic acid ester monomer represented by the general formula (1) and / or the (meth) acrylic acid ester monomer (Ba) represented by the formula (2) has a carbocyclic ring in the molecule, that is, It is a carbocycle itself or includes a hydrocarbon group composed of a carbon chain to which the carbocycle is bonded. The carbocycle may be an alicyclic ring such as a cyclohexane ring or an aromatic ring such as a benzene ring and a naphthalene ring. These carbocycles may be substituted with an alkyl group. In the present invention, the notation of (meth) acrylate indicates that both methacrylate and acrylate are included, and the notation of (meth) acrylic acid ester indicates that both methacrylic acid ester and acrylic acid ester are included.

  Specific examples of the (meth) acrylic acid ester represented by the general formula (1) or the formula (2) include cyclohexyl (meth) acrylate, 3,4,5-trimethylcyclohexyl (meth) acrylate, and 4-tert-butyl. Cyclohexyl (meth) acrylate, cyclohexylmethyl (meth) acrylate, 3-cyclohexylpropyl (meth) acrylate, 2-cyclohexylpropyl (meth) acrylate, phenyl (meth) acrylate, 4-methylphenyl (meth) acrylate, 4-tert- Butylphenyl (meth) acrylate, benzyl (meth) acrylate, 4-methylbenzyl (meth) acrylate, 1-phenylethyl (meth) acrylate, 2-phenylethyl (meth) acrylate, 3-phenylpropyl ( Acrylate), 2-phenylpropyl (meth) acrylate, 2-naphthyl (meth) acrylate, cyclohexoxymethyl (meth) acrylate, 2-cyclohexoxyethyl (meth) acrylate, 3-cyclohexoxypropyl (meth) acrylate, 3 , 4,5-trimethylcyclohexoxymethyl (meth) acrylate, 2- (3,4,5-trimethylcyclohexoxy) ethyl (meth) acrylate, 3- (3,4,5-trimethylcyclohexoxy) propyl (meth) Acrylate, 4-tert-butylcyclohexoxymethyl (meth) acrylate, 2- (4-tert-butylcyclohexoxy) ethyl (meth) acrylate, 3- (4-tert-butylcyclohexoxy) propyl (meth) acrylate, Noxymethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, 3-phenoxypropyl (meth) acrylate, 2-phenoxypropyl (meth) acrylate, 4-tert-butylphenoxymethyl (meth) acrylate, 2- (4- tert-Butylphenoxy) ethyl (meth) acrylate, 3- (4-tert-butylphenoxy) propyl (meth) acrylate, 3,4-dimethylphenyl (meth) acrylate, 3,4,5-trimethylphenyl (meth) acrylate 4-methylphenoxymethyl (meth) acrylate, 2- (4-methylphenoxy) ethyl (meth) acrylate, 3- (4-methylphenoxy) propyl (meth) acrylate, 2- (4-methylphenoxy) propyl (meth) Acry , 2-naphthoxymethyl (meth) acrylate, 2- (2-naphthoxy) ethyl (meth) acrylate, and 3- (2-naphthoxy) propyl (meth) acrylate, 2- (2-naphthoxy) propyl (meth) An acrylate etc. are mentioned, These are used by 1 type or in combination of 2 or more types.

  Among these, in the present invention, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, 4-methylphenyl (meth) acrylate, benzyl (meth) acrylate, 4-methylbenzyl (meth) acrylate, 4-tert-butyl Cyclohexyl (meth) acrylate, 4-tert-butylphenyl (meth) acrylate, cyclohexoxymethyl (meth) acrylate, 2-cyclohexoxyethyl (meth) acrylate, phenoxymethyl (meth) acrylate, and 2-phenoxyethyl (meth) Acrylates are preferred, cyclohexyl methacrylate and phenyl methacrylate are more preferred, and phenyl methacrylate is particularly preferred.

  The copolymer of component B used in the present invention is mainly a (meth) acrylate monomer represented by the general formula (1) and / or a (meth) acrylate ester represented by the formula (2). Although composed of units formed from the monomer (Ba) and the aromatic alkenyl compound monomer (Bb), other copolymerizable monomers may be used in combination as necessary. Examples of such monomers include alkyl (meth) acrylates having an alkyl group having 2 to 20 carbon atoms such as methyl (meth) acrylate and ethyl (meth) acrylate, and vinyl cyanide compounds. These can be used alone or in combination of two or more. Still other copolymerizable monomers include amino groups, hydroxy groups, mercapto groups, carboxylic acids such as maleic anhydride, (meth) acrylic acid, glycidyl (meth) acrylate, and hydroxyethyl (meth) acrylate. It may be a monomer containing various functional groups such as an acid group, a carboxylic acid anhydride, a dicarboxylic acid, a halogen group, and a carbonyl halide.

  A monomer having two or more unsaturated groups can be used as a copolymerizable monomer. By using such a monomer, a macromonomer having one or more unsaturated double bonds at the side chain or terminal of the polymer is synthesized, and the other monomer is polymerized in the presence thereof to graft copolymer. A polymer can be produced.

  Specific examples of the monomer having two or more unsaturated groups include allyl (meth) acrylate, triallyl cyanurate, triallyl isocyanurate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, Examples thereof include 1,3-butylene glycol di (meth) acrylate and 1,4-butylene glycol di (meth) acrylate. In consideration of the fluidity of the polycarbonate resin composition, monomers having two or more unsaturated groups having different reactivities such as allyl (meth) acrylate, triallyl cyanurate, and triallyl isocyanurate are preferable. Triallyl cyanurate and triallyl isocyanurate have three allyl groups, but the reactivity of the allyl group that reacts first is different from the reactivity of the allyl group that reacts second and third. Allyl (meth) acrylate is particularly preferable.

Examples of the polymerization initiator include peroxides such as tert-butyl hydroperoxide and cumene hydroperoxide, azo initiators such as azobisisobutyronitrile, and redox in which an oxidizing agent and a reducing agent are combined. A system initiator is mentioned.
Specific examples of redox initiators include sulfoxylate initiators in which ferrous sulfate, ethylenediaminetetraacetic acid disodium salt, Rongalite, and hydroperoxide are combined.

Examples of the chain transfer agent include n-octyl mercaptan and tert-dodecyl mercaptan.
The chain transfer agent is preferably 0.1 to 5 parts by weight, more preferably 0.3 to 1.5 parts by weight per 100 parts by weight in total of the monomers forming the B component copolymer.

  Examples of the aromatic alkenyl compound monomer (Bb) include styrene, α-methyl styrene, o-methyl styrene, p-methyl styrene, vinyl xylene, ethyl styrene, dimethyl styrene, p-tert-butyl styrene, and vinyl naphthalene. In particular, styrene and α-methylstyrene, particularly styrene, is preferably 90% by weight or more in 100% by weight of the monomer (Bb). In a most preferred embodiment, the total amount of the monomer (Bb) is styrene.

  If the molecular weight distribution of the copolymer of component B is too wide, the flowability of the resin composition is decreased, or relatively low molecular weight is increased. There is a high possibility that problems such as mechanical stains and poor appearance such as fish eyes will occur. Therefore, the molecular weight distribution expressed by weight average molecular weight / number average molecular weight (Mw / Mn) is preferably 1-30. The upper limit is more preferably 10, and still more preferably 3. In addition, the calculation method of this molecular weight is based on the above-mentioned GPC measurement. The lower limit is practically preferably 1.3, more preferably 1.8. Further, within the range in which the molecular weight of the copolymer is measured, the peak of the molecular weight distribution by GPC measurement may be single or plural. A copolymer having a single peak is preferable because it can be easily produced.

  An embodiment in which the component B is a graft copolymer will be described. A preferred embodiment when the B component of the present invention is a graft copolymer is a graft copolymer obtained by graft polymerization of the monomer (Bb) in the presence of the polymer formed from the monomer (Ba). A graft copolymer obtained by graft polymerization of a monomer (Ba) in the presence of a polymer or a polymer formed from the monomer (Bb). In any embodiment, such a graft copolymer is more preferably produced using a macromonomer formed from the monomer (Ba) or a macromonomer formed from the monomer (Bb) as described above. preferable.

In such a macromonomer, in consideration of the balance of fluidity, impact resistance, and delamination resistance, it has two or more unsaturated groups with respect to 100 parts by weight of the monomer (Ba) or monomer (Bb). More preferably, the monomer content is 0.7 to 5 parts by weight, and still more preferably 0.8 to 3 parts by weight. When the amount of the monomer having two or more unsaturated groups is less than 0.5 parts by weight, the macromonomer may not form a necessary and sufficient graft bond with the monomer (Bb). When the content of one or more monomers is too large, the proportion of the crosslinked structure insoluble in the organic solvent increases, and the excellent fluidity improving effect is impaired.
The production of such a macromonomer can be performed according to the production of the copolymer. In the polymerization system of the obtained macromonomer, a mixture containing a monomer to be grafted and, if necessary, other monomers copolymerizable with the monomer, a polymerization initiator, a chain transfer agent, and the like is supplied. The polymerization is carried out at a high temperature.

As the polymerization initiator, chain transfer agent and the like, the same ones as described in the production of the copolymer can be applied.
The above is basically a case where a macromonomer is a trunk and a polymer unit formed from a monomer to be grafted is a branch, but only a macromonomer having an unsaturated double bond at the terminal is used. The macromonomer is a branch, and a polymer unit formed from the monomer is a trunk.

(III) Impact improver (component C)
The impact improver (component C) used in the present invention comprises a polymer composed of a rubber component having a glass transition temperature of 10 ° C. or lower, preferably −10 ° C. or lower, more preferably −30 ° C. or lower, and the rubber component. Preferred is a copolymer obtained by bonding another polymer chain to the resulting polymer. Furthermore, the rubber component is preferably a polymer containing at least 35% by weight, more preferably 45% by weight, in 100% by weight of the rubbery polymer. The upper limit of the rubber component content is preferably about 90% by weight in practice.

  The impact improver is more preferably a copolymer formed by bonding other polymer chains. In the production of a rubbery polymer in which another polymer chain is grafted to a rubber component, it is widely known that not a few polymers or copolymers are not grafted on the rubber component. The component C of the present invention may contain such a free polymer or copolymer.

  More specifically, as the impact improver for component C, SB (styrene-butadiene) copolymer, ABS (acrylonitrile-butadiene-styrene) copolymer, MBS (methyl methacrylate-butadiene-styrene) copolymer, MABS ( Methyl methacrylate-acrylonitrile-butadiene-styrene copolymer, MB (methyl methacrylate-butadiene) copolymer, ASA (acrylonitrile-styrene-acrylic rubber) copolymer, AES (acrylonitrile-ethylenepropylene rubber-styrene) copolymer MA (methyl methacrylate-acrylic rubber) copolymer, MAS (methyl methacrylate-acrylic rubber-styrene) copolymer, methyl methacrylate-acrylic-butadiene rubber copolymer, methyl methacrylate-acrylic rubber Diene - styrene copolymer, methyl methacrylate - and the like (acrylic silicone IPN rubber) copolymer. These copolymers are preferably core-shell type graft copolymers in which a polymer chain composed of the above monomer is bonded to a polymer core composed of a rubber component. For example, as rubber components mainly composed of butadiene rubber, acrylic rubber, or butadiene-acrylic composite rubber, Kaneka's Kane Ace B series (for example, B-56 etc.), Mitsubishi Rayon Co., Ltd. Metabrene C series ( For example, C-223A, etc.), W series (eg, W-450A, etc.), Kureha Chemical Co., Ltd. paraloid EXL series (eg, EXL-2602), HIA series (eg, HIA-15, etc.), BTA series (eg, BTA) -III, etc.), KCA series, Rohm & Haas Paraloid EXL series, KM series (eg KM-336P, KM-357P, etc.), Ube modifier's UCL modifier resin series (UMG AB Co., Ltd.) ) UMG AX Resin Series), with acrylic as a rubber component - as consisting mainly of silicone composite rubber include those commercially available under the tradename METABLEN S-2001 or SRK-200 from Mitsubishi Rayon. In particular, a core-shell type graft copolymer in which the rubber component is made of butadiene rubber is a preferred mode in terms of improving impact.

  The rubber particle diameter of the impact improver is preferably 0.1 to 5.0 μm, more preferably 0.2 to 3.0 μm, and particularly preferably 0.2 to 1.5 μm. As the distribution of the rubber particle diameter, either a single distribution or a rubber particle having two or more peaks can be used, and the rubber particles form a single phase in the morphology. Alternatively, it may have a salami structure by containing an occluded phase around the rubber particles.

In the rubbery polymer of the graft copolymer, the weight ratio of the grafted component to the rubber substrate (graft ratio (% by weight)) is preferably 10 to 100%, more preferably 15 to 70%, still more preferably. 15-40%.
In the production of the graft copolymer, it is also possible to obtain a mixture of a relatively large amount of styrene-based hard polymer that is not grafted by the production method and a rubbery polymer of the graft copolymer. For example, an ABS resin produced by a bulk polymerization method is a typical example.

Examples of the impact improver of the present invention include various thermoplastic elastomers composed of a hard segment and a soft segment. Examples of such thermoplastic elastomers include polyester elastomers, polyurethane elastomers, styrene elastomers, and olefin elastomers.
The content of the impact improver (component C) in the present invention is 1 to 10 parts by weight, preferably 1 to 9 parts by weight, and 2 to 8 parts by weight with respect to a total of 100 parts by weight of the component A and component B. Further preferred. Above the lower limit, a sufficient impact-modifying effect can be obtained, and below the upper limit, problems such as fluidity, heat resistance, strength and rigidity are unlikely to occur.

In the polycarbonate resin composition of the present invention, a thermoplastic resin other than the component A and the component C can be blended as long as the target characteristics are not impaired.
Examples of the thermoplastic resin other than the A component and the C component include hard styrene resins excluding the C component (for example, acrylonitrile-styrene copolymer resin (AS resin) and polystyrene resin), aromatic polyester resins (polyethylene terephthalate resin). (PET resin), polybutylene terephthalate resin (PBT resin), cyclohexanedimethanol copolymerized polyethylene terephthalate resin (so-called PET-G resin), polyethylene naphthalate resin, polybutylene naphthalate resin, etc.) polymethyl methacrylate resin (PMMA resin) ), Cyclic polyolefin resin, thermoplastic fluororesin (represented by, for example, polyvinylidene fluoride resin), and polyolefin resin (polyethylene resin, ethylene- (α-olefin) copolymer resin, Polypropylene resins, and propylene - such as (alpha-olefin) copolymer resins) and the like. The other thermoplastic resin is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, based on 100 parts by weight of the total of the A component and the B component.

(IV) Pentaerythritol ester (component D)
The pentaerythritol ester (component D) used in the present invention is preferably an ester compound of pentaerythritol and an aliphatic carboxylic acid, and the aliphatic carboxylic acid preferably has 3 to 32 carbon atoms, particularly carbon. An aliphatic carboxylic acid having several tens to 22 is preferred. Examples of the aliphatic carboxylic acid include decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid), nonadecanoic acid, behenic acid, Mention may be made of saturated aliphatic carboxylic acids such as icosanoic acid and docosanoic acid, and unsaturated aliphatic carboxylic acids such as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, eicosapentaenoic acid, and cetreic acid . Among the above, aliphatic carboxylic acids having 14 to 20 carbon atoms are preferable. Of these, saturated aliphatic carboxylic acids are preferred. In particular, stearic acid and palmitic acid are preferred.

  The above aliphatic carboxylic acids such as stearic acid and palmitic acid are usually produced from natural fats and oils such as animal fats such as beef tallow and lard and vegetable oils such as palm oil and sunflower oil. Therefore, these aliphatic carboxylic acids are usually a mixture containing other carboxylic acid components having different numbers of carbon atoms. Accordingly, in the production of the fatty acid ester of the present invention, aliphatic carboxylic acids produced from such natural fats and oils and in the form of a mixture containing other carboxylic acid components, particularly stearic acid and palmitic acid are preferably used.

  The pentaerythritol ester used in the present invention may be either a partial ester or a total ester (full ester). However, partial esters are more preferably full esters because they usually have a high hydroxyl value and tend to induce decomposition of the resin at high temperatures.

  The acid value in the pentaerythritol ester used in the present invention is preferably 30 or less, more preferably in the range of 4 to 20, and still more preferably in the range of 4 to 12, from the viewpoint of thermal stability. The acid value can be substantially zero. The hydroxyl value of the pentaerythritol ester is preferably in the range of 0.1-30. Further, the iodine value is preferably 10 or less. The iodine value can be substantially zero. These characteristics can be obtained by a method defined in JIS K 0070.

The TGA 5% weight loss temperature in the pentaerythritol ester used in the present invention is preferably 200 ° C. or higher, more preferably 250 ° C. or higher, from the viewpoint of thermal stability.
The content of the pentaerythritol ester is 0.05 to 0.5 parts by weight, preferably 0.1 to 0.4 parts by weight, based on 100 parts by weight of the total of component A and component B. Within such a range, a polycarbonate resin composition having good fluidity and impact properties can be obtained.

(V) Inorganic filler (E component)
The inorganic filler (E component) used in the present invention can be freely selected from fibrous, flaky, spherical and hollow shapes, for the purpose of improving the strength, rigidity and heat resistance of the resin composition, and dimensional stability. Is preferably in the form of fibers or flakes. For example, as the fibrous inorganic filler, glass fiber, carbon fiber, metal fiber, ceramic fiber, slag fiber, rock wool, zonotlite, wollastonite, and various whiskers (potassium titanate whisker, aluminum borate whisker, Boron whisker, basic magnesium sulfate whisker and the like) are exemplified, and examples of the flaky inorganic filler include glass flake, metal flake, graphite flake, smectite, kaolin clay, mica and talc. In addition, for example, a hollow filler such as a glass balloon may be crushed by melt-kneading with a resin to obtain an effect of improving rigidity in the same manner as a plate-like inorganic filler. The flaky filler of the present invention includes those that exhibit such effects. These inorganic fillers include those in which different materials are surface-coated. Typical examples of the different materials include metals, alloys, and metal oxides. A coating such as a metal or an alloy can impart high conductivity and may improve the design. In some cases, the metal oxide coating can provide functions such as photoconductivity, and the design can be improved.
In the present invention, mica, talc, and wollastonite are particularly suitable in terms of impact resistance, appearance, dimensional stability, cost, and the like.

(Vi) Mica As the average particle diameter of mica used in the present invention, the average particle diameter (D50 (median diameter of particle diameter distribution)) measured by a laser diffraction / scattering method is preferably 1 to 50 μm. Preferably those having 2 to 20 μm, more preferably 2 to 10 μm can be used. When the average particle diameter of mica is less than 1 μm, the effect of improving the rigidity is not sufficient, and when it exceeds 50 μm, the appearance is liable to be deteriorated. As the thickness of mica, a thickness measured by observation with an electron microscope is preferably 0.01 to 1 μm, more preferably 0.03 to 0.3 μm. The aspect ratio is preferably 5 to 200, more preferably 10 to 100. Mica may be a pulverized natural mineral or a synthetic product. The mica is preferably mascobite mica, and its Mohs hardness is about 3. Muscovite mica can achieve higher rigidity and strength than other mica such as phlogopite. The mica may be pulverized by either dry pulverization or wet pulverization. The dry pulverization method is more inexpensive and more common, while the wet pulverization method is effective for pulverizing mica more thinly and finely. As a result, the rigidity improvement effect of the resin composition becomes higher.

(V-ii) Talc The talc used in the present invention is hydrous magnesium silicate in terms of chemical composition, generally represented by the chemical formula 4SiO ₂ .3MgO · 2H ₂ O, and usually a scale having a layered structure. a Jo particles, also compositionally the SiO ₂ 56-65 wt%, the MgO 28 to 35 wt%, and a _{H 2} O about 5 wt%. As other minor components, Fe ₂ O ₃ is 0.03 to 1.2% by weight, Al ₂ O ₃ is 0.05 to 1.5% by weight, CaO is 0.05 to 1.2% by weight, K ₂ O. Is 0.2 wt% or less, Na ₂ O is 0.2 wt% or less. The composition of more preferred _talc, SiO 2: 62-63.5 wt%, MgO: from 31 to 32.5 _{wt%, Fe} 2 O 3: _{0.03~0.15 wt%,} Al _{2 O} 3: 0.05-0.25 weight% and CaO: 0.05-0.25 weight% are preferable. Further, the loss on ignition is preferably 2 to 5.5% by weight. With such a suitable composition, a resin composition having good thermal stability and hue can be obtained, and a good molded product can be produced by further increasing the molding processing temperature. As a result, the composition of the present invention can be further fluidized, and can be used for thin molded products having larger or complex shapes.

As for the particle diameter of talc, the average particle diameter measured by the sedimentation method is 0.1 to 50 μm (more preferably 0.1 to 10 μm, still more preferably 0.2 to 5 μm, particularly preferably 0.2 to 3.5 μm). ) Is preferable. Therefore, a more preferable talc of the present invention is a talc having the above-mentioned preferable composition and having an average particle diameter of 0.2 to 5 μm. Furthermore, it is particularly preferable to use talc having a bulk density of 0.5 (g / cm ³ ) or more as a raw material. As an example of talc satisfying such conditions, “Upn HS-T0.8” manufactured by Hayashi Kasei Kogyo Co., Ltd. is exemplified. The average particle size of talc refers to D50 (median diameter of particle size distribution) measured by an X-ray transmission method which is one of liquid phase precipitation methods. As a specific example of an apparatus for performing such a measurement, Sedigraph 5100 manufactured by Micromeritics Inc. can be cited.

  In addition, there is no particular restriction on the manufacturing method when talc is crushed from raw stone, and the axial flow mill method, the annular mill method, the roll mill method, the ball mill method, the jet mill method, the container rotary compression shearing mill method, etc. are used. can do. Further, the talc after pulverization is preferably classified by various classifiers and having a uniform particle size distribution. There are no particular restrictions on classifiers, impactor type inertial force classifiers (variable impactors, etc.), Coanda effect type inertial force classifiers (elbow jets, etc.), centrifugal field classifiers (multistage cyclone, microplex, dispersion separator) , Accucut, Turbo Classifier, Turboplex, Micron Separator, and Super Separator).

  Further, talc is preferably in an agglomerated state in view of its handleability and the like, and as such a production method, there are a method by deaeration compression, a method of compression using a sizing agent, and the like. In particular, the degassing compression method is preferable in that the sizing agent resin component which is simple and unnecessary is not mixed into the resin composition of the present invention.

(V-iii) Wollastonite The average fiber diameter of wollastonite used in the present invention is preferably from 0.1 to 10 μm, more preferably from 0.1 to 5 μm, still more preferably from 0.1 to 3 μm. The aspect ratio (average fiber length / average fiber diameter) is preferably 3 or more. The upper limit of the aspect ratio is 30 or less. Here, the average fiber diameter is obtained by observing the reinforcing filler with an electron microscope, obtaining individual fiber diameters, and calculating the number average fiber diameter from the measured values. The electron microscope is used because it is difficult for an optical microscope to accurately measure the size of a target level. A filler to be measured for fiber diameter is randomly extracted from an image obtained by observation with an electron microscope, and the fiber diameter is measured near the center of each filler. The number average fiber diameter is calculated from the obtained measured value. The observation magnification is about 1000 times, and the number of measurement is 500 or more (600 or less is suitable for work). On the other hand, the measurement of average fiber length observes a filler with an optical microscope, calculates | requires individual length, and calculates a number average fiber length from the measured value. Observation with an optical microscope begins with the preparation of a dispersed sample so that the fillers do not overlap each other. Observation is performed under the condition of 20 times the objective lens, and the observed image is taken as image data into a CCD camera having about 250,000 pixels. From the obtained image data, the fiber length is calculated using a program for obtaining the maximum distance between two points of the image data using an image analysis apparatus. Under such conditions, the size per pixel corresponds to a length of 1.25 μm, and the number of measurement is 500 or more (600 or less is suitable for work).

The wollastonite in the present invention sufficiently reflects the inherent whiteness in the resin composition, so that the iron content mixed in the raw material ore and the iron content mixed due to equipment wear when pulverizing the raw material ore are magnetically separated. It is preferable to remove as much as possible. It is preferable that the iron content in wollastonite is 0.5% by weight or less in terms of Fe ₂ O ₃ by such magnetic separator processing. Therefore, the more preferable wollastonite of the present invention has a fiber diameter of 0.1 to 10 μm, more preferably 0.1 to 5 μm, still more preferably 0.1 to 3 μm, and the iron content is Fe _2. It is wollastonite of 0.5% by weight or less in terms of O ₃ . Wollastonite may be a pulverized natural mineral or a synthetic product.

  The inorganic filler (component E) includes a silane coupling agent (including alkylalkoxysilane and polyorganohydrogensiloxane), a higher fatty acid ester, an acid compound (for example, phosphorous acid, phosphoric acid, carboxylic acid, and carboxylic acid). Surface treatment with various surface treatment agents such as acid anhydrides) and waxes. Furthermore, it may be granulated with a sizing agent such as various resins, higher fatty acid esters, and waxes.

  The content of the inorganic filler (E component) in the present invention is preferably 100 parts by weight or less, more preferably 40 parts by weight or less, and still more preferably 30 parts by weight or less with respect to 100 parts by weight of the total of the A component and the B component. It is. On the other hand, when E component is blended, it is preferably 0.1 parts by weight or more, more preferably 3 parts by weight or more, and further preferably 5 parts by weight or more. When the content is at least the lower limit, the effects of improving the strength and imparting rigidity are likely to be obtained, and when the content is not more than the upper limit, problems such as thermal stability, a decrease in surface appearance and an increase in specific gravity are difficult to occur.

  When the inorganic filler (E component) is blended, the polycarbonate resin composition of the present invention may contain a surface coating lubricant for suppressing breakage of the reinforcing filler and improving the thermal stability of the resin composition. it can. The surface coating lubricant inhibits adhesion between the matrix resin and the reinforcing filler, reduces stress acting on the reinforcing filler during melt-kneading, and suppresses filler bending. The effects of the surface coating lubricant include (I) improved rigidity (increases the filler aspect ratio), (II) improved toughness (easily exerting the toughness of the matrix resin, especially an aromatic polycarbonate resin with particularly good toughness) And (III) improved thermal stability, and (IV) improved conductivity (in the case of a conductive filler). Such a surface coating lubricant includes (i) a lubricant containing a functional group having reactivity with a silicate mineral, and (ii) a lubricant whose surface has been previously coated on a silicate mineral. Accordingly, among the above-mentioned surface treatment agents for silicate minerals, those having a lubricant effect act as a surface coating lubricant. A suitable surface coating lubricant is an acidic group-containing lubricant or an alkylalkoxysilane or alkylhydrogensilane having an alkyl group having 60 or less carbon atoms.

  The number of carbon atoms in the alkyl group of such a silane compound is preferably 4 or more. Furthermore, such carbon number is preferably 20 or less, more preferably 18 or less, and still more preferably 16 or less. The alkyl group in such a silane compound is preferably 1 or 2, particularly preferably 1. Further, preferred examples of the alkoxy group include a methoxy group and an ethoxy group.

  On the other hand, examples of the acidic group in the acidic group-containing lubricant include a carboxyl group, a carboxylic anhydride group, a sulfonic acid group, a sulfinic acid group, a phosphonic acid group, and a phosphinic acid group. Suitable acidic groups are at least one of carboxyl groups, carboxylic anhydride groups, sulfonic acid groups, sulfinic acid groups, phosphonic acid groups and phosphinic acid groups. In particular, a lubricant having at least one acidic group selected from a carboxyl group, a carboxylic acid anhydride group and a phosphonic acid group is preferable, and a lubricant having a carboxyl group and / or a carboxylic acid anhydride group is particularly preferable. In the acidic group-containing lubricant, the concentration of the acidic group is in the range of 0.05 to 10 meq / g, more preferably in the range of 0.1 to 6 meq / g, and still more preferably in the range of 0.5 to 4 meq / g.

  Here, the lubricant is a compound widely known for reducing friction with an apparatus or a mold in plastic molding and obtaining a good mold release, and specifically includes olefin wax, higher fatty acid (for example, Examples thereof include aliphatic carboxylic acids having 16 to 60 carbon atoms, polyalkylene glycols having a polymerization degree of about 10 to 200, silicone oils, and fluorocarbon oils. Examples of olefin waxes include paraffin wax, microcrystalline wax, Fischer-Tropsch wax, and α-olefin polymer as paraffin wax. Examples of polyethylene wax include polyethylene having a molecular weight of about 1,000 to 15,000. Examples include polypropylene. This molecular weight is a weight average molecular weight calculated based on a calibration curve obtained from standard polystyrene in GPC (gel permeation chromatography).

  Examples of a method for bonding carboxyl groups to such a lubricant (excluding higher fatty acids) include, for example, (a) a method of copolymerizing a monomer having a carboxyl group and an α-olefin monomer, and (b) the above The method etc. which couple | bond or copolymerize the compound or monomer which has carboxyl groups with respect to a lubricant can be mentioned.

  In the method (a), a living polymerization method can be employed in addition to radical polymerization methods such as solution polymerization, emulsion polymerization, suspension polymerization, and bulk polymerization. Furthermore, a method of once forming a macromonomer and then polymerizing is also possible. The form of the copolymer can be used as a copolymer of various forms such as an alternating copolymer, a block copolymer, and a tapered copolymer in addition to the random copolymer. In the method (b), a radical generator such as peroxide or 2,3-dimethyl-2,3-diphenylbutane (commonly called “dicumyl”) is added to a lubricant, particularly an olefinic wax, if necessary, and a high temperature. A method of reacting or copolymerizing under the above can be adopted. In this method, a reactive site is thermally generated in the lubricant, and a compound or monomer that reacts with the active site is reacted. Other methods for generating active sites required for the reaction include irradiation with radiation and electron beam, and application of external force by mechanochemical technique. Furthermore, a method in which a monomer that generates an active site required for the reaction is copolymerized in advance in the lubricant. Examples of the active site for the reaction include an unsaturated bond and a peroxide bond, and a method for obtaining the active site includes a nitroxide-mediated radical polymerization method represented by TEMPO.

  Examples of the compound or monomer having a carboxyl group include acrylic acid, methacrylic acid, maleic acid, fumaric acid, maleic anhydride, and citraconic anhydride, and maleic anhydride is particularly preferable.

As the acidic group-containing lubricant, the carboxyl group is preferably 0.05 to 10 meq / g, more preferably 0.1 to 6 meq / g, still more preferably 0.5 to 4 meq / g per gram of the carboxyl group-containing lubricant. Carboxy group-containing olefin waxes contained in a concentration are preferred. Furthermore, the molecular weight of the olefin wax is preferably 1,000 to 10,000. Furthermore, a copolymer of an α-olefin and maleic anhydride that satisfies the conditions of such concentration and molecular weight is preferable. Such a copolymer can be produced by melt polymerization or bulk polymerization in the presence of a radical catalyst according to a conventional method. Here, as the α-olefin, those having 10 to 60 carbon atoms as an average value can be preferably exemplified. More preferable examples of the α-olefin include those having an average carbon number of 16 to 60, and more preferably 25 to 55.
Such a surface coating lubricant is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 3 parts by weight, and further 0.05 to 1 part by weight based on 100 parts by weight of the total of component A and component B. preferable.

(VI) Thermal stabilizer (F component)
Various stabilizers can be used in the polycarbonate resin composition of the present invention in order to stabilize the molecular weight and hue during molding. Examples of such stabilizers include phosphorus stabilizers and hindered phenol stabilizers.

(VI-i) Phosphorus stabilizer Examples of the phosphorous stabilizer used in the present invention include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof, and tertiary phosphine.
Specifically, as the phosphite compound, for example, triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl Phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, tris (diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di -N-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, dis Allyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, bis {2,4-bis (1-methyl-1-phenylethyl) phenyl} pentaerythritol diphosphite, phenylbisphenol A Examples include pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, and dicyclohexyl pentaerythritol diphosphite.

  Further, as other phosphite compounds, those which react with dihydric phenols and have a cyclic structure can be used. For example, 2,2′-methylenebis (4,6-di-tert-butylphenyl) (2,4-di-tert-butylphenyl) phosphite, 2,2′-methylenebis (4,6-di-tert- Examples include butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite and 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite.

  Examples of the phosphate compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, Examples thereof include diisopropyl phosphate, and triphenyl phosphate and trimethyl phosphate are preferable.

  Examples of the phosphonite compound include tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3′-biphenylenedi. Phosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3′-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite Tetrakis (2,6-di-tert-butylphenyl) -4,3′-biphenylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3′-biphenylene diphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-di tert-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-n-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl)- 4-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -3-phenyl-phenylphosphonite, and the like, and tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite, bis (Di-tert-butylphenyl) -phenyl-phenylphosphonite is preferred, tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl)- More preferred is phenyl-phenylphosphonite. Such a phosphonite compound is preferable because it can be used in combination with a phosphite compound having an aryl group in which two or more alkyl groups are substituted.

  Examples of the phosphonate compound include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate.

  Tertiary phosphine includes triethylphosphine, tripropylphosphine, tributylphosphine, trioctylphosphine, triamylphosphine, dimethylphenylphosphine, dibutylphenylphosphine, diphenylmethylphosphine, diphenyloctylphosphine, triphenylphosphine, tri-p-tolyl. Examples include phosphine, trinaphthylphosphine, and diphenylbenzylphosphine. A particularly preferred tertiary phosphine is triphenylphosphine.

  The phosphorus stabilizers can be used alone or in combination of two or more. Among the phosphorus stabilizers, phosphonite compounds or phosphite compounds represented by the following general formula (3) are preferable.

（式（３）中、ＲおよびＲ’は炭素数６〜３０のアルキル基または炭素数６〜３０のアリール基を表し、互いに同一であっても異なっていてもよい。）

(In Formula (3), R and R ′ represent an alkyl group having 6 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and may be the same or different from each other.)

  As described above, tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite is preferable as the phosphonite compound, and the stabilizer containing phosphonite as a main component is Sandostab P-EPQ (trademark, manufactured by Clariant). ) And Irgafos P-EPQ (trademark, manufactured by CIBA SPECIALTY CHEMICALS) and both can be used.

  Among the above formulas (3), more preferred phosphite compounds are distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di). -Tert-butyl-4-methylphenyl) pentaerythritol diphosphite, and bis {2,4-bis (1-methyl-1-phenylethyl) phenyl} pentaerythritol diphosphite.

  Distearyl pentaerythritol diphosphite is commercially available as ADK STAB PEP-8 (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.) and JPP681S (trademark, manufactured by Johoku Chemical Industry Co., Ltd.), and any of them can be used. Bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite is ADK STAB PEP-24G (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.), Alkanox P-24 (trademark, manufactured by Great Lakes), Ultranox. P626 (trademark, manufactured by GE Specialty Chemicals), Doverphos S-9432 (trademark, manufactured by Dover Chemical), and Irgafos126 and 126FF (trademark, manufactured by CIBA SPECIALTY CHEMICALS) are also available. Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite is commercially available as ADK STAB PEP-36 (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.) and can be easily used. Further, bis {2,4-bis (1-methyl-1-phenylethyl) phenyl} pentaerythritol diphosphite is produced by ADK STAB PEP-45 (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.) and Doverphos S-9228 (trademark). , Manufactured by Dober Chemical Co.) and any of them can be used.

(VI-ii) Hindered phenolic antioxidants As the hindered phenolic antioxidants used in the present invention, various compounds that are usually blended in resins can be used. Examples of such hindered phenol-based antioxidants include α-tocopherol, butylhydroxytoluene, sinapir alcohol, vitamin E, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2-tert-butyl-6- (3′-tert-butyl-5′-methyl-2′-hydroxybenzyl) -4-methylphenyl acrylate, 2,6-di-tert-butyl-4- (N, N -Dimethylaminomethyl) phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis ( 4-ethyl-6-tert-butylphenol), 4,4′-methylenebis ( , 6-di-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-cyclohexylphenol), 2,2′-dimethylene-bis (6-α-methyl-benzyl-p-cresol), 2 2,2′-ethylidene-bis (4,6-di-tert-butylphenol), 2,2′-butylidene-bis (4-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-) 6-tert-butylphenol), triethylene glycol-N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 1,6-hexanediol bis [3- (3,5 -Di-tert-butyl-4-hydroxyphenyl) propionate], bis [2-tert-butyl-4-methyl 6- (3-ter -Butyl-5-methyl-2-hydroxybenzyl) phenyl] terephthalate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1 , -Dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, 4,4′-thiobis (6-tert-butyl-m-cresol), 4,4′-thiobis (3 -Methyl-6-tert-butylphenol), 2,2'-thiobis (4-methyl-6-tert-butylphenol), bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4,4 '-Di-thiobis (2,6-di-tert-butylphenol), 4,4'-tri-thiobis (2,6-di-tert-butylphenol), 2,2-thi Diethylenebis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,4-bis (n-octylthio) -6- (4-hydroxy-3,5-di-tert -Butylanilino) -1,3,5-triazine, N, N'-hexamethylenebis- (3,5-di-tert-butyl-4-hydroxyhydrocinnamide), N, N'-bis [3- ( 3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5- Trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl-4-hydroxyphenyl) ) Isocyanurate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanate 1,3,5-tris 2 [3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate, tetrakis [methylene-3- (3,5-di-tert- Butyl-4-hydroxyphenyl) propionate] methane, triethylene glycol-N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, triethylene glycol-N-bis-3- ( 3-tert-butyl-4-hydroxy-5-methylphenyl) acetate, 3,9-bi [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) acetyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] Undecane, tetrakis [methylene-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] methane, 1,3,5-trimethyl-2,4,6-tris (3-tert-butyl- Examples thereof include 4-hydroxy-5-methylbenzyl) benzene and tris (3-tert-butyl-4-hydroxy-5-methylbenzyl) isocyanurate.

  Among the above compounds, tetrakis [methylene-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] methane, octadecyl-3- (3,5-di-tert-butyl-) is used in the present invention. 4-hydroxyphenyl) propionate, and 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4 , 8,10-Tetraoxaspiro [5,5] undecane is preferably used. In particular, 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxa Spiro [5,5] undecane is preferred. The said hindered phenolic antioxidant can be used individually or in combination of 2 or more types.

  As an antioxidant based on tetrakis [methylene-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] methane, commercially available as Irganox 1010 (trademark, manufactured by CHIBA SPECIALTY CHEMICALS). Available. Antioxidants based on octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate include Irganox 1076 (trademark, manufactured by CHIBA SPECIALTY CHEMICALS) and Adeka Stab AO-18 (trademark, Asahi) It is commercially available as Denka Kogyo Co., Ltd.) and any of them can be used. 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] An antioxidant mainly composed of undecane is commercially available as AO-80 (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.) and can be used.

  The phosphorus stabilizer or / and the hindered phenol antioxidant is preferably 0.0001 to 1 part by weight, more preferably 0.001 to 0.1 part, based on 100 parts by weight of the total of the component A and the component B. It is blended in a proportion of parts by weight, more preferably 0.005 to 0.1 parts by weight. When these are used in combination, 0.01 to 0.3 parts by weight of a phosphorus stabilizer and 0.01 to 0.3 parts by weight of hindered, based on a total of 100 parts by weight of component A and component B A phenolic antioxidant is preferably blended.

(VI-iii) Other Heat Stabilizers The polycarbonate resin composition of the present invention may contain other heat stabilizers other than the above phosphorus stabilizers and hindered phenol antioxidants. Such other heat stabilizers are preferably used in combination with any of these stabilizers and antioxidants, and particularly preferably used in combination with both. Examples of such other heat stabilizers include lactone stabilizers represented by the reaction product of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene (such stabilizers). Is described in detail in JP-A-7-233160). Such a compound is commercially available as Irganox HP-136 (trademark, manufactured by CIBA SPECIALTY CHEMICALS) and can be used. Furthermore, a stabilizer obtained by mixing the compound with various phosphite compounds and hindered phenol compounds is commercially available. For example, Irganox HP-2921 manufactured by the above company is preferably exemplified. In the present invention, such a premixed stabilizer can also be used. The blending amount of the lactone stabilizer is preferably 0.0005 to 0.05 parts by weight, more preferably 0.001 to 0.03 parts by weight, based on 100 parts by weight of the total of the A component and the B component. .

  Other stabilizers include sulfur-containing stabilizers such as pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), and glycerol-3-stearylthiopropionate. Illustrated. Such a stabilizer is particularly effective when the resin composition is applied to rotational molding. The amount of the sulfur-containing stabilizer is preferably 0.001 to 0.1 parts by weight, more preferably 0.01 to 0.08 parts by weight, based on a total of 100 parts by weight of component A and component B. .

(VII) Other Additives The aromatic polycarbonate resin composition of the present invention comprises, as necessary, known ultraviolet absorbers, dyes and pigments, compounds having heat ray absorbing ability, flame retardants, anti-dripping agents, antistatic agents, and the like. You may mix | blend an additive.

(VII-i) Ultraviolet Absorber The polycarbonate resin composition of the present invention can contain an ultraviolet absorber. Specific examples of the ultraviolet absorber of the present invention include, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4 in the benzophenone series. -Benzyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydridolate benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2, 2 ′, 4,4′-tetrahydroxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxy-5-sodiumsulfoxybenzophenone, bis (5-Benzoyl-4-hydroxy-2- Examples include methoxyphenyl) methane, 2-hydroxy-4-n-dodecyloxybenzophenone, and 2-hydroxy-4-methoxy-2′-carboxybenzophenone.

  Specific examples of the ultraviolet absorber include benzotriazole-based compounds such as 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2 -(2-hydroxy-3,5-dicumylphenyl) phenylbenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2,2'-methylenebis [ 4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- (2-hydroxy-3,5-di-tert-butylphenyl) benzo Triazole, 2- (2-hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazol 2- (2-hydroxy-3,5-di-tert-amylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-5-tert- Butylphenyl) benzotriazole, 2- (2-hydroxy-4-octoxyphenyl) benzotriazole, 2,2′-methylenebis (4-cumyl-6-benzotriazolephenyl), 2,2′-p-phenylenebis ( 1,3-benzoxazin-4-one), and 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimidomethyl) -5-methylphenyl] benzotriazole, and 2- (2 ′ -Hydroxy-5-methacryloxyethylphenyl) -2H-benzotriazole and copolymer with the monomer 2 such as a copolymer with a possible vinyl monomer and a copolymer of 2- (2′-hydroxy-5-acryloxyethylphenyl) -2H-benzotriazole with a vinyl monomer copolymerizable with the monomer. Examples include polymers having a -hydroxyphenyl-2H-benzotriazole skeleton.

  Specific examples of the ultraviolet absorber include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol and 2- (4) in hydroxyphenyltriazine series. , 6-Diphenyl-1,3,5-triazin-2-yl) -5-methyloxyphenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-ethyloxy Phenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-propyloxyphenol, and 2- (4,6-diphenyl-1,3,5-triazine-2- Yl) -5-butyloxyphenol and the like. Furthermore, the phenyl group of the above exemplary compounds such as 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-hexyloxyphenol is 2,4-dimethyl. Examples of the compound are phenyl groups.

  As the ultraviolet absorber, specifically, in the cyclic imino ester type, for example, 2,2′-p-phenylenebis (3,1-benzoxazin-4-one), 2,2 ′-(4,4′-diphenylene) ) Bis (3,1-benzoxazin-4-one), 2,2 ′-(2,6-naphthalene) bis (3,1-benzoxazin-4-one) and the like.

  Further, as the ultraviolet absorber, specifically, for cyanoacrylate, for example, 1,3-bis-[(2′-cyano-3 ′, 3′-diphenylacryloyl) oxy] -2,2-bis [(2- Examples include cyano-3,3-diphenylacryloyl) oxy] methyl) propane and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl) oxy] benzene.

  Further, the ultraviolet absorber has a structure of a monomer compound capable of radical polymerization, whereby the ultraviolet-absorbing monomer and / or the light-stable monomer having a hindered amine structure, and an alkyl (meth) acrylate. A polymer type ultraviolet absorber obtained by copolymerization with a monomer such as may be used. Preferred examples of the UV-absorbing monomer include compounds containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic imino ester skeleton, and a cyanoacrylate skeleton in the ester substituent of (meth) acrylate. The

  Among them, benzotriazole and hydroxyphenyltriazine are preferable from the viewpoint of ultraviolet absorption ability, and cyclic imino ester and cyanoacrylate are preferable from the viewpoint of heat resistance and hue. You may use the said ultraviolet absorber individually or in mixture of 2 or more types.

  The content of the ultraviolet absorber is 0.01 to 2 parts by weight, preferably 0.03 to 2 parts by weight, more preferably 0.04 to 1 part by weight, based on 100 parts by weight of the total of component A and component B. More preferably, it is 0.05 to 0.5 parts by weight.

(VII-ii) Compound having heat ray absorbing ability The polycarbonate resin composition of the present invention may contain a compound having heat ray absorbing ability. Such compounds include phthalocyanine-based near-infrared absorbers, metal oxide-based near-infrared absorbers such as ATO, ITO, iridium oxide and ruthenium oxide, and metal boride-based near infrared rays such as lanthanum boride, cerium boride and tungsten boride. Preferred examples include various metal compounds having excellent near-infrared absorption ability such as an absorber, and carbon filler. As such a phthalocyanine-based near infrared absorber, for example, MIR-362 manufactured by Mitsui Chemicals, Inc. is commercially available and easily available. Examples of carbon fillers include carbon black, graphite (including both natural and artificial, and whiskers), carbon fibers (including those produced by vapor phase growth), carbon nanotubes, and fullerenes, preferably carbon. Black and graphite. These can be used alone or in combination of two or more. The content of the phthalocyanine-based near-infrared absorber is preferably 0.0005 to 0.2 parts by weight, more preferably 0.0008 to 0.1 parts by weight, based on 100 parts by weight of the total of component A and component B. 0.001-0.07 part by weight is more preferable. The content of the metal oxide near-infrared absorber, the metal boride-based near infrared absorber, and the carbon filler is preferably in the range of 0.1 to 200 ppm (weight ratio) in the resin composition of the present invention. A range of ˜100 ppm is more preferable.

(VII-iii) White pigment for high light reflection The polycarbonate resin composition of the present invention can be provided with a light reflection effect by blending a white pigment for high light reflection. As such a white pigment, a titanium dioxide (particularly titanium dioxide treated with an organic surface treating agent such as silicone) pigment is particularly preferred. The content of the white pigment for high light reflection is preferably 3 to 30 parts by weight, more preferably 8 to 25 parts by weight based on the total of 100 parts by weight of the A component and the B component. Two or more kinds of white pigments for high light reflection can be used in combination.

(VII-iv) Flame Retardant Various compounds known as flame retardants for polycarbonate resin may be blended in the polycarbonate resin composition of the present invention. The compounding of the compound used as the flame retardant not only improves the flame retardancy but also provides, for example, an improvement in antistatic properties, fluidity, rigidity, and thermal stability based on the properties of each compound.
Examples of such flame retardants include (i) organometallic salt flame retardants (for example, alkali (earth) organic sulfonate metal salts, borate metal salt flame retardants, stannate metal salt flame retardants, etc.), and (ii) Organophosphorous flame retardants (for example, monophosphate compounds, phosphate oligomer compounds, phosphonate oligomer compounds, phosphonitrile oligomer compounds, and phosphonic acid amide compounds), (iii) silicone flame retardants comprising silicone compounds, and (iv) halogens And flame retardant (for example, brominated epoxy resin, brominated polystyrene, brominated polycarbonate (including oligomers), brominated polyacrylate, chlorinated polyethylene, etc.).

(VII-v) Anti-dripping agent The polycarbonate resin composition of the present invention may contain an anti-dripping agent. By using such an anti-dripping agent in combination with the above flame retardant, better flame retardancy can be obtained. Examples of the anti-dripping agent include a fluorinated polymer having a fibril-forming ability. Examples of such a polymer include polytetrafluoroethylene, tetrafluoroethylene copolymers (for example, tetrafluoroethylene / hexafluoropropylene copolymers). , Etc.), partially fluorinated polymers as shown in U.S. Pat. No. 4,379,910, polycarbonate resins produced from fluorinated diphenols, etc., preferably polytetrafluoroethylene (hereinafter referred to as PTFE). Is).

Polytetrafluoroethylene (fibrillated PTFE) having fibril-forming ability has a very high molecular weight, and exhibits a tendency to bind PTFE to each other by an external action such as shearing force to form a fiber. Its number average molecular weight ranges from 1.5 million to tens of millions. The lower limit is more preferably 3 million. The number average molecular weight is calculated based on the melt viscosity of polytetrafluoroethylene at 380 ° C. as disclosed in JP-A-6-145520. That is, the fibrillated PTFE has a melt viscosity at 380 ° C. measured by the method described in this publication in the range of 10 ⁷ to 10 ¹³ poise, preferably in the range of 10 ⁸ to 10 ¹² poise.

  Such PTFE can be used in solid form or in the form of an aqueous dispersion. In addition, PTFE having such fibril-forming ability can improve the dispersibility in the resin, and it is also possible to use a PTFE mixture in a mixed form with other resins in order to obtain better flame retardancy and mechanical properties. is there. Further, as disclosed in JP-A-6-145520, those having a structure having such a fibrillated PTFE as a core and a low molecular weight polytetrafluoroethylene as a shell are also preferably used.

  Examples of commercially available fibrillated PTFE include Teflon (registered trademark) 6J from Mitsui DuPont Fluorochemical Co., Ltd., Polyflon MPA FA500, F-201L from Daikin Chemical Industries, Ltd., and the like. Commercially available aqueous dispersions of fibrillated PTFE include: Fluon AD-1, AD-936 manufactured by Asahi IC Fluoropolymers, Fluon D-1, D-2 manufactured by Daikin Industries, Ltd., Mitsui A representative example is Teflon (registered trademark) 30J manufactured by DuPont Fluorochemical Co., Ltd.

  As a mixed form of fibrillated PTFE, (1) a method in which an aqueous dispersion of fibrillated PTFE and an aqueous dispersion or solution of an organic polymer are mixed and co-precipitated to obtain a co-agglomerated mixture (JP-A-60-258263). (2) A method of mixing an aqueous dispersion of fibrillated PTFE and dried organic polymer particles (Japanese Patent Laid-Open No. 4-272957). Described method), (3) A method in which an aqueous dispersion of fibrillated PTFE and an organic polymer particle solution are uniformly mixed, and the respective media are simultaneously removed from the mixture (Japanese Patent Laid-Open Nos. 06-220210, (Method described in Japanese Patent Application Laid-Open No. 08-188653), (4) A method of polymerizing monomers forming an organic polymer in an aqueous dispersion of fibrillated PTFE (Method described in JP-A-9-95583), and (5) an aqueous dispersion of PTFE and an organic polymer dispersion are uniformly mixed, and then a vinyl monomer is further polymerized in the mixed dispersion. Thereafter, those obtained by a method for obtaining a mixture (a method described in JP-A No. 11-29679) can be used. Examples of commercially available fibrillated PTFE in a mixed form include “Metablene A3800” (trade name) manufactured by Mitsubishi Rayon Co., Ltd. and “BLENDEX B449” (trade name) manufactured by GE Specialty Chemicals.

In order to more effectively utilize the good mechanical properties and surface appearance properties of the polycarbonate resin composition of the present invention, the fibrillated PTFE is preferably finely dispersed as much as possible. As a means of achieving such fine dispersion, the above mixed form of fibrillated PTFE is advantageous. A method of directly supplying an aqueous dispersion in a melt kneader is also advantageous for fine dispersion. However, in the case of the aqueous dispersion form, consideration is required in that the hue is slightly deteriorated. The proportion of fibrillated PTFE in the mixed form is preferably 10 to 80% by weight, more preferably 15 to 75% by weight, in 100% by weight of the mixture. When the ratio of fibrillated PTFE is in such a range, good dispersibility of fibrillated PTFE can be achieved.
The content of fibrillated PTFE in the polycarbonate resin composition is preferably 0.001 to 1 part by weight, more preferably 0.1 to 0.7 part by weight, based on 100 parts by weight of the total of component A and component B. It is.

(VII-vi) Antistatic Agent The polycarbonate resin composition of the present invention may require antistatic performance, and in such a case, it is preferable to include an antistatic agent. Examples of the antistatic agent include (1) aryl sulfonic acid phosphonium salts represented by dodecylbenzenesulfonic acid phosphonium salts, organic sulfonic acid phosphonium salts such as alkyl sulfonic acid phosphonium salts, and tetrafluoroboric acid phosphonium salts. Examples thereof include phosphonium borate salts. The content of the phosphonium salt is suitably 5 parts by weight or less, preferably 0.05 to 5 parts by weight, more preferably 1 to 3.5 parts by weight, based on a total of 100 parts by weight of component A and component B. Parts, more preferably in the range of 1.5 to 3 parts by weight.

  Examples of the antistatic agent include: (2) lithium organic sulfonate, organic sodium sulfonate, organic potassium sulfonate, cesium organic sulfonate, rubidium organic sulfonate, calcium organic sulfonate, magnesium organic sulfonate, and barium organic sulfonate. And organic sulfonate alkali (earth) metal salts. Such metal salts are also used as flame retardants as described above. More specific examples of such metal salts include metal salts of dodecylbenzene sulfonic acid and metal salts of perfluoroalkane sulfonic acid. The content of the organic sulfonate alkali (earth) metal salt is suitably 0.5 parts by weight or less based on the total of 100 parts by weight of component A and component B, preferably 0.001 to 0.3 weights. Parts, more preferably 0.005 to 0.2 parts by weight. In particular, alkali metal salts such as potassium, cesium, and rubidium are preferable.

  Examples of the antistatic agent include (3) organic sulfonic acid ammonium salts such as alkyl sulfonic acid ammonium salt and aryl sulfonic acid ammonium salt. The ammonium salt is suitably 0.05 parts by weight or less based on a total of 100 parts by weight of the component A and the component B. Examples of the antistatic agent include (4) a polymer containing a poly (oxyalkylene) glycol component such as polyether ester amide as a constituent component. The polymer is suitably 5 parts by weight or less based on a total of 100 parts by weight of the component A and the component B.

(VII-vii) Other additives In addition to the additives described above, the polycarbonate resin composition of the present invention may include a colorant (for example, a pigment such as carbon black or titanium oxide, a dye), or a light diffusing agent. Agents (for example, acrylic crosslinked particles, silicone crosslinked particles, calcium carbonate particles), fluorescent dyes, fluorescent brighteners, inorganic phosphors (for example, phosphors having aluminate as a mother crystal), bluing agents, light diffusing agents, Antibacterial agents, dispersants such as liquid paraffin, photocatalytic antifouling agents, heat ray absorbents and photochromic agents can be blended.

(VIII) Production of Polycarbonate Resin Composition and Molded Article An arbitrary method is adopted to produce the polycarbonate resin composition of the present invention. For example, A component, B component, C component and D component and optionally other additives are necessary after thoroughly mixing using premixing means such as V-type blender, Henschel mixer, mechanochemical device, extrusion mixer, etc. Depending on the method, granulation of the premixed mixture using an extrusion granulator or briquetting machine, etc., followed by melt kneading with a melt kneader represented by a vent type twin screw extruder, followed by pelletizing with a pelletizer Is mentioned.

  In addition, a method of supplying each component independently to a melt kneader represented by a vent type twin screw extruder, or a part of each component is premixed and then supplied to the melt kneader independently of the remaining components. The method of doing is also mentioned. Examples of the method of premixing a part of each component include a method in which components other than the component A are premixed in advance and then the aromatic polycarbonate resin of the component A is mixed or directly supplied to the extruder.

  As a premixing method, for example, when a component having a powder form is included as the component A, a part of the powder and an additive to be blended are mixed to produce a master batch of the additive diluted with the powder. A method using a master batch can be mentioned. Furthermore, the method etc. which supply one component independently from the middle of a melt extruder are mentioned. In addition, when there exists a liquid thing in the component to mix | blend, what is called a liquid injection apparatus or a liquid addition apparatus can be used for supply to a melt extruder.

As the extruder, one having a vent capable of degassing moisture in the raw material and volatile gas generated from the melt-kneaded resin can be preferably used. From the vent, a vacuum pump is preferably installed for efficiently discharging generated moisture and volatile gas to the outside of the extruder. It is also possible to remove a foreign substance from the resin composition by installing a screen for removing the foreign substance mixed in the extrusion raw material in the zone in front of the extruder die. Examples of such a screen include a wire mesh, a screen changer, a sintered metal plate (such as a disk filter), and the like.
Examples of the melt kneader include a banbury mixer, a kneading roll, a single screw extruder, a multi-screw extruder having three or more axes, in addition to a twin screw extruder.

  The resin extruded as described above is directly cut into pellets, or after forming strands, the strands are cut with a pelletizer to be pelletized. When it is necessary to reduce the influence of external dust during pelletization, it is preferable to clean the atmosphere around the extruder. Furthermore, in the manufacture of such pellets, various methods already proposed for polycarbonate resin for optical discs are used to narrow the shape distribution of pellets, reduce miscuts, and reduce fine powder generated during transportation or transportation. In addition, it is possible to appropriately reduce bubbles (vacuum bubbles) generated inside the strands and pellets. By these prescriptions, it is possible to increase the molding cycle and reduce the occurrence rate of defects such as silver. Moreover, although the shape of a pellet can take common shapes, such as a cylinder, a prism, and a spherical shape, it is a cylinder more suitably. The diameter of such a cylinder is preferably 1 to 5 mm, more preferably 1.5 to 4 mm, and still more preferably 2 to 3.3 mm. On the other hand, the length of the cylinder is preferably 1 to 30 mm, more preferably 2 to 5 mm, and still more preferably 2.5 to 3.5 mm.

  The polycarbonate resin composition of the present invention can be produced in various products by usually injection-molding the pellets produced as described above to obtain molded products. In such injection molding, not only ordinary molding methods but also injection compression molding, injection press molding, gas assist injection molding, foam molding (including a method of injecting a supercritical fluid), insert molding, in-mold coating molding, heat insulation Examples thereof include mold molding, rapid heating / cooling mold molding, two-color molding, sandwich molding, and ultra-high speed injection molding. In addition, either a cold runner method or a hot runner method can be selected for molding.

  The polycarbonate resin composition of the present invention can also be used in the form of various shaped extruded products, sheets, films, etc. by extrusion molding. For forming sheets and films, an inflation method, a calendar method, a casting method, or the like can also be used. It is also possible to form a heat-shrinkable tube by applying a specific stretching operation. Further, the polycarbonate resin composition of the present invention can be formed into a molded product by rotational molding or blow molding.

  Furthermore, various surface treatments can be performed on the molded article made of the resin composition of the present invention. Surface treatment here refers to a new layer on the surface of resin molded products such as vapor deposition (physical vapor deposition, chemical vapor deposition, etc.), plating (electroplating, electroless plating, hot dipping, etc.), painting, coating, printing, etc. A method used for ordinary polycarbonate resin is applicable. Specific examples of the surface treatment include various surface treatments such as hard coat, water / oil repellent coat, ultraviolet absorption coat, infrared absorption coat, and metalizing (evaporation). Hard coat is a particularly preferred and required surface treatment. In addition, the resin composition of the present invention is preferably applied by vapor deposition and plating.

Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited thereto.
(Evaluation of copolymer polycarbonate resin composition)
(I) Pencil hardness Using a mold having a cavity surface with an arithmetic average roughness (Ra) of 0.03 μm, and using a Japanese steel mill injection molding machine J-75E3, cylinder temperature 280 ° C., mold temperature Under the condition of 80 ° C., the width is 50 mm, the length is 90 mm, the thickness is 3 mm (length 20 mm), 2 mm (length 45 mm), 1 mm (length 25 mm) with a holding time of 20 seconds and a cooling time of 20 seconds. A three-stage plate was formed. The pencil hardness at a thickness of 2 mm of the three-stage plate was measured according to JIS K5600.
(Ii) Charpy impact strength Charpy impact strength with a notch was measured according to ISO 179.
(Iii) Fluidity Using Sumitomo Heavy Industries, Ltd. SG-150U molding machine, the flow length was evaluated with an Archimedes spiral flow mold (channel thickness 2 mm, channel width 8 mm). The conditions were a cylinder temperature of 280 ° C., a mold temperature of 80 ° C., and an injection pressure of 100 MPa.
(Iv) Chemical resistance A test piece was produced in accordance with ISO 179 in the same manner as in (ii). The manufactured specimen was immersed in essoregular gasoline for 30 minutes in an atmosphere at 23 ° C. with bending strain applied.
(V) Evaluation of fatty acid ester (D-1 to 3) (vi) Acid value, hydroxyl value, iodine value of fatty acid ester JIS was measured. The acid value, hydroxyl value, and iodine value were determined by neutralization titration in accordance with K0070.
(V-ii) 5% weight loss temperature by thermogravimetric measurement of fatty acid ester Hi-Res TGA2950 Thermographic Analyzer manufactured by TA-instruments was used and heated at 20 ° C./min under N ₂ atmosphere to reduce the weight of the sample Was measured as the weight loss temperature of 5% by weight of TGA.
The results of (vi) and (v-ii) are shown in Table 1.

[Examples 1 to 16, Comparative Examples 1 to 23]
The mixture which consists of a component except the E component (inorganic filler) with the composition shown in Table 3 and Table 4 was supplied from the 1st supply port of the extruder. Such a mixture was obtained by mixing with a V-type blender. Moreover, all E components were supplied from the 2nd supply port using the side feeder. Here, the first supply port is a supply port farthest from the die, and the second supply port is a supply port located between the die of the extruder and the first supply port. The mixture by the tumbler is a stirring blade provided on a measuring instrument (CWF manufactured by Kubota Corporation) from the first input port of the screw using a vent type twin screw extruder (Nippon Steel Works TEX30XSST) having a diameter of 30 mmφ. Supplied from a type feeder. On the other hand, the E component is supplied to a side feeder provided in the middle of the extruder cylinder barrel so as to have a predetermined ratio using a vibratory supply device provided on the measuring device, and supplied to the extruder through the feeder. It was. Both the cylinder and the die were extruded at a temperature of 270 ° C., and a strand was produced at a screw rotation speed of 130 rpm, a discharge rate of 20 kg / hour, and a vent suction of 10,000 Pa, and then pelletized by a pelletizer.
A part of the obtained pellets was dried with a hot air circulation dryer at 120 ° C. for 6 hours, and then a test piece for evaluation was molded using an injection molding machine.
The manufacturing method of the polycarbonate resin described in Table 3 and Table 4 is as follows. The composition ratio and the viscosity average molecular weight are shown in Table 2.

(Production of copolymer polycarbonate resin (PC-1))
A reactor equipped with a thermometer, a stirrer and a reflux condenser was charged with 3844 parts of a 48% aqueous sodium hydroxide solution and 22,380 parts of ion-exchanged water, and 2,2-bis (4-hydroxy-3-methyl) was added thereto. Phenyl) propane (Bis-C, manufactured by Honshu Chemical) 1,992 parts, 2,2-bis (4-hydroxyphenyl) propane (Bis-A, manufactured by Nippon Steel Chemical) 1,773 parts, and hydrosulfite 7 After dissolving 53 parts (manufactured by Wako Pure Chemical Industries, Ltd.), 13,210 parts of methylene chloride was added, and 2,000 parts of phosgene was blown in at about 15-25 ° C. over about 60 minutes with stirring. After completion of the phosgene blowing, 640 parts of a 48% aqueous sodium hydroxide solution and 93.2 parts of p-tert-butylphenol were added and stirring was resumed. After emulsification, 3.24 parts of triethylamine was added and further stirred at 28 to 33 ° C. for 1 hour. The reaction was terminated. After completion of the reaction, the product is diluted with methylene chloride, washed with water, acidified with hydrochloric acid, washed with water, and further washed with water until the conductivity of the aqueous phase becomes substantially the same as that of ion-exchanged water. Obtained. Next, this solution is passed through a filter having an aperture of 0.3 μm, and further dropped into warm water in a kneader with an isolation chamber having a foreign matter outlet at the bearing, and the polycarbonate resin is flaked while distilling off methylene chloride. The liquid-containing flakes were pulverized and dried to obtain a powder. Thereafter, tris (2,4-di-tert-butylphenyl) phosphite was added to the powder in an amount of 0.05% by weight and stearic acid monoglyceride to 0.1% by weight. Carbon black (Mitsubishi Kasei Kogyo Co., Ltd. # 3600) 1 wt%, NUBIAN BLACK PC-5857 (Orient Chemical Industry Co., Ltd.) 0.1% by weight, two or more types of black mixed dyes, and then mixed with the powder A polycarbonate resin was obtained after melt-kneading while degassing with a type twin screw extruder [KTX-46, manufactured by Kobe Steel, Ltd.].

(Production of copolymer polycarbonate resin (PC-2)) A polycarbonate resin was obtained in the same manner as in Example 1, except that p-tert-butylphenol was changed to 81.6 parts by weight.
(Production of copolymer polycarbonate resin (PC-3))
A polycarbonate resin was obtained in the same manner as in Example 1 except that p-tert-butylphenol was changed to 69.9 parts by weight.
(Production of copolymer polycarbonate resin (PC-4))
The same procedure as in Example 1 except that 1,593 parts of 2,2-bis (4-hydroxy-3-methylphenyl) propane and 2,128 parts of 2,2-bis (4-hydroxyphenyl) propane were changed. A polycarbonate resin was obtained.
(Production of copolymer polycarbonate resin (PC-5))
In the same manner as in Example 1 except that 3,187 parts of 2,2-bis (4-hydroxy-3-methylphenyl) propane and 709 parts of 2,2-bis (4-hydroxyphenyl) propane were changed. A polycarbonate resin was obtained.
(Manufacture of polycarbonate resin (PC-6))
The same procedure as in Example 1 was performed except that Teijin Chemicals Panlite L-1225WX was used as the polycarbonate resin.
(Production of copolymer polycarbonate resin (PC-7))
The same procedure as in Example 1 except that 1,195 parts of 2,2-bis (4-hydroxy-3-methylphenyl) propane and 2,483 parts of 2,2-bis (4-hydroxyphenyl) propane were changed. A polycarbonate resin was obtained.
(Manufacture of polycarbonate resin (PC-8))
The same procedure as in Example 1 except that 2,2-bis (4-hydroxyphenyl) propane was not used and the amount was changed to 3,984 parts of 2,2-bis (4-hydroxy-3-methylphenyl) propane. A polycarbonate resin was obtained.
(Production of copolymer polycarbonate resin (PC-9))
A polycarbonate resin was obtained in the same manner as in Example 1 except that p-tert-butylphenol was changed to 116.6 parts by weight.
(Manufacture of polycarbonate resin (PC-10))
A polycarbonate resin was obtained in the same manner as in Example 1 except that p-tert-butylphenol was changed to 46.4 parts by weight.

(Production of copolymer polycarbonate resin (PC-11))
A reactor equipped with a thermometer, a stirrer and a reflux condenser was charged with 5236 parts of a 48% aqueous sodium hydroxide solution and 20,000 parts of ion-exchanged water, and 1,1-bis (4-hydroxy-3-methyl) was added thereto. After dissolving 4704 parts of phenyl) cyclohexane (Bis-OC-Z) and 9.4 parts of hydrosulfite, 17,540 parts of methylene chloride was added, and 2,200 parts of phosgene were added at 15-25 ° C. with stirring. Blowed over 60 minutes. After completion of the phosgene blowing, 654 parts of a 48% aqueous sodium hydroxide solution and 81.6 parts of p-tert-butylphenol were added and stirring was resumed. After emulsification, 4.32 parts of triethylamine was added and further stirred at 28 to 33 ° C. for 1 hour. The reaction was terminated. After completion of the reaction, the product is diluted with methylene chloride, washed with water, acidified with hydrochloric acid, washed with water, and further washed with water until the conductivity of the aqueous phase becomes substantially the same as that of ion-exchanged water. Obtained. Next, this solution is passed through a filter having an aperture of 0.3 μm, and further dropped into warm water in a kneader with an isolation chamber having a foreign matter outlet at the bearing, and the polycarbonate resin is flaked while distilling off methylene chloride. The liquid-containing flakes were pulverized and dried to obtain a powder. Thereafter, tris (2,4-di-tert-butylphenyl) phosphite is added to the powder so as to be 0.0025% by weight and stearic acid monoglyceride to be 0.1% by weight. The powder was melt-kneaded while degassing with a vent type twin screw extruder [KTX-46, manufactured by Kobe Steel, Ltd.] to obtain a copolymer polycarbonate resin.

(Production of copolymer polycarbonate resin (PC-12))
A reactor equipped with a thermometer, a stirrer and a reflux condenser was charged with 5236 parts of a 48% aqueous sodium hydroxide solution and 20,000 parts of ion-exchanged water, and 1,1-bis (4-hydroxy-3-methyl) was added thereto. Phenyl) cyclohexane (Bis-OC-Z) 2,533 parts, bisphenol A 1948 parts and hydrosulfite 9.4 parts were dissolved, methylene chloride 17,540 parts was added, and phosgene was added at 15-25 ° C. with stirring. 2,200 parts were blown in over about 60 minutes. After completion of the phosgene blowing, 654 parts of a 48% aqueous sodium hydroxide solution and 102 parts of p-tert-butylphenol were added and stirring was resumed. After emulsification, 4.32 parts of triethylamine was added, and the mixture was further stirred at 28 to 33 ° C. for 1 hour. The reaction was terminated. After completion of the reaction, the product is diluted with methylene chloride, washed with water, acidified with hydrochloric acid, washed with water, and further washed with water until the conductivity of the aqueous phase becomes substantially the same as that of ion-exchanged water. Obtained. Next, this solution is passed through a filter having an aperture of 0.3 μm, and further dropped into warm water in a kneader with an isolation chamber having a foreign matter outlet at the bearing, and the polycarbonate resin is flaked while distilling off methylene chloride. The liquid-containing flakes were pulverized and dried to obtain a powder. Thereafter, tris (2,4-di-tert-butylphenyl) phosphite is added to the powder so as to be 0.0025% by weight and stearic acid monoglyceride to be 0.1% by weight. The powder was melt-kneaded while degassing with a vent type twin screw extruder [KTX-46, manufactured by Kobe Steel, Ltd.] to obtain a copolymer polycarbonate resin.

(B component)
B-1: Fluidity improver having a weight average molecular weight of 58,000 (Metbrene TP003 (trade name) manufactured by Mitsubishi Rayon Co., Ltd.). The fluidity improver is a methacrylic acid in which the monomer (Ba) is phenyl methacrylate, the monomer (Bb) is styrene, and the weight ratio of Ba to Bb (Ba: Bb) is 16:84. It was a phenyl-styrene copolymer. When 1 g of the copolymer was mixed with 10 ml of chloroform and stirred for 30 minutes, the copolymer was insoluble and contained substantially no crosslinked structure. Its molecular weight distribution (Mw / Mn) was 2.3.
B-2: Fluidity improver comprising a polystyrene oligomer having a weight average molecular weight of 2,800 and a molecular weight distribution of 2.1 (manufactured by BASF: JONCRYL ADF-1300)
(GPC measurement of B-1)
GPC measurement was performed in a clean air environment at a temperature of 23 ° C. and a relative humidity of 50%, and two columns of ResiPore (length 300 mm, inner diameter 7.5 mm) manufactured by Polymer Laboratories were connected in series as a column, chloroform as a mobile phase, Using a polymer laboratory Easy Cal PS-2 as a standard substance, a photodiode array detector at a wavelength of 254 nm as a detector, using chloroform as a developing solvent, a solution in which 10 mg of a sample was dissolved per 5 ml of chloroform was dissolved in GPC. 50 μl was injected into the measuring device, GPC measurement was performed under conditions of a column temperature of 40 ° C. and a flow rate of 1 ml / min, the molecular weight of the flow modifier was measured, and the weight average molecular weight was calculated. The measuring apparatus is pump: L-6000 manufactured by Hitachi, Ltd., autosampler: L-7200 manufactured by Hitachi, Ltd., column oven: L-7300 manufactured by Hitachi, Ltd., photodiode array detector: (stock) ) L-2450 manufactured by Hitachi, Ltd.

(C component)
C-1: Core-shell graft copolymer (Rohm and Haas: Paraloid EXL-2602 (trade name))
C-2: Core-shell graft copolymer (manufactured by Mitsubishi Rayon Co., Ltd .: Metablen S-2001 (trade name)
C-3: Core-shell graft copolymer (Mitsubishi Rayon Co., Ltd .: Methabrene W-450A (trade name)
(D component)
D-1: Full ester of pentaerythritol and aliphatic carboxylic acid (manufactured by Riken Vitamin Co., Ltd .; Riquester EW-400 (trade name))
D-2: Full ester of dipentaerythritol and aliphatic carboxylic acid (manufactured by Riken Vitamin Co., Ltd .; Riquester SL-02 (trade name))
D-3: Stearin monostearate (Riken Vitamin Co., Ltd .; Riquemar S-100A (trade name))
(E component)
TALC: Talc (Hayashi Kasei Co., _Ltd.: U PN _{HS-T 0.8)}
WSN: Wollastonite (manufactured by NYCO: NYGLOS4)

  The polycarbonate resin composition of the present invention includes automotive parts, OA exterior parts such as PC exteriors and printer housings, dummy bottles, protective covers for display devices, IC magazine cases, silicon wafer containers, glass substrate storage containers, and optical disk cartridge cases. It can be used for building roofing materials. Among these, it is suitably used for vehicle exterior parts due to its excellent surface hardness, chemical resistance, fluidity, and impact characteristics. Such vehicle exterior parts include back panel, fender panel, bumper, door panel, pillar cover, side protector, side molding, rear protector, rear molding, various spoilers, bonnet, roof panel, trunk lid, detachable top, outer door handle, front These include grills, rear body panels, motorbike cowls, truck bed covers, wheel covers and wind reflectors.

Claims (9)

The aromatic dihydroxy component comprises 2,2-bis (4-hydroxy-3-methylphenyl) propane component (component a-1) and 2,2-bis (4-hydroxyphenyl) propane component (component a-2). And a ratio of the component a-1 is 40 to 90 mol% with respect to 100 mol of the wholly aromatic dihydroxy component, and the viscosity average molecular weight is 1.8 × 10 ^{4 to} 3.2 × 10 ^4. With respect to a total of 100 parts by weight of 98 to 85 parts by weight of resin (component A) and 2 to 15 parts by weight of fluidity improver (component B), 1 to 10 parts by weight of impact improver (component C) and pentaerythritol ester ( D component) An aromatic polycarbonate resin composition containing 0.05 to 0.5 parts by weight, wherein the fluidity improver (component B) is represented by (i) the following general formula (1): (Meth) acrylic A unit comprising a unit formed from an acid ester monomer and / or a (meth) acrylic acid ester monomer (Ba) represented by formula (2) and an aromatic alkenyl compound monomer (Bb) as a main constituent unit The ratio of the monomer (Ba) and the monomer (Bb) in the B component is 80% by weight or more in 100% by weight of the B component, and the total of both in 100% by weight. The monomer (Ba) is 1 to 80% by weight and the monomer (Bb) is 20 to 99% by weight, and (ii) the chloroform-soluble component has a weight average molecular weight of 10,000 to 200,000. A copolymer polycarbonate resin composition.

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents a carbocyclic group itself or a hydrocarbon group composed of a carbon chain bonded to a carbocyclic ring.)

(In the formula, R ³ represents a hydrogen atom or a methyl group, R ⁴ represents a carbocyclic group itself or a hydrocarbon group composed of a carbon chain bonded to a carbocyclic ring, and n represents an integer of 1 to 4. )   The copolymer polycarbonate resin composition according to claim 1, wherein the impact improver (component C) contains at least one rubber-modified resin selected from butadiene, acrylic, and silicone, or a copolymer thereof.   The copolymer polycarbonate resin composition according to any one of claims 1 to 2, comprising an inorganic filler (E component) in an amount of 0.1 parts by weight to 100 parts by weight with respect to 100 parts by weight of the total of the A component and the B component. object.   The copolymer polycarbonate resin composition according to claim 1, wherein the monomer (Ba) in the component B is phenyl methacrylate.   The monomer (Bb) in said B component is styrene, The copolymer polycarbonate resin composition in any one of Claims 1-4.   The copolymer polycarbonate resin composition according to any one of claims 1 to 5, comprising 0.0001 to 1 part by weight of a heat stabilizer (F component) based on 100 parts by weight of the total of the A component and the B component.   A molded article obtained from the copolymerized polycarbonate resin composition according to any one of claims 1 to 6.   The molded article according to claim 7 obtained by injection molding.   The molded article according to any one of claims 7 to 8, which is a member for an automobile.