JP2011098545A - Method for manufacturing polycarbonate resin molded product, and molded product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for efficiently manufacturing a polycarbonate resin molded product excelling in surface gloss, flaw resistance, mechanical strength and flame retardancy. <P>SOLUTION: The method for manufacturing the polycarbonate resin molded article includes injection-molding a polycarbonate resin composition containing 5-40 mass% of glass beads and a flame retardant selected out of a condensed phosphate-based compound and organic sulfonate metal salt, by heating a die surface immediately before filling molten resin to a glass transition temperature of the resin composition or higher. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for producing a polycarbonate resin molded article and a molded article, and more particularly relates to a method for producing a polycarbonate resin molded article having excellent surface gloss and scratch resistance, and excellent mechanical strength and flame retardancy. .

Polycarbonate resin is a general-purpose engineering plastic that excels in transparency, impact resistance, heat resistance, dimensional stability, etc., and its excellent characteristics make it an excellent choice in a wide range of fields such as electrical / electronic / OA equipment parts, machine parts, and vehicle parts. in use.
Among these, polycarbonate resins reinforced with glass fillers such as glass fibers exhibit various excellent performances such as dimensional stability, mechanical strength, heat resistance, and electrical characteristics. Widely used in the field.
In addition, in electrical and electronic parts and OA equipment parts, there is a strong demand for flame retardancy, and flame retardancy is performed by including various flame retardants.

In recent years, in the electric and electronic parts and OA equipment parts, the resin molded product to be used has been made thinner, and a material having a good appearance and a high rigidity has been required, and an inorganic filler such as a small particle diameter talc is contained. A flame retardant resin composition has been proposed (see, for example, Patent Document 1: Japanese Patent Application Laid-Open No. 2004-59898).
However, a polycarbonate resin composition containing talc has a good molded product surface appearance, but has a problem that the polycarbonate resin is decomposed due to the strong basicity of talc, resulting in poor thermal stability and impact resistance. It was. Furthermore, in the resin composition containing a non-halogen flame retardant, there is also a problem that the flame retardancy decreases as the talc content increases.

  Furthermore, while the glass-based filler-reinforced polycarbonate resin composition has the above-described excellent performance, the moldability (fluidity) is reduced, or the glass-based filler is raised on the surface of the molded product. There is a drawback that the appearance is remarkably impaired. For example, the surface appearance and scratch resistance of molded products such as housings of OA equipment such as personal computers and printers are particularly important for use in parts where importance is attached. There were restrictions.

  As described above, polycarbonate resin molded products with excellent surface gloss and scratch resistance, and excellent mechanical strength and flame retardancy can be produced with high production efficiency from polycarbonate resin compositions containing glass fillers in polycarbonate resins. There was a strong demand for manufacturing technology.

JP 2004-59898 A

  The purpose of the present invention is to eliminate the above-mentioned drawbacks of the prior art, and to produce polycarbonate resin molded products with excellent surface gloss and scratch resistance, and excellent mechanical strength and flame resistance by injection molding with high production efficiency. It is to provide a way to do.

  As a result of intensive research to achieve the above object, the inventors of the present invention blended a specific amount of glass beads and a specific flame retardant into the polycarbonate resin, injection molding, and the mold surface immediately before resin filling. By heating to a specific temperature or higher, it was found that a polycarbonate resin molded article having excellent surface gloss and scratch resistance, mechanical strength and flame retardancy can be produced with high production efficiency, and the present invention was completed. It was.

  That is, according to the first invention of the present invention, a polycarbonate resin composition containing 5 to 40% by mass of glass beads and a flame retardant selected from a condensed phosphate ester compound or an organic sulfonic acid metal salt is melted. There is provided a method for producing a polycarbonate resin molded product, characterized in that the mold surface immediately before resin filling is heated to a temperature equal to or higher than the glass transition temperature of the resin composition and injection molding is performed.

  According to the second invention of the present invention, in the first invention, the flame retardant is a condensed phosphate ester compound, and the content thereof is 5 to 20% by mass in the total composition. A method for producing a polycarbonate resin molded product is provided.

  According to the third invention of the present invention, in the first invention, the flame retardant is an organic sulfonic acid metal salt, and the content thereof is 0.01 to 1% by mass in the total composition. A method for producing a featured polycarbonate resin molded product is provided.

  According to a fourth aspect of the present invention, there is provided the method for producing a polycarbonate resin molded product according to any one of the first to third aspects, wherein the composition further contains an elastomer.

  According to a fifth aspect of the present invention, there is provided a method for producing a polycarbonate resin molded product according to the fourth aspect, wherein the elastomer is a core / shell type graft copolymer.

  According to the sixth invention of the present invention, in the fourth or fifth invention, the polycarbonate resin molded product characterized in that the elastomer content is 0.1 to 10% by mass in the total composition. A manufacturing method is provided.

  According to a seventh aspect of the present invention, there is provided a method for producing a polycarbonate resin molded product according to the first aspect, wherein the glass beads (B) have an average particle size of 10 to 30 μm. The

  According to an eighth aspect of the present invention, there is provided a method for producing a polycarbonate resin molded product according to the first aspect, wherein the mold surface is heated by high frequency electromagnetic induction heating.

  According to the ninth aspect of the present invention, there is provided a polycarbonate resin molded article produced by the method of the first to eighth aspects.

  According to a tenth aspect of the present invention, in the ninth aspect, a polycarbonate resin molded product is provided in which the molded product is a casing.

  According to the method for producing a polycarbonate resin molded article of the present invention, a polycarbonate resin molded article having excellent surface gloss and scratch resistance and excellent mechanical strength and flame retardancy can be produced with high production efficiency. The resulting molded product has high gloss, high surface hardness, excellent scratch resistance, can be used as a final product without painting, and also has excellent flame resistance and impact resistance. It has excellent performance as various electric and electronic parts, OA equipment parts, particularly as its casing.

  Hereinafter, the present invention will be described in detail with reference to embodiments and examples, but the present invention is not limited to the following embodiments and examples and the like, and is within the scope of the present invention. Any change can be made.

[1. Overview]
The method for producing a polycarbonate resin molded body according to the present invention comprises a polycarbonate resin composition containing a specific amount of glass beads and a flame retardant selected from a condensed phosphate ester compound or an organic sulfonic acid metal salt. The mold surface temperature is heated to the glass transition temperature or higher of the resin composition, and then injection molding is performed.
Hereinafter, each component which comprises the polycarbonate resin composition used in this invention is demonstrated first.

[2. Polycarbonate resin (A)]
Examples of the polycarbonate resin (A) used in the present invention include an aromatic polycarbonate resin, an aliphatic polycarbonate resin, and an aromatic-aliphatic polycarbonate resin, preferably an aromatic polycarbonate resin. A thermoplastic aromatic polycarbonate polymer or copolymer obtained by reacting an aromatic dihydroxy compound with phosgene or a diester of carbonic acid is used.

Aromatic dihydroxy compounds include 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), tetramethylbisphenol A, α, α'-bis (4-hydroxyphenyl) -p-diisopropylbenzene, hydroquinone, resorcinol 4,4′-dihydroxydiphenyl and the like. Further, as a part of the dihydroxy compound, when the above-mentioned aromatic dihydroxy compound is combined with one or more tetraalkylphosphonium sulfonates, or a polymer or oligomer containing both terminal phenolic OH groups having a siloxane structure, A highly flame-retardant polycarbonate resin can be obtained.
Preferred examples of the polycarbonate resin used in the present invention include 2,2-bis (4-hydroxyphenyl) propane as a dihydroxy compound, or 2,2-bis (4-hydroxyphenyl) propane and another aromatic dihydroxy compound. The polycarbonate resin used together is mentioned.

  The molecular weight of the polycarbonate resin used in the present invention is a viscosity average molecular weight converted from the solution viscosity measured at a temperature of 25 ° C. using methylene chloride as a solvent, and is usually 14,000 to 30,000, preferably 18,000 to 29. , 000. When the viscosity average molecular weight is within this range, a molded product having good moldability (fluidity) and high mechanical strength can be obtained. The most preferred molecular weight range of the polycarbonate resin is 22,000-28,000.

The method for producing the polycarbonate resin is not particularly limited, but it is usually produced by any of an interfacial polymerization method (phosgene method) and a melting method (transesterification method).
In the interfacial polymerization method, the polymerization reaction is usually carried out in the presence of an organic solvent inert to the reaction and an aqueous alkaline solution, and the pH is usually kept at 9 or higher. An aromatic dihydroxy compound and, if necessary, a molecular weight modifier (end stopper) And an antioxidant for preventing oxidation of the aromatic dihydroxy compound, and after reacting with phosgene, a polymerization catalyst such as a tertiary amine or a quaternary ammonium salt is added, and interfacial polymerization is carried out to obtain a polymer. A sulfonate resin is obtained. The addition of the molecular weight regulator is not particularly limited as long as it is from the time of phosgenation to the start of the polymerization reaction. In addition, reaction temperature is 0-40 degreeC, for example, and reaction time is several minutes (for example, 10 minutes)-several hours (for example, 6 hours), for example.

  Here, examples of the organic solvent inert to the reaction include chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, monochlorobenzene and dichlorobenzene, and aromatic hydrocarbons such as benzene, toluene and xylene. . Examples of the alkali compound used in the alkaline aqueous solution include hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide.

  Examples of the molecular weight regulator include compounds having a monovalent phenolic hydroxyl group, such as m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, and p-tert. Preferred examples include -butylphenol and p-long chain alkyl-substituted phenol. The amount of the molecular weight regulator used is preferably 50 to 0.5 mol, more preferably 30 to 1 mol, per 100 mol of the aromatic dihydroxy compound.

  Polymerization catalysts include tertiary amines such as trimethylamine, triethylamine, tributylamine, tripropylamine, trihexylamine, pyridine, and quaternary ammonium salts such as trimethylbenzylammonium chloride, tetramethylammonium chloride, and triethylbenzylammonium chloride. Etc.

Next, the melting method will be described.
The polymerization reaction in this production method is, for example, a transesterification reaction between a carbonic acid diester and an aromatic dihydroxy compound. Examples of the carbonic acid diester include dialkyl carbonate compounds such as dimethyl carbonate, diethyl carbonate and di-tert-butyl carbonate, and substituted diphenyl carbonates such as diphenyl carbonate and ditolyl carbonate. An example is a bonate. The carbonic acid diester is preferably diphenyl carbonate or substituted diphenyl carbonate, more preferably diphenyl carbonate.

In the aromatic polycarbonate resin, the amount of terminal hydroxyl groups greatly affects the thermal stability, hydrolysis stability, color tone, etc. of the product polycarbonate resin, and may be adjusted as appropriate by any conventionally known method. . In the melt transesterification reaction, usually, the mixing ratio of the carbonic acid diester and the aromatic dihydroxy compound and the degree of pressure reduction during the transesterification reaction are adjusted to obtain an aromatic polycarbonate resin having the desired molecular weight and terminal hydroxyl group content adjusted. be able to.
Usually, in the melt transesterification reaction, an equimolar amount or more of carbonic acid diester is used with respect to 1 mol of the aromatic dihydroxy compound, among which 1.001 to 1.3 mol, particularly 1.01 to 1.2 mol is used. preferable. Further, as a more aggressive adjustment method, there is a method of adding a terminal terminator separately at the time of reaction, and examples of the terminal terminator in this case include monohydric phenols, monovalent carboxylic acids, and carbonic acid diesters. It is done.
By increasing the number of moles of carbonic acid diester per mole of aromatic dihydroxy compound to more than 1.001, the increase in terminal OH groups of the fused aromatic polycarbonate resin is suppressed, and the thermal stability and hydrolysis resistance are improved. Although the terminal OH group of the melt-processed aromatic polycarbonate resin is reduced by being within 1.3, the aromatic polycarbonate resin has a desired molecular weight while maintaining the transesterification rate under the same conditions. This is preferable because it tends to be easy to produce.

  Furthermore, the polycarbonate resin (A) used in the present invention may be not only a polycarbonate resin as a virgin raw material but also a polycarbonate resin regenerated from a used product, a so-called material recycled polycarbonate resin.

[2. Glass beads (B)]
The glass beads (B) used in the present invention are usually spherical ones having an average particle diameter of 3 to 100 μm. The compounding quantity of a glass bead is 5-40 mass% of the whole polycarbonate resin composition.
If the blending amount of the glass beads is less than 5% by mass, the effect of improving the surface gloss and scratch resistance, the improvement of rigidity and the reinforcing effect are insufficient, and if it exceeds 40% by mass, a polycarbonate resin having a low molecular weight and a low melt viscosity is used. Even if it is used, the fluidity is poor, the moldability is deteriorated, and the flame retardancy is difficult. The preferable compounding amount of the glass beads is 10 to 35% by mass, more preferably 10 to 30% by mass.
Further, the glass composition of the glass beads is preferable because glass composition such as A glass, C glass and E glass, particularly E glass which is alkali-free glass does not adversely affect the polycarbonate resin.

The preferable particle diameter of the glass beads is 10 to 30 μm in average particle diameter. If the average particle size is less than 10 μm, the moldability of the polycarbonate resin composition tends to be impaired, and if it exceeds 30 μm, the surface appearance of the molded product tends to be impaired, and the scratch resistance tends to be insufficient.
As long as the characteristics of the polycarbonate resin composition of the present invention are not impaired, the glass beads may be surface-treated with, for example, a silane compound or an epoxy compound in order to improve the affinity with the polycarbonate resin.

[3. Flame retardant (C)]
In the present invention, a condensed phosphate ester compound (C1) or an organic sulfonic acid metal salt (C2) is used as a flame retardant.

[3-1. Condensed phosphate ester compound (C1)]
The condensed phosphate ester (C1) used in the present invention is preferably one represented by the following general formula.

（式中、Ｒ^１、Ｒ^２、Ｒ^３およびＲ^４は、それぞれ独立して水素原子または有機基を表す。ただし、Ｒ^１、Ｒ^２、Ｒ^３およびＲ^４が全て水素原子の場合を除く。Ｘは２価の有機基を表し、ｐは０または１であり、ｑは１以上の整数、ｒは０または１以上の整数を表す。）

(In the formula, R ¹ , R ² , R ³ and R ⁴ each independently represents a hydrogen atom or an organic group, except that R ¹ , R ² , R ³ and R ⁴ are all hydrogen atoms. X represents a divalent organic group, p is 0 or 1, q represents an integer of 1 or more, and r represents 0 or an integer of 1 or more.)

  In the above general formula, the organic group includes, for example, an alkyl group, a cycloalkyl group, and an aryl group with or without a substituent, and the substituent includes an alkyl group, an alkoxy group, an alkylthio group, and an aryl group. Group, aryloxy group, arylthio group, halogen atom, halogenated aryl group and the like. Further, a group in which these substituents are combined, or a group in which these substituents are combined by combining with an oxygen atom, a sulfur atom, a nitrogen atom or the like may be used. The divalent organic group refers to a divalent or higher group formed by removing one carbon atom from the above organic group. Examples thereof include an alkylene group, a phenylene group, a substituted phenylene group, and a polynuclear phenylene group derived from bisphenols.

  Specific examples of the condensed phosphate ester represented by the above general formula include, for example, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, tricresyl Phenyl phosphate, octyl diphenyl phosphate, diisopropyl phenyl phosphate, tris (chloroethyl) phosphate, tris (dichloropropyl) phosphate, tris (chloropropyl) phosphate, bis (2,3-dibromopropyl) phosphate, Bis (2,3-dibromopropyl) -2,3-dichlorophosphate, bis (chloropropyl) monooctyl phosphate, bisphenol A tetraphenyl phosphate, Scan phenol A tetra cresyl diphosphate, bisphenol A tetra xylylene distearate phosphate, hydroquinone tetraphenyl diphosphate, hydroquinone tetra cresyl phosphate, various ones such as hydroquinone tetra xylylene distearate phosphate are exemplified.

  The preferable content of the condensed phosphate ester compound is 5 to 20% by mass, more preferably 7 to 18% by mass, and particularly 8 to 15% by mass in 100% by mass of the polycarbonate resin composition. When the content is less than 5% by mass, the flame retardancy tends to be insufficient, and when it exceeds 20% by mass, the heat resistance and the mechanical properties are likely to decrease.

[3-2. Organic sulfonic acid metal salt (C2)]
Examples of the organic sulfonic acid metal salt (C2) used in the present invention include aliphatic sulfonic acid metal salts and aromatic sulfonic acid metal salts. Among them, aromatic sulfone sulfonic acid metal salts and perfluoroalkane sulfonic acid metal salts. A salt is preferred, and a perfluoroalkanesulfonic acid metal salt is particularly preferred.
The metal of the organic sulfonic acid metal salt is not particularly limited but preferably includes alkali metals such as sodium, lithium, potassium, rubidium and cesium, and alkaline earth metals such as beryllium, magnesium, calcium, strontium and barium. It is done. Of these, potassium is preferred from the viewpoints of flame retardancy and hydrolysis resistance. These organic sulfonic acid metal salts may be used in combination of two or more.

The aromatic sulfonesulfonic acid metal salt is preferably an aromatic sulfonesulfonic acid alkali metal salt, an aromatic sulfonesulfonic acid alkaline earth metal salt, or the like. The acid alkaline earth metal salt may be a polymer.
Specific examples of the aromatic sulfonesulfonic acid metal salt include sodium salt of diphenylsulfone-3-sulfonic acid, potassium salt of diphenylsulfone-3-sulfonic acid, sodium 4 / 4'-dibromodiphenyl-sulfone-3-sulfone Salt, potassium salt of 4,4′-dibromodiphenylsulfone-3-sulfone, calcium salt of 4-chloro-4′-nitrodiphenylsulfone-3-sulfonic acid, diphenylsulfone-3,3′-disulfonic acid di Examples thereof include sodium salts and dipotassium salts of diphenylsulfone-3,3′-disulfonic acid.

The perfluoroalkanesulfonic acid metal salt is preferably an alkali metal salt of perfluoroalkanesulfonic acid, an alkaline earth metal salt of perfluoroalkanesulfonic acid, or the like, more preferably a perfluoroalkane having 4 to 8 carbon atoms. Examples include sulfonic acid alkali metal salts having an alkane group and sulfonic acid alkaline earth metal salts having a C 4-8 perfluoroalkane group.
Specific examples of the perfluoroalkanesulfonic acid metal salt include sodium perfluorobutanesulfonate, potassium perfluorobutanesulfonate, sodium perfluoromethylbutanesulfonate, potassium perfluoromethylbutanesulfonate, sodium perfluorooctanesulfonate, Examples include potassium perfluorooctane sulfonate and tetraethylammonium salt of perfluorobutane sulfonic acid.
Among these, potassium perfluorobutanesulfonate is particularly preferable.

The preferable content of the organic sulfonic acid metal salt is 0.01 to 1% by mass, more preferably 0.05 to 0.5% by mass, particularly 0.1 to 0.3% in 100% by mass of the polycarbonate resin composition. % By mass. When the content is less than 0.01% by mass, it is difficult to obtain sufficient flame retardancy, and when it exceeds 1% by mass, the thermal stability and hydrolysis resistance tend to be lowered.
In the field where transparency of the molded product is required, it is preferable to use an organic sulfonic acid metal salt rather than the above-described condensed phosphate.

[4. Method of injection molding of resin composition]
In the method of the present invention, a polycarbonate resin composition containing glass beads, the above flame retardant, and other components as necessary is injection-molded. At that time, the mold surface immediately before filling the mold with the molten resin, The resin composition is heated above the glass transition temperature (Tg) of the resin composition, and then the molten resin composition is injected and molded into the mold cavity.
The mold surface may be heated by heating only the cavity surface of the mold, and it is not necessary to heat the entire mold. As such a heating method, a method of heating by incorporating a heat transfer heater near the cavity surface inside the mold, a method of heating by infrared heating etc. by inserting a heater on the cavity side with the male and female molds opened Alternatively, a method of injecting high-temperature steam between both male and female molds and heating can be used.

As a preferable heating means, it is possible to use high frequency electromagnetic induction heating, in particular, insert a donut-shaped high frequency induction coil for high frequency electromagnetic induction heating, for example, between both dies when the male and female molds are opened, Preferably only the cavity surface is heated rapidly. Due to electromagnetic induction, an induced current is generated on the mold surface, Joule heat is generated, and only the mold surface generates heat in a short time. The heating may be performed by adjusting the heating output and the time while detecting the temperature with a temperature sensor. Usually, the heating time is about 1 second to 1 minute, preferably 1 second to 30 seconds.
The temperature of the mold surface immediately before resin filling is not the glass transition temperature of the polycarbonate resin alone, but the glass transition temperature (Tg) of the polycarbonate resin composition or higher. As is well known, the glass transition temperature of the polycarbonate resin composition is measured by a differential thermal analyzer (DSC). However, as far as the inventors have studied, the above-described composition of the present invention has a single endothermic peak. As shown, it is determined from the peak temperature.

The mold surface temperature immediately before filling is set to be higher than the Tg of the resin composition, but is 5 ° C. to 60 ° C., more preferably 10 ° C. to 50 ° C., particularly 20 ° C. to Tg of the resin composition. The temperature is preferably increased by 40 ° C.
The mold temperature other than the mold cavity surface is preferably set to an optimum mold temperature for injection molding the polycarbonate resin composition, usually about 40 ° C to 120 ° C.
By raising the mold surface temperature immediately before filling to Tg or more of the resin composition, the glass pearl is prevented from floating on the mold surface during injection injection, and a molded article having excellent surface gloss and scratch resistance can be obtained. . It is common sense in the field of injection molding that mold temperature is too high and the mold surface is likely to be in close contact with the mold surface, resulting in defective mold release and deformation after mold release. The temperature at the time is kept high only on the mold surface, but the others are normal temperatures. Therefore, after filling, the mold is cooled as usual, and the molded product is taken out.

  The type of injection molding is not particularly limited, and any method that falls within the category of injection molding generally employed for polycarbonate resin compositions can be arbitrarily employed. Examples thereof include an injection molding method, an ultra-high speed injection molding method, an injection compression molding method and the like.

[5. Elastomer (D)]
The polycarbonate resin composition used in the present invention preferably contains an elastomer (D). A preferable blending amount of the elastomer is 0.1 to 10% by mass in 100% by mass of the polycarbonate resin composition. Thus, the impact resistance of a polycarbonate resin composition can be improved by containing an elastomer.
If the elastomer content is less than 0.1% by mass, the impact resistance improving effect by the elastomer is insufficient, and if it exceeds 10% by mass, the molded product molded from the polycarbonate resin composition has poor appearance and heat resistance. A decrease occurs. The lower limit of the content is more preferably 1% by mass or more, and the upper limit of the content is preferably 7.5% by mass or less, more preferably 5% by mass or less, and particularly preferably 4% by mass or less. .

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

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

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

The graft copolymer obtained by copolymerizing the rubber component is preferably of the core / shell type graft copolymer type from the viewpoint of impact resistance and surface appearance. Among them, at least one rubber component selected from polybutadiene-containing rubber, polybutyl acrylate-containing rubber, polyorganosiloxane rubber, IPN type composite rubber composed of polyorganosiloxane rubber and polyalkyl acrylate rubber is used as a core layer, and around it. A core / shell type graft copolymer comprising a shell layer formed by copolymerizing (meth) acrylic acid ester is particularly preferred.
In the said core / shell type graft copolymer, what contains 40 mass% or more of rubber components is preferable, and what contains 60 mass% or more is further more preferable. Moreover, what contains 10 mass% or more of (meth) acrylic acid is preferable.

  Preferable specific examples of these core / shell type graft copolymers include methyl methacrylate-butadiene-styrene copolymer (MBS), methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (MABS), and methyl methacrylate-butadiene copolymer. Copolymer (MB), methyl methacrylate-acrylic rubber copolymer (MA), methyl methacrylate-acrylic rubber-styrene copolymer (MAS), methyl methacrylate-acrylic-butadiene rubber copolymer, methyl methacrylate-acrylic-butadiene rubber- Examples thereof include styrene copolymers and methyl methacrylate- (acryl / silicone IPN rubber) copolymers. Such rubbery polymers may be used alone or in combination of two or more.

  Examples of such a core / shell type graft copolymer include “Paraloid (registered trademark, hereinafter the same) EXL2602”, “Paraloid EXL2603”, “Paraloid EXL2655”, “Paraloid” manufactured by Rohm and Haas Japan. “EXL2311”, “Paraloid EXL2313”, “Paraloid EXL2315”, “Paraloid KM330”, “Paraloid KM336P”, “Paraloid KCZ201”, “Metabrene (registered trademark, the same shall apply hereinafter) C-223A”, “Metabrene E” manufactured by Mitsubishi Rayon Co., Ltd. -901 "," Metabrene S-2001 "," Metabrene SRK-200 "," Kaneace (registered trademark, the same applies hereinafter) M-511 "," Kaneace M-600 "," Kaneace M-400 "manufactured by Kaneka Corporation "Kane Ace M-580 , "Kane Ace MR-01", and the like.

[6. Fluorine resin (E) having fibril-forming ability]
The polycarbonate resin composition used in the present invention is preferably blended with a fluororesin (E) having a fibril forming ability. The fluororesin used as the component B of the present invention is an anti-drip agent that easily disperses in a resin composition and shows a tendency to form a fibrous structure by bonding polymers to each other. Is a fluorine-based resin. The molecular weight of the fluororesin tree having the ability to form fibrils has a very high molecular weight of 1,000,000 to 10,000,000, and shows a tendency to join together the fluororesins by an external action such as shearing force to form a fiber. is there. Examples of the fluororesin include tetrafluoroethylene (TFE) resin, perfluoroalkoxy (PFA) resin, and fluorinated ethylene propylene (FEP) resin, and polytetrafluoroethylene is particularly preferable.
Examples of polytetrafluoroethylene having fibril-forming ability include Teflon (registered trademark) 6J manufactured by Mitsui DuPont Fluorochemical Co., Ltd. and polyflon manufactured by Daikin Chemical Industries, Ltd.
As an aqueous dispersion of polytetrafluoroethylene, Teflon (registered trademark) 30J manufactured by Mitsui DuPont Fluorochemical Co., Ltd., Fullon (registered trademark) D-1 manufactured by Daikin Chemical Industries, Ltd., and vinyl monomers are used. A polytetrafluoroethylene polymer having a multilayer structure formed by polymerization, for example, Metabrene A-3800 manufactured by Mitsubishi Rayon Co., Ltd. may be mentioned.

  The blending amount of the fluororesin (E) having fibril-forming ability is preferably 0.01 to 1% by mass in 100% by mass of the polycarbonate resin composition. When the amount of the resin composition exceeds 1% by mass, the mechanical strength and processing fluidity of the resin composition are liable to be lowered, and the appearance of the molded product is liable to be deteriorated, more preferably 0.03 to 0.8. By mass%, it is particularly preferably 0.05 to 0.6 mass%.

[7. Other ingredients]
In the polycarbonate resin composition used in the present invention, other components other than those described above may be blended as necessary as long as the desired physical properties are not significantly impaired. Examples of other components include resins other than polycarbonate resins and various resin additives. In addition, 1 type may contain other components and 2 or more types may contain them by arbitrary combinations and ratios.

Other resins Examples of other resins include thermoplastic polyester resins such as polyethylene terephthalate resin (PET resin), polytrimethylene terephthalate (PTT resin), and polybutylene terephthalate resin (PBT resin);
Polystyrene resin (PS resin), high impact polystyrene resin (HIPS), acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene-acrylic rubber copolymer (ASA) Resin), styrene resin such as acrylonitrile-ethylene propylene rubber-styrene copolymer (AES resin);

Polyolefin resins such as polyethylene resin (PE resin), polypropylene resin (PP resin), cyclic cycloolefin resin (COP resin), cyclic cycloolefin copolymer (COP) resin;
Polyamide resin (PA resin); Polyimide resin (PI resin); Polyetherimide resin (PEI resin); Polyurethane resin (PU resin); Polyphenylene ether resin (PPE resin); Polyphenylene sulfide resin (PPS resin); Polysulfone resin (PSU) Resin); polymethacrylate resin (PMMA resin); and the like.

-Resin additives Examples of resin additives include mold release agents, heat stabilizers, diffusing agents, antioxidants, UV absorbers, dyes and pigments, antistatic agents, antifogging agents, lubricants, antiblocking agents, and fluidity. Examples include improvers, plasticizers, dispersants, antibacterial agents, and other fillers. In addition, 1 type may contain resin additive and 2 or more types may contain it by arbitrary combinations and a ratio.
Hereinafter, the example of an additive suitable for the polycarbonate resin composition of this invention is demonstrated concretely.

.. Release agent Examples of the release agent include aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15,000, polysiloxane silicone oil, and the like. Can be mentioned.
Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic monovalent, divalent or trivalent carboxylic acid. Here, the aliphatic carboxylic acid includes alicyclic carboxylic acid. Among these, preferable aliphatic carboxylic acids are monovalent or divalent carboxylic acids having 6 to 36 carbon atoms, and aliphatic saturated monovalent carboxylic acids having 6 to 36 carbon atoms are more preferable.
Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, mellicic acid, tetrariacontanoic acid, montanic acid, adipine Examples include acids and azelaic acid.

  As aliphatic carboxylic acid in ester of aliphatic carboxylic acid and alcohol, the same thing as the said aliphatic carboxylic acid can be used, for example. Examples of the alcohol include saturated or unsaturated monovalent or polyhydric alcohols, and these alcohols may have a substituent such as a fluorine atom or an aryl group. Among these, a monovalent or polyvalent saturated alcohol having 30 or less carbon atoms is preferable, and an aliphatic or alicyclic saturated monohydric alcohol or aliphatic saturated polyhydric alcohol having 30 or less carbon atoms is more preferable.

Specific examples of such alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol, and the like. Is mentioned.
Specific examples of esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture based on myricyl palmitate), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, glycerin monostearate Examples thereof include rate, glycerol distearate, glycerol tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate and the like.

Examples of the aliphatic hydrocarbon having a number average molecular weight of 200 to 15,000 include liquid paraffin, paraffin wax, microwax, polyethylene wax, Fischer-Tropsch wax, and α-olefin oligomer having 3 to 12 carbon atoms. Here, the aliphatic hydrocarbon includes alicyclic hydrocarbons.
Among these, paraffin wax, polyethylene wax, or a partial oxide of polyethylene wax is preferable, and paraffin wax and polyethylene wax are more preferable.
The number average molecular weight of the aliphatic hydrocarbon is preferably 5,000 or less.

  The content of the release agent is usually 0.001 part by mass or more, preferably 0.01 part by mass or more, and usually 2 parts by mass or less, preferably 1 part by mass or less with respect to 100 parts by mass of the polycarbonate resin. It is. When the content of the release agent is not more than the lower limit of the above range, the effect of releasability may not be sufficient, and when the content of the release agent exceeds the upper limit of the above range, hydrolysis resistance And mold contamination during injection molding may occur.

.. Heat stabilizer Examples of the heat stabilizer include phosphorus compounds. Any known phosphorous compound can be used. Specific examples include phosphorus oxo acids such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, and polyphosphoric acid; acidic pyrophosphate metal salts such as acidic sodium pyrophosphate, acidic potassium pyrophosphate, and acidic calcium pyrophosphate; phosphoric acid Examples thereof include phosphates of Group 1 or Group 10 metals such as potassium, sodium phosphate, cesium phosphate, and zinc phosphate; organic phosphate compounds, organic phosphite compounds, and organic phosphonite compounds.

  Among them, triphenyl phosphite, tris (monononylphenyl) phosphite, tris (monononyl / dinonyl phenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, monooctyl diphenyl phosphite, Dioctyl monophenyl phosphite, monodecyl diphenyl phosphite, didecyl monophenyl phosphite, tridecyl phosphite, trilauryl phosphite, tristearyl phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) ) Organic phosphites such as octyl phosphite are preferred.

As such an organic phosphite compound, specifically, for example, “Adeka Stub 1178”, “Adeka Stub 2112”, “Adeka Stub HP-10”, manufactured by Adeka Co., Ltd. Examples thereof include “JP-351”, “JP-360”, “JP-3CP”, “Irgaphos 168” manufactured by Ciba Specialty Chemicals.
In addition, 1 type may contain the heat stabilizer and 2 or more types may contain it by arbitrary combinations and a ratio.

  The content of the heat stabilizer is usually 0.001 part by mass or more, preferably 0.01 part by mass or more, more preferably 0.03 part by mass or more, based on 100 parts by mass of the polycarbonate resin. It is not more than part by mass, preferably not more than 0.7 part by mass, more preferably not more than 0.5 part by mass. If the amount of the heat stabilizer is too small, the heat stabilization effect may be insufficient. If the amount of the heat stabilizer is too large, the effect may reach a peak and may not be economical.

.. Antioxidants Examples of antioxidants include hindered phenol antioxidants. Specific examples thereof include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl). ) Propionate, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexane-1,6-diylbis [3- (3,5-di-) tert-butyl-4-hydroxyphenylpropionamide), 2,4-dimethyl-6- (1-methylpentadecyl) phenol, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl ] Methyl] phosphoate, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert-butyl-a, a ′, a ″-(mesi Tylene-2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4- Hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris (3,5-di-tert- Butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert-butyl-4- (4,6-bis ( Octylthio) -1,3,5-triazin-2-ylamino) phenol and the like.

Among them, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate preferable. Specific examples of such phenolic antioxidants include “Irganox 1010” (registered trademark, the same shall apply hereinafter) manufactured by Ciba Specialty Chemicals, “Irganox 1076”, and “Adeka Stub” manufactured by Adeka. AO-50 "," ADK STAB AO-60 "and the like.
In addition, 1 type may contain antioxidant and 2 or more types may contain it by arbitrary combinations and a ratio.

  The content of the antioxidant is usually 0.001 part by mass or more, preferably 0.01 part by mass or more, and usually 1 part by mass or less, preferably 0.5 part by mass with respect to 100 parts by mass of the polycarbonate resin. Or less. When the content of the antioxidant is less than or equal to the lower limit of the range, the effect as an antioxidant may be insufficient, and when the content of the antioxidant exceeds the upper limit of the range, There is a possibility that the effect reaches its peak and is not economical.

-Dye / pigment Examples of the dye / pigment include inorganic pigments, organic pigments, and organic dyes.
Examples of inorganic pigments include sulfide pigments such as carbon black, cadmium red, and cadmium yellow; silicate pigments such as ultramarine blue; titanium oxide, zinc white, petal, chromium oxide, iron black, titanium yellow, zinc- Oxide pigments such as iron brown, titanium cobalt green, cobalt green, cobalt blue, copper-chromium black and copper-iron black; chromic pigments such as chrome lead and molybdate orange; Examples include Russian pigments.

Examples of organic pigments and organic dyes include phthalocyanine dyes such as copper phthalocyanine blue and copper phthalocyanine green; azo dyes such as nickel azo yellow; thioindigo, perinone, perylene, quinacridone, dioxazine, iso Examples thereof include condensed polycyclic dyes such as indolinone and quinophthalone; quinoline, anthraquinone, heterocyclic and methyl dyes.
Among these, titanium oxide, carbon black, cyanine-based, quinoline-based, anthraquinone-based, phthalocyanine-based dyes and the like are preferable from the viewpoint of thermal stability.
In addition, 1 type may contain the dye / pigment, and 2 or more types may contain it by arbitrary combinations and a ratio. In addition, dyes and pigments may be used as masterbatches with polystyrene resins, polycarbonate resins, and acrylic resins for the purpose of improving handling during extrusion and improving dispersibility in the resin composition. Good.

  The content of the dye / pigment is usually 5 parts by mass or less, preferably 3 parts by mass or less, more preferably 2 parts by mass or less with respect to 100 parts by mass of the polycarbonate resin. If the content of the dye / pigment is too large, the impact resistance may not be sufficient.

[8. Production of polycarbonate resin composition]
Mixing of each component to obtain a polycarbonate resin composition containing the above components is uniformly performed using a known mixing device such as a Henschel mixer, a super mixer, a tumbler, a Banbury mixer, a turnbull mixer, a ribbon blender, or the like. be able to.
The temperature of the polycarbonate resin at the time of mixing is preferably 20 to 80 ° C., more preferably 20 to 60 ° C. for uniform dispersion. Aggregation tends to occur if the temperature rises too much. It is also preferable to carry out in an inert gas atmosphere such as nitrogen.
The method of melt-kneading after mixing is not particularly limited, but it is preferable to melt-knead using a twin-screw extruder in order to further achieve good dispersion of the polycarbonate resin and other components. The screw shape of the extruder may be a normal one or a kneading strengthened type.
The resin extruded from the extruder is directly cut into pellets, or after forming a strand, the resin is cut with a pelletizer and pelletized. Moreover, it is also possible to make a resin by melt-kneading with an injection molding machine without going through pellets.

[9. Molding]
The polycarbonate resin composition of the present invention can be injection-molded by the above-described method to obtain a molded product having an arbitrary shape.
Examples of molded products include parts such as electrical and electronic equipment, OA equipment, information terminal equipment, lighting equipment parts, machine parts, home appliances, vehicle parts, building members, various containers, leisure goods and miscellaneous goods, and the like. . Among these, it is particularly suitable for use in parts such as electric and electronic equipment, OA equipment, information terminal equipment, home appliances, etc. Especially, parts of electric and electronic equipment, especially housings for display screens such as personal computers and liquid crystal / plasma televisions. It is suitable for use.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples, and can be arbitrarily modified and implemented without departing from the gist of the present invention.

[Materials used]
The materials used in Examples and Comparative Examples are as follows.
(A) Aromatic polycarbonate resin Poly-4,4-isopropylidenediphenyl carbonate "Iupilon (registered trademark) S-3000" manufactured by Mitsubishi Engineering Plastics
Viscosity average molecular weight 22,000

(B) Glass additive The glass beads and other glass fillers shown in Table 1 below were used. (The dimensions are the values described in the catalog values for each product.)

(C) Phosphate ester-based flame retardant (C1): Phenol condensate of 2,2-bis (p-hydroxyphenyl) propane / trichlorophosphine oxide polycondensate (degree of polymerization 1 to 3) “ADEKA STAB FP-” manufactured by ADEKA 700 "
(C2): 1,3-phenylenebis (di-2,6-xylenyl phosphate)
“PX-200” aromatic condensed phosphate ester (C ′) organic sulfonic acid metal salt flame retardant (C3): perfluorobutanesulfonic acid potassium salt (C ₄ F ₉ SO ₃ K) manufactured by Daihachi Chemical Industry Co., Ltd.
Product name “Bayowet C4” manufactured by Bayer

(D) Elastomer (core / shell type graft copolymer)
(D1): Butadiene / alkyl acrylate / alkyl methacrylate copolymer, trade name “Paraloid EXL2603” manufactured by Rohm & Haas
(D2): Acrylonitrile / Styrene / Dimethylsiloxane Alkyl Acrylate Copolymer Product name “Metbrene SRK200” manufactured by Mitsubishi Rayon Co., Ltd.
(D3): Alkyl acrylate / alkyl methacrylate copolymer, trade name “Paraloid EXL2315” manufactured by Rohm & Haas

(E) Polyfluoroethylene (PTFE)
Product name "Polyflon F-201L" manufactured by Daikin Industries
(F) Thermal stabilizer Tris (2,4-di-tert-butylphenyl) phosphite Product name “ADEKA STAB 2112” manufactured by ADEKA
(G) Mold release agent Stearyl stearate Octadecyl stearate NOF Corporation trade name “Unistar M9676”

(Examples 1-9, Comparative Examples 1-6)
Each component described above was blended in the proportions (mass%) shown in Tables 2 and 3 below, mixed with a tumbler, and then charged into the hopper of a twin-screw extruder (TEX30HSST, 12 blocks) manufactured by Nippon Steel Works. did. Each resin component was melt-kneaded under the conditions of a cylinder temperature of 270 ° C., 250 rpm, and an extrusion rate of 20 kg / hour, the molten resin composition extruded in a strand shape was quenched in a water tank, pelletized with a pelletizer, and polycarbonate A pellet of the resin composition was obtained.

  The obtained resin composition pellets were measured for glass transition temperature (Tg) using a differential thermal analysis (DSC) apparatus manufactured by SEIKO Instrument. The measurement is carried out using nitrogen gas with a carrier gas of 60 ml / min, and the measurement temperature change is 30 ° C. (20 ° C./min)→250° C., hold for 3 minutes (20 ° C./min)→30° C., hold for 3 minutes (20 ° C./min) ) → It was carried out under the condition of 250 ° C. Tg of each pellet is shown in Tables 2-3.

Using each of the above pellets, the mold cavity surface temperature immediately before injection filling was set to the temperatures shown in Tables 2 to 3, and various test pieces were injection molded by the methods described below.
The mold is heated by inserting a high frequency induction coil of a high frequency electromagnetic induction heating device between the male and female molds in an open state, and heating the cavity surface at a frequency of 20 KHz and an output of 15 KW on the cavity surface of the female mold. I went there. The mold surface temperature was adjusted by adjusting the irradiation time between 1 second and 20 seconds.
The induction coil was immediately extracted, the mold was closed to a predetermined clearance, the molten resin composition was immediately injected and filled into the mold cavity, and water cooling was performed until the mold cooled to 80 ° C.
After cooling, the mold was opened and the molded product was taken out.

[Molding and property evaluation of each specimen]
(1) Surface hardness Using each pellet, using the injection molding machine SE100DU manufactured by Sumitomo Heavy Industries, Ltd. at a set temperature of 270 ° C., the mold surface immediately before filling is set to the temperature described in Tables 2-3, and 100 mm × A plate-like test piece having a thickness of 100 mm × 2 mm was injection molded.
As the evaluation of the surface hardness, the pencil hardness was used, and it was performed according to JIS K5400. When the pencil hardness was HB or higher, it was judged as [◯], and when HB was not satisfied, it was judged as [×].

(2) Glossiness The glossiness of the plate was measured using the same plate-shaped test piece as for surface hardness measurement. The measurement was performed at a measurement angle of 60 degrees using a gloss meter (GROSS METER VG2000) manufactured by Nippon Denshoku Industries Co., Ltd.

(3) Combustibility Using an injection molding machine J50 manufactured by Nippon Steel Works, set the temperature of the mold immediately before filling to 260 ° C. and the temperature described in Tables 2 to 3, and the mold set temperature of 60 ° C. Injection molding was performed to obtain a molded article having a length of 127 mm, a width of 12.7 mm, and a wall thickness of 1.5 mm as a test piece.
About the obtained test piece, the vertical combustion test based on UL94 was done, the flammability result was V-0, V-1, and V-2 from the favorable order, and the thing outside a specification was classified as NG.

(4) Charpy impact properties Using an injection molding machine SG75 manufactured by Sumitomo Heavy Industries, Ltd., a set temperature of 270 ° C., the mold surface immediately before filling is set to the temperature shown in Tables 2-3, and the mold set temperature is 60 ° C. Below, a test piece having a thickness of 4 mm, a length of 80 mm, a width of 10 mm and no notch was injection molded.
The Charpy impact property was evaluated according to ISO 179-2.

(5) Bending Weld Strength Using Nippon Steel Corporation's injection molding machine J50, the set temperature is 270 ° C., the mold surface immediately before filling is set to the temperature shown in Tables 2-3, and the mold set temperature is 60 ° C. A test piece having a length of 127 mm, a width of 12.7 mm, and a thickness of 1.6 mm in which a weld portion was formed at the center was injection molded.
Weld strength was evaluated by using a universal testing machine 2 kN manufactured by Instron, applying a load to the weld at the center of the test piece at a test speed of 2 mm / min, and judging the evaluation result based on the bending strain when the test piece cracked. . Regarding the bending strain, 0 to 3% was set as “x”, 3.1% to 6% was set as “Δ”, and if it was 6.1% or more, it was set as “◯”.

(6) Drop weight impact strength Using a molded product similar to the surface hardness evaluation, measurement was performed in accordance with ASTM-D2794.
The measurement is performed with a DuPont impact tester manufactured by Toyo Seiki Co., Ltd., with a weight of 1 kg. If the weight is dropped from a height of 1.5 m and the molded product does not break, [◎] is given. [○] when it enters but does not break, and [×] when small pieces are scattered and cracked.

(7) Continuous formability As an evaluation of continuous formability, from the viewpoint of product production efficiency, it is necessary to specify what was formed when molding a test piece for surface hardness measurement. The molding cycle time (including injection pressure holding time, cooling time, and intermediate time) was within 1 minute [O], and when it was 1 minute or longer, it was marked [X].

(8) Deflection temperature under load Using Sumitomo Heavy Industries, Ltd. injection molding machine SG75, the set temperature is 270 ° C., the mold surface just before filling is set to the temperature described in Tables 2-3, and the mold set temperature is 60 ° C. Below, a test piece having a thickness of 4 mm, a length of 80 mm and a width of 10 mm was injection molded.
As an evaluation of the deflection temperature under load, measurement was performed in accordance with ISO75.
The evaluation results are shown in Table 2 (Examples) and Table 3 (Comparative Examples).

(Examples 10-23, Comparative Examples 7-12)
In the same manner as described above, an injection-molded article was produced using a composition containing an elastomer.
The results are shown in Tables 4 and 5.

  According to the method for producing a polycarbonate resin molded article of the present invention, a polycarbonate resin molded article having excellent surface gloss and scratch resistance and excellent mechanical strength and flame retardancy can be produced with high production efficiency. Electrical and electronic equipment, OA equipment, information terminal equipment, lighting equipment parts, machine parts, home appliances, vehicle parts, building parts, various containers, leisure goods and miscellaneous parts, especially electrical and electronic equipment, OA equipment, information terminal equipment It is suitable for use in parts of home appliances and the like, and in particular, it is suitable for use in housings of display screens such as personal computers and liquid crystal / plasma televisions, and has high industrial applicability.

Claims (10)

  5 to 40% by mass of glass beads and a polycarbonate resin composition containing a flame retardant selected from a condensed phosphate ester compound or an organic sulfonic acid metal salt, and the mold surface immediately before filling the molten resin with the glass of the resin composition A method for producing a polycarbonate resin molded article, characterized by heating to a temperature above the transition temperature and injection molding.   The method for producing a polycarbonate resin molded article according to claim 1, wherein the flame retardant is a condensed phosphate ester compound, and the content thereof is 5 to 20% by mass in the total composition.   The method for producing a polycarbonate resin molded article according to claim 1, wherein the flame retardant is an organic sulfonic acid metal salt, and the content thereof is 0.01 to 1% by mass in the total composition.   The method for producing a polycarbonate resin molded article according to any one of claims 1 to 3, wherein the composition further contains an elastomer.   5. The method for producing a polycarbonate resin molded article according to claim 4, wherein the elastomer is a core / shell type graft copolymer.   Content of an elastomer is 0.1-10 mass% in all the compositions, The manufacturing method of the polycarbonate resin molded product of any one of Claims 4-5 characterized by the above-mentioned.   2. The method for producing a polycarbonate resin molded article according to claim 1, wherein the glass beads (B) have an average particle size of 10 to 30 μm.   2. The method for producing a polycarbonate resin molded article according to claim 1, wherein the mold surface is heated by high frequency electromagnetic induction heating.   The polycarbonate resin molded product manufactured by the method of any one of Claims 1-8.   The polycarbonate resin molded product according to claim 9, wherein the molded product is a casing.