CN102875988A - Excellent-appearance molded product consisting of aromatic polycarbonate resin composition - Google Patents

Abstract

The present invention relates to a molded article composed of an aromatic polycarbonate resin composition having excellent appearance, characterized in that, in the aromatic polycarbonate resin composition, relative to (A) aromatic polycarbonate resin ( Component A), (B) graft copolymer (component B) obtained by graft-copolymerizing vinyl cyanide monomer and aromatic vinyl monomer with rubber polymer, including 0.1 to 20 parts by weight in total of 100 parts by weight (C) Polymerization obtained by copolymerizing an alkyl (meth)acrylate monomer or a mixture of an alkyl (meth)acrylate monomer and a monomer copolymerizable therewith by emulsion polymerization in the presence of a rubber component (component C), the sodium contained in the polymer is 0-50ppm, the phosphorus is 100-1000ppm, the mold temperature during molding and the glass transition temperature (Tg) of the resin composition satisfy the conditions of formula 1: Tg-30 ≤Mold temperature (°C)≤Tg+50...(1).

Description

Molded article made of aromatic polycarbonate resin composition with excellent appearance

technical field

The present invention relates to an improved appearance obtained by injection molding a resin composition composed of an aromatic polycarbonate resin, a graft copolymer, and a rubber-containing acrylic polymer having a specific residual metal amount using a high-temperature mold A molded product, the graft copolymer is composed of rubber polymer, vinyl cyanide monomer and aromatic vinyl monomer. In more detail, the present invention relates to the improvement of the bad appearance of white mist generated during injection molding with a high-temperature mold by compounding a rubber-containing acrylic polymer having a specific amount of residual metal, and the resistance to heat and humidity, heat, etc. A molded product that is excellent in stability and mechanical properties including surface impact strength.

Background technique

Polymer alloys of aromatic polycarbonate resins and graft copolymers represented by ABS resins are widely used in the fields of office automation equipment (OA equipment), electronic and electrical equipment, and automotive field, etc. In recent years, among the measures aimed at reducing the environmental load, researches have been made on the non-painting of plastic molded products, focusing on applications such as office automation equipment, home appliances, and automobiles. Among them, in products that are used by individuals such as flat panel displays and notebook computers, in order to improve the designability thereof, high-gloss, high-quality casing materials with no weld seams are also required.

It is known that in order to obtain molded products with high gloss and no weld seams and high appearance quality without painting, a high-temperature mold molding method of molding at a high mold temperature has been developed, and it is suitable for polycarbonate-based resins. For example, it is proposed to control the temperature of the mold by using a heating medium and a cooling medium to perform high-temperature mold molding of glass fiber-reinforced polycarbonate resin, polycarbonate resin and ABS resin alloy materials, and obtain a mold with no filler floating out and no weld seams. molded products with high-quality appearance (Patent Document 1, Patent Document 2). In addition, it is disclosed in other documents that the alloy material of polycarbonate resin and ABS resin reinforced by fillers is subjected to high-temperature mold molding with a heat insulating layer on the mold surface to obtain a high-gloss, weld-free molded product (Patent Document 3 ). However, although the above-mentioned molding method can obtain a high-gloss, non-welded appearance for most compositions, if the alloy material of polycarbonate resin and ABS resin is mixed with rubber containing rubber for improving impact strength The composition of the acrylic polymer, there is a problem that white fog-like defects are partially generated on the surface of the molded article, and a molded article with a high-quality appearance cannot be obtained.

On the other hand, as for the materials of components such as flat panel displays and notebook PCs, which are promoted to be non-painted, excellent moisture and heat resistance is further required due to the lack of coating.

Regarding the improvement of the heat-and-moisture resistance of the alloy material of the polycarbonate resin and the ABS resin, a method of using ABS with a small amount of a specific alkali metal (Patent Document 4), and a method of adding a rubber component with a small amount of a specific alkali metal are mentioned. (Patent Document 5), however, there is a problem that if high-temperature mold molding is performed, no matter what composition is used, white fog-like defects are partially generated on the surface of the molded product, and a molded product with a high-quality appearance cannot be obtained.

As described above, none of the methods discloses the high gloss, no weld seam, and no white haze defect of the resin composition composed of graft copolymers such as aromatic polycarbonate resin and ABS resin. Effective recognition of molded products with excellent appearance and heat and humidity resistance.

prior art literature

patent documents

Patent Document 1: Japanese Patent Application Laid-Open No. 10-100216

Patent Document 2: Japanese Patent Laid-Open No. 2001-150506

Patent Document 3: Japanese Patent Laid-Open No. 2002-275275

Patent Document 4: Japanese Patent Laid-Open No. 2000-19186

Patent Document 5: Japanese Patent Laid-Open No. 2003-171548

Contents of the invention

In view of the above circumstances, the object of the present invention is to provide an aromatic compound with high gloss and high-quality appearance that maintains the original mechanical properties such as heat and humidity resistance, thermal stability, and surface impact strength, and has no white mist appearance. A molded article composed of a polycarbonate resin composition.

The inventors of the present invention have made intensive studies in order to achieve the above object, and as a result, have found that the object can be achieved by using an aromatic polycarbonate resin composition blended with a rubber-containing acrylic polymer having a specific amount of residual metal. Further intensive studies, The present invention has been accomplished.

According to the present invention, the above-mentioned problems can be achieved by a finished product obtained by injection molding the following aromatic polycarbonate resin composition under molding conditions satisfying the conditions of the following formula (1): In the carbonate resin composition, 10 to 95 parts by weight of (A) aromatic polycarbonate resin (component A), (B) grafting of vinyl cyanide monomer and aromatic vinyl monomer to rubber polymer A total of 100 parts by weight of 5 to 90 parts by weight of the graft copolymer (component B) obtained by copolymerization contains 0.1 to 20 parts by weight of (C) a rubber-modified polymer (component C), and the rubber-modified polymer ( C component) is obtained by copolymerizing an alkyl (meth)acrylate monomer or a mixture of an alkyl (meth)acrylate monomer and a monomer that can be copolymerized with it by emulsion polymerization in the presence of a rubber component , and the sodium content is 0-50ppm, and the phosphorus content is 100-1000ppm.

Tg-30≤mold temperature (℃)≤Tg+50...(1)

(In the formula, Tg is the glass transition temperature of the aromatic polycarbonate resin composition.)

Among them, the rubber component of component C is preferably butadiene.

The molded article is obtained by making the resin composition contain 3 to 30 parts by weight of (D) an organophosphorus-based flame retardant (component D) and 0.01 to 2 parts by weight of (E) A resin composition containing a fluorine anti-dripping agent (component E) to realize a molded article excellent in flame retardancy.

Furthermore, it is preferable that the said resin composition is a resin composition containing 0.1-50 weight part of (F) inorganic fillers (F component) with respect to the total 100 weight part of A component and B component. As the inorganic filler, fillers such as talc, wollastonite, mica, glass fiber, carbon fiber, and glass flake are preferably used. Among them, silicate minerals are particularly preferable, and talc, wollastonite, and mica are particularly preferable. Talc, wollastonite, and mica can realize a resin composition having good rigidity while suppressing a decrease in impact strength.

Hereinafter, the details of the present invention will be further described.

(Component A: aromatic polycarbonate resin)

The aromatic polycarbonate resin (component A) of the present invention is obtained by reacting a dihydric phenol with 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.

Representative examples of dihydric phenols used here include hydroquinone, resorcinol, 4,4'-biphenol, 1,1-bis(4-hydroxyphenyl)ethane, 2, 2-bis(4-hydroxyphenyl)propane (commonly known as bisphenol A), 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane Alkane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis(4-hydroxyphenyl)pentane, 4,4'-(p-phenylene diisopropylidene)biphenol, 4, 4'-(m-phenylenediisopropylidene)biphenol, 1,1-bis(4-hydroxyphenyl)-4-isopropylcyclohexane, bis(4-hydroxyphenyl)ether, bis (4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)ketone, bis(4-hydroxyphenyl)ester , bis(4-hydroxy-3-methylphenyl)sulfide, 9,9-bis(4-hydroxyphenyl)fluorene and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, etc. . Preferable dihydric phenols are bis(4-hydroxyphenyl)alkanes. Among them, bisphenol A (hereinafter sometimes abbreviated as "BPA") is particularly preferable and widely used because of its excellent toughness.

In the present invention, in addition to the bisphenol A-based polycarbonate which is a general-purpose polycarbonate, special polycarbonates produced from other dihydric phenols can also be used as the A component.

For example, 4,4'-(m-phenylene diisopropylidene)biphenol (hereinafter sometimes abbreviated as "BPM"), 1,1-bis(4-hydroxy Phenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (hereinafter sometimes referred to as "Bis-TMC"), 9,9-bis( Polycarbonates (homopolymers or copolymers) of 4-hydroxyphenyl)fluorene and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene (hereinafter sometimes abbreviated as "BCF") are suitable for Applications that require particularly severe dimensional changes and shape stability due to water absorption. The usage-amount of the dihydric phenol other than said BPA is preferably 5 mol% or more of the whole dihydric phenol component which comprises this polycarbonate, Especially preferably, it is 10 mol% or more.

In particular, when high rigidity and better hydrolysis resistance are required, a copolycarbonate in which the A component constituting the resin composition is the following (1) to (3) is particularly preferable.

(1) In 100 mol% of the dihydric phenol component constituting the polycarbonate, BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, further preferably 45 to 65 mol%), and BCF is 20 to 80 mol%. 80 mol% (more preferably 25 to 60 mol%, still more preferably 35 to 55 mol%) copolycarbonate.

(2) In 100 mol% of dihydric phenol components constituting the polycarbonate, BPA is 10 to 95 mol% (more preferably 50 to 90 mol%, further preferably 60 to 85 mol%), and BCF is 5 to 85 mol%. 90 mol% (more preferably 10 to 50 mol%, and still more preferably 15 to 40 mol%) copolycarbonate.

(3) In 100 mol% of dihydric phenol components constituting the polycarbonate, BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, and still more preferably 45 to 65 mol%), and Bis-TMC is 20-80 mol% (more preferably 25-60 mol%, still more preferably 35-55 mol%) copolycarbonate.

These special polycarbonates may be used alone or in combination of two or more as appropriate. In addition, they can also be mixed with general-purpose bisphenol A polycarbonate.

The production methods and characteristics of these special polycarbonates are described in detail in, for example, Japanese Patent Application Laid-Open No. 6-172508, Japanese Patent Laid-Open No. 8-27370, Japanese Patent Laid-Open No. 2001-55435 and Japanese Patent Laid-Open No. 2002- Publication No. 117580 et al.

In addition, among the above-mentioned various polycarbonates, the polycarbonate whose water absorption rate and Tg (glass transition temperature) are in the following ranges by adjusting the copolymerization composition, etc., has good hydrolysis resistance of the polymer itself, and has a low temperature after molding. It is also particularly excellent in bendability, so it is particularly suitable for fields requiring shape stability.

(i) a polycarbonate having a water absorption of 0.05 to 0.15%, preferably 0.06 to 0.13%, and a Tg of 120 to 180°C, or

(ii) Polycarbonate having a Tg of 160 to 250°C, preferably 170 to 230°C, and a water absorption of 0.10 to 0.30%, preferably 0.13 to 0.30%, more preferably 0.14 to 0.27%.

Here, the water absorption of the polycarbonate was measured as a value of the moisture content after immersion in water at 23° C. for 24 hours using a disk-shaped test piece with a diameter of 45 mm and a thickness of 3.0 mm in accordance with ISO62-1980. In addition, Tg (glass transition temperature) is the value calculated|required by the differential scanning calorimeter (DSC) measurement based on JISK7121.

As the carbonate precursor, carbonyl halides, carbonic diesters, or haloformates are used, and specific examples include phosgene, diphenyl carbonate, or dihaloformates of dihydric phenols.

When producing the polycarbonate resin by the interfacial polymerization method of the dihydric phenol and the carbonate precursor, a catalyst, a terminator, an antioxidant for preventing oxidation of the dihydric phenol, etc. may be used as necessary. In addition, the polycarbonate resin of the present invention includes a branched polycarbonate resin obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound, and a branched polycarbonate resin obtained by copolymerizing an aromatic or aliphatic (including alicyclic) difunctional carboxylic acid. Polyester carbonate resin formed by copolymerization of difunctional alcohol (including alicyclic) and polyester carbonate resin obtained by copolymerization of difunctional carboxylic acid and difunctional alcohol. In addition, a mixture obtained by mixing two or more types of polycarbonates obtained may be used.

The branched polycarbonate resin increases the melt tension of the resin composition of the present invention, and based on this characteristic, the molding processability in extrusion molding, foam molding, and blow molding can be improved. As a result, molded articles formed by these molding methods with better dimensional accuracy can be obtained.

As the trifunctional or higher polyfunctional aromatic compound used in the branched polycarbonate resin, 4,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)heptene is preferably exemplified -2,2,4,6-trimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1, 1-tris(4-hydroxyphenyl)ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane, 2,6-bis(2-hydroxy-5- Methylbenzyl)-4-methylphenol, and 4-[4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene]-α,α-dimethylbenzylphenol and other triphenols . In addition, examples of polyfunctional aromatic compounds include phloroglucinol, phloroglucol, tetrakis(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1,4-bis( 4,4-dihydroxytriphenylmethyl)benzene, trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, acid chlorides of these acids, and the like. Among them, 1,1,1-tris(4-hydroxyphenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferred, and 1,1 , 1-tris(4-hydroxyphenyl)ethane.

The structural unit derived from the polyfunctional aromatic compound in the branched polycarbonate resin is preferably 0.03 in a total of 100 mol% of the structural unit derived from the dihydric phenol and the structural unit derived from the polyfunctional aromatic compound. ~1 mol%, more preferably 0.07-0.7 mol%, especially preferably 0.1-0.4 mol%.

In addition, this branched structural unit can be derived not only from a polyfunctional aromatic compound, but also can be derived without using a polyfunctional aromatic compound as a side reaction in a melt transesterification reaction. It should be noted that the ratio of the branched structure can be calculated by ¹ H-NMR measurement.

On the other hand, the aliphatic difunctional carboxylic acid is preferably α,ω-dicarboxylic acid, and specific examples thereof include decanedioic acid, dodecanedioic acid, tetradecanedioic acid, Linear saturated aliphatic dicarboxylic acids such as octadecanedioic acid and eicosanedioic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. As the difunctional alcohol, an alicyclic diol is preferable, for example, cyclohexanedimethanol, cyclohexanediol, tricyclodecanedimethanol, etc. can be illustrated. Furthermore, a polycarbonate polyorganosiloxane copolymer copolymerized with a polyorganosiloxane unit can also be used.

Component A may be a component formed by mixing two or more kinds of polycarbonates having different dihydric phenol components, polycarbonates containing branched components, various polyester carbonates, polycarbonate polyorganosiloxane copolymers, and the like. Furthermore, it is also possible to use a component obtained by mixing two or more types of polycarbonates having different production methods and polycarbonates having different terminators.

等叔胺、季铵化合物、季

化合物等催化剂。通常优选反应温度为0～40℃、反应时间为10分钟～5小时，反应中的pH优选保持在9以上。The reaction by the interfacial polycondensation method is usually the reaction of dihydric phenol and phosgene, which is reacted in the presence of an acid binder and an organic solvent. As the acid binder, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide or amine compounds such as pyridine are used. As the organic solvent, halogenated hydrocarbons such as dichloromethane and chlorobenzene are used. In addition, in order to promote the reaction, triethylamine, tetra-n-butylammonium bromide, tetra-n-butyl bromide can also be used

Tertiary amines, quaternary ammonium compounds, quaternary

compounds and other catalysts. Usually, the reaction temperature is preferably 0 to 40° C., the reaction time is 10 minutes to 5 hours, and the pH during the reaction is preferably maintained at 9 or higher.

In addition, in this polymerization reaction, a terminator is generally used. As the terminator, monofunctional phenols can be used. As a specific example of monofunctional phenols, monofunctional phenols are preferably used. As the monofunctional phenols, phenol, p-tert-butylphenol, p-cumylphenol, etc. are preferable, and in addition, decylphenol, dodecylphenol, tetradecylphenol, hexadecane phenol, octadecylphenol, eicosylphenol, behenylphenol, triacylphenol, etc. These terminators may be used alone or in combination of two or more.

The reaction utilizing the melt transesterification method is a transesterification reaction of a dihydric phenol and a carbonate, and is generally carried out by the following method: while heating a dihydric phenol and a carbonate in the presence of an inert gas, they are mixed, and the resulting alcohol or Phenol distills off. The reaction temperature is generally in the range of 120 to 350°C, although it varies depending on the boiling point of the alcohol or phenol to be produced. In the later stage of the reaction, the reaction system is decompressed to about 1.33×103～13.3Pa, so that the generated alcohol or phenol can be easily distilled off. The reaction time is usually about 1 to 4 hours.

Examples of carbonates include esters of optionally substituted aryl groups having 6 to 10 carbon atoms, aralkyl groups, or alkyl groups having 1 to 4 carbon atoms, among which diphenyl carbonate is preferred.

Polymerization catalysts can be used in the reaction, for example, alkali metal compounds such as sodium hydroxide, potassium hydroxide, dihydric phenol sodium salt, potassium salt; alkaline earth metal compounds such as calcium hydroxide, barium hydroxide, magnesium hydroxide; Nitrogen-containing basic compounds such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylamine, triethylamine; and other catalysts. Furthermore, alkali (earth) metal alkoxides, alkali (earth) metal organic acid salts, boron compounds, germanium compounds, antimony compounds, titanium compounds, zirconium compounds, etc., which are usually used for esterification Catalyst for reaction, transesterification reaction. These catalysts may be used alone or in combination of two or more. The amount of the polymerization catalyst used is usually in the range of 1×10 ^-9 to 1×10 ^-5 equivalents, more preferably in the range of 1×10 ^-8 to 5×10 ^-6 equivalents, based on 1 mol of the raw material dihydric phenol.

盐等

盐、十二烷基苄基硫酸四乙基铵等铵盐。In the melt transesterification method, in order to reduce the phenol end groups in the obtained polymer, 2-chlorophenyl phenyl carbonate, 2-methoxycarbonylphenyl phenyl carbonate, 2-ethoxycarbonylphenyl carbonate and other compounds. Furthermore, in the melt transesterification process, it is preferable to use a deactivator which neutralizes the activity of the catalyst. The deactivator is preferably used in a ratio of 0.5 to 50 moles relative to 1 mole of the remaining catalyst. The usage ratio is preferably 0.01 to 500 ppm, more preferably 0.01 to 300 ppm, and still more preferably 0.01 to 100 ppm based on the polymerized aromatic polycarbonate. As a preferred deactivator, tetrabutyl dodecylbenzenesulfonate can be mentioned

salt etc.

Salt, ammonium salts such as tetraethylammonium dodecylbenzylsulfate.

As the aromatic polycarbonate of the component A of the present invention, not only fresh raw materials but also polycarbonate resins regenerated from used products, so-called aromatic polycarbonates obtained through material regeneration, can be used. Examples of used products include various glazing materials such as soundproof walls, glass windows, light-transmitting roof materials, and automotive sunshade roofs, windshields, and automotive headlamp lenses. Transparent parts such as water bottles, containers such as water bottles, and optical recording media. These products do not contain a large amount of additives, other resins, etc., and it is easy to obtain the target quality stably. In particular, automotive headlamp lenses, optical recording media, and the like can be cited as preferred embodiments because they satisfy the above-mentioned more preferable conditions for the viscosity average molecular weight. It should be noted that the aforementioned fresh raw materials refer to raw materials that have not been used in the market after their manufacture.

The viscosity average molecular weight of the aromatic polycarbonate is preferably 10,000 to 50,000, more preferably 14,000 to 30,000, still more preferably 18,000 to 25,000. In the range of 18,000 to 25,000, the coexistence of good impact resistance and fluidity is particularly excellent. Most preferably, it is 21,000 to 24,000. In addition, what is necessary is just to satisfy this viscosity average molecular weight as a whole as A component, and the A component which satisfies this range by the mixture of 2 or more types with which molecular weight differs is contained.

The viscosity average molecular weight of the present invention is obtained as follows: First, using an Ostwald viscometer, obtain the solution obtained by dissolving 0.7g of aromatic polycarbonate in 100ml of dichloromethane at 20°C and calculate according to the following formula: specific viscosity,

Specific viscosity (η _sp )=(tt ₀ )/t ₀

[ _t0 is the falling seconds of dichloromethane, and t is the falling seconds of the sample solution]

The viscosity average molecular weight M was obtained by substituting the obtained specific viscosity into the following formula.

η _sp /c=[η]+0.45×[η] ² c (where [η] is intrinsic viscosity)

[η]=1.23×10 ^-4 M ^0.83

c=0.7

(Component B: graft copolymer)

The graft copolymer as the B component in the present invention is a graft copolymer formed by graft-copolymerizing a vinyl cyanide compound and an aromatic vinyl compound with a rubber polymer, and may contain the graft copolymer, vinyl Copolymer of cyanide compounds and aromatic vinyl compounds.

In addition, the copolymer of the vinyl cyanide compound and the aromatic vinyl compound may also be a copolymer that is by-produced when the vinyl cyanide compound and the aromatic vinyl compound are graft-copolymerized with the rubber polymer, or may be blended with A copolymer of a vinyl compound copolymer obtained by separately copolymerizing an aromatic vinyl compound and a vinyl cyanide compound.

The rubber polymer of the present invention can be enumerated polybutadiene, diene copolymer (for example, random copolymer and block copolymer of styrene.butadiene, acrylonitrile.butadiene copolymer, and Copolymers of alkyl (meth)acrylate and butadiene, etc.), polyisoprene, copolymers of ethylene and α-olefins (for example, random copolymers and block copolymers of ethylene-propylene, ethylene Random copolymers and block copolymers of butene, etc.), copolymers of ethylene and unsaturated carboxylic acid esters (such as ethylene-methacrylate copolymers, and ethylene-butyl acrylate copolymers, etc.), ethylene and Copolymers of aliphatic vinyl compounds (such as ethylene-vinyl acetate copolymers, etc.), terpolymers of ethylene, propylene and non-conjugated dienes (such as ethylene-propylene-hexadiene copolymers, etc.) ), acrylic rubber (for example, polybutyl acrylate, poly(2-ethylhexyl acrylate), and copolymers of butyl acrylate and 2-ethylhexyl acrylate, etc.), and silicone rubber (for example, poly Organosiloxane rubber, an IPN type rubber composed of a polyorganosiloxane rubber component and a polyalkyl (meth)acrylate rubber component, that is, a rubber having a structure in which two rubber components are intertwined in an inseparable manner, And IPN type rubber composed of polyorganosiloxane rubber component and polyisobutylene rubber component, etc.). Among them, polybutadiene, diene copolymers, polyisoprene, acrylic resins, terpolymers of ethylene, propylene, and non-conjugated dienes are more preferable, and among them, particularly preferable Polybutadiene, diene copolymer.

The preferred range of the weight average particle size of the rubber particles of the rubber polymer is preferably 0.20 to 2.0 μm, more preferably 0.25 to 1.5 μm, particularly preferably 0.28 to 1.3 μm. If the weight-average particle diameter of the rubber particles is smaller than 0.2 μm, the impact improvement effect by adding the graft polymer will decrease, which is not preferable. Moreover, when it exceeds 2.0 micrometers, since the dispersion|distribution state with polycarbonate resin will be inferior and impact fall etc. will occur, it is unpreferable.

The weight-average particle diameter of the rubber particles is a value measured with a transmission electron microscope. Specifically, a drop of latex-like rubbery polymer is dropped on a transmission electron microscope measuring net, and dyed with vapor of osmium tetroxide or ruthenium tetroxide. Next, a sample of the dyed rubber-like polymer was photographed with a transmission electron microscope (manufactured by FEI, TECNAI G2, accelerating voltage 120kv), and the weight average was calculated from 200 rubber particles in the photographed image using image processing software (Nexus NewQube). particle size.

Examples of the vinyl cyanide monomer in the present invention include acrylonitrile, methacrylonitrile, and the like, and acrylonitrile is particularly preferable.

Examples of the aromatic vinyl monomers of the present invention include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, vinylxylene, ethylstyrene, dimethyl Styrene, p-tert-butylstyrene, vinylnaphthalene, methoxystyrene, monobromostyrene, dibromostyrene, fluorostyrene, tribromostyrene, etc., particularly preferably styrene.

The copolymer of vinyl cyanide compound of the present invention and aromatic vinyl compound preferably uses the copolymer of acrylonitrile and styrene, and the weight-average molecular weight of this copolymer is by GPC (gelpermeation chromatography, gel permeation chromatography) method with standard polymer The value measured in terms of styrene is preferably in the range of 3.0×10 ⁴ to 2.0×10 ⁵ , more preferably in the range of 6.0×10 ⁴ to 1.4×10 ⁵ , and still more preferably in the range of 9.0×10 ⁴ to 1.2×10 ⁵ range.

The preferred content of the rubber polymer in the graft copolymer of the present invention is in the range of 1 to 70% by weight, more preferably 5 to 30% by weight, particularly preferably 10 to 25% by weight. If the content exceeds 70% by weight, the fluidity improving effect becomes insufficient, which is not preferable. In addition, when the amount of the rubber is less than 1% by weight, the impact improving effect becomes insufficient, which is not preferable.

In addition, the ratio of the vinyl cyanide compound and the aromatic vinyl compound grafted onto the rubber polymer component (the ratio of the weight of the grafted component to the weight of the rubber polymer), that is, the grafting rate (% by weight), is preferably 20 to 200%, more preferably 20 to 80%.

The production method of the graft copolymer of the present invention is not particularly specified, and graft polymers produced by known polymerization methods such as emulsion polymerization, bulk polymerization, and solution polymerization can be preferably used.

Specific examples of the graft copolymer of the present invention include ABS resin, AES resin, ASA resin, and the like, all of which can be easily obtained. Among them, ABS resin is more preferable.

ABS resin has excellent molding processability for thin-walled molded products, and also has good impact resistance. In particular, combination with polycarbonate resin exhibits preferable characteristics.

(Component C: rubber-modified polymer)

The rubber-modified polymer as the C component in the present invention is an alkyl (meth)acrylate monomer, or an alkyl (meth)acrylate monomer and a copolymerizable polymer in the presence of a rubber component. The mixture of monomers is copolymerized by emulsion polymerization, and the sodium content is 0-50ppm, and the phosphorus content is 100-1000ppm.

The rubber component of the present invention is a polymer having rubber elasticity, and examples of the rubber component include polybutadiene, polyisoprene, and diene-based copolymers (for example, styrene-butadiene-free Regular copolymers and block copolymers, acrylonitrile-butadiene copolymers, and acrylic-butadiene rubbers (copolymers of alkyl acrylates or methacrylates and butadiene), etc.), ethylene and Copolymers of α-olefins (for example, random copolymers and block copolymers of ethylene-propylene, random copolymers and block copolymers of ethylene-butylene, etc.), copolymers of ethylene and unsaturated carboxylic acid esters (such as ethylene-methacrylate copolymer, and ethylene-butyl acrylate copolymer, etc.), copolymers of ethylene and aliphatic vinyl ester (such as ethylene-vinyl acetate copolymer, etc.), ethylene and propylene and Terpolymers of non-conjugated dienes (for example, copolymers of ethylene-propylene-hexadiene, etc.), acrylic rubbers (for example, polybutyl acrylate, poly(2-ethylhexyl acrylate), and butyl acrylate ester and 2-ethylhexyl acrylate, etc.), and silicon-based rubber (for example, polyorganosiloxane rubber consisting of polyorganosiloxane rubber components and polyalkyl(meth)acrylate rubber components IPN-type rubber, that is, rubber with a structure in which two rubber components are intertwined in an inseparable manner, and IPN-type rubber composed of polyorganosiloxane rubber components and polyisobutylene components, etc.). Furthermore, examples of other rubber components include urethane rubber, amide rubber, phosphazene rubber, and fluorine-containing rubber. Among them, polybutadiene, polyisoprene, and diene-based copolymers are preferable, and polybutadiene is more preferable. The glass transition temperature of the rubber component is preferably 10°C or lower, more preferably -10°C or lower, even more preferably -30°C or lower.

The particle size of the rubber component of the present invention is preferably 0.10 to 0.50 μm, more preferably 0.15 to 0.40 μm, and still more preferably 0.15 to 0.35 μm in terms of weight average particle size. If the particle size of the diene rubber is less than 0.10 μm, the impact improving effect will not be seen, and if it exceeds 0.50 μm, it will cause poor dispersion and cause a decrease in appearance and impact strength, which is not preferable. The weight-average particle diameter of the rubber particles in the present invention is a value measured by the same method as the method for measuring the weight-average particle diameter of the rubber polymer of component B, and is calculated based on an image of rubber particles taken with a transmission electron microscope. value.

The ratio of the rubber component of the rubber-modified polymer in the present invention is preferably 40 to 90 parts by weight, more preferably 42 to 85 parts by weight, and even more preferably 45 to 80 parts by weight in component C. The amount of the monomer or monomer mixture is preferably in the following range: preferably 60-10 parts by weight, more preferably 58-15 parts by weight, further preferably 55-20 parts by weight. In addition, when a monomer mixture is used, it is preferable that the alkyl (meth)acrylate monomer as an essential component is at least 25% by weight or more, more preferably 40% by weight or more, in the total of the monomer mixture.

The monomer that can be copolymerized with the rubber component of the present invention is an alkyl (meth)acrylate monomer, or, an alkyl (meth)acrylate monomer and a monomer that can be copolymerized therewith, as (meth)acrylic acid Examples of the alkyl ester monomer include methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate, among which methyl methacrylate and butyl methacrylate are preferred. In addition, examples of monomers copolymerizable with the alkyl (meth)acrylate monomer include styrene, α-methylstyrene, p-methylstyrene, chlorostyrene, and dibromostyrene. , tribromostyrene and other aromatic vinyl monomers, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and other alkyl acrylates. Among them, aromatic vinyl monomers are preferred, and styrene is particularly preferred.

The above-mentioned vinyl monomers may be used alone or in combination of two or more.

Specific examples of the rubber-modified polymer in the present invention include MBS resin, MB resin, MABS resin, and MAS resin, all of which are readily available. Among them, MBS resin is more preferable.

The rubber-modified polymer used in the present invention is obtained by combining an alkyl (meth)acrylate monomer, or a mixture of an alkyl (meth)acrylate and other monomers copolymerized therewith, with the rubber component constituted above. Latex is obtained by one or more steps of graft polymerization.

It should be noted that the graft polymerization itself can be performed by adding the monomer or monomer mixture at one time, or the monomer or the monomer mixture can be added in two or more times, and the graft polymerization can be performed in multiple steps.

As a method of graft polymerization, a method of emulsion polymerization is used. When performing this graft copolymerization, as a polymerization initiator, persulfates such as potassium persulfate, ammonium persulfate, and sodium persulfate; tert-butyl hydroperoxide, cumene hydroperoxide, benzoyl peroxide, Organic peroxides such as lauroyl peroxide and diisopropylbenzene hydroperoxide; azo compounds such as azobisisobutyronitrile and azobisisovaleronitrile, etc. In addition, the above-mentioned oxidant compound can also be used as a redox system initiator in combination with sulfite, bisulfite, thiosulfate, metalloid salt, sodium formaldehyde sulfoxylate, dextrose, etc. .

The reaction temperature in graft copolymerization can be suitably selected in the range of 40-80 degreeC, for example according to the kind of the polymerization initiator used. In addition, at the time of emulsion polymerization, a known emulsifier can be appropriately used as an emulsifier for the latex of the rubber component.

The resulting graft copolymer is spray-dried (directly powdered) by adding or not adding appropriate antioxidants and additives as required to the reaction solution; or adding sulfuric acid, hydrochloric acid, phosphoric acid and other acids or chlorine to the reaction solution Calcium chloride, sodium chloride and other salts and other coagulants are used to coagulate, and then heat-treated to solidify. Thereafter, it is dehydrated, washed, and finally dried and powdered for use.

In addition, the rubber-modified polymer in the present invention has a sodium content of 0 to 50 ppm and a phosphorus content of 100 to 1000 ppm, preferably a sodium content of 1 to 45 ppm and a phosphorus content of 120 to 800 ppm, more preferably a sodium content of 3 to 40 ppm, The phosphorus content is 150-600ppm. If the sodium content is more than 50 ppm, it is not preferable because a white mist-like appearance defect will occur when injection molding is performed in a high-temperature mold. In addition, if the phosphorus content is 100 ppm or less, thermal stability is insufficient, and a white mist-like appearance defect occurs during injection molding with a high-temperature mold, which is not preferable. When phosphorus exceeds 1000 ppm, heat-and-moisture resistance falls, which is not preferable.

It should be noted that the sodium of the rubber-modified polymer in the present invention is an impurity during emulsion polymerization, which can be prepared by acidizing or salting out the latex of the rubber component after emulsion polymerization to make a slurry, and then using pentane, hexane The slurry is washed and removed with a paraffinic solvent such as , heptane or the like.

The sodium content was quantified as follows: 0.3 g of a sample was thermally decomposed with a mixed solution of sulfuric acid and nitric acid at 300° C. for 2 hours, and then made a test solution with ultrapure water to constant volume, and quantified by the ICP-AES method.

In addition, the phosphorus in the rubber-modified polymer in the present invention depends on the antioxidant added at the time of polymerization. The phosphorus content is measured by measuring with a fluorescent X-ray analyzer after solidifying a sample into a tablet form.

(Component D: organophosphorus flame retardant)

As the organophosphorus-based flame retardant of the present invention, an aryl phosphate compound is preferable. The phosphoric acid ester compound is effective in improving flame retardancy, and since the phosphoric acid ester compound has a plasticizing effect, it is advantageous in improving the molding processability of the resin composition of the present invention although the heat resistance is lowered. As the phosphoric acid ester compound, various phosphoric acid ester compounds conventionally known as flame retardants can be used, and more preferably, one or more phosphoric acid ester compounds represented by the following general formula (1) are used.

(wherein, X in the above formula represents a dihydric organic group derived from a dihydric phenol, R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ represent a monohydric organic group derived from a monohydric phenol, and n represents 0 to 5 integer.)

The phosphoric acid ester compound of above-mentioned formula (1) can be the mixture with the compound of different n number, and under the situation of this mixture, the scope of average n number is preferably 0.5～1.5, more preferably 0.8～1.2, more preferably 0.95～ 1.15, particularly preferably 1 to 1.14.

Preferable specific examples of dihydric phenols derived from the aforementioned X include hydroquinone, resorcinol, bis(4-hydroxydiphenyl)methane, bisphenol A, dihydroxybiphenyl, dihydroxynaphthalene, bisphenol (4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)ketone, and bis(4-hydroxyphenyl)sulfide, among which resorcinol, bisphenol A, and dihydroxybiphenyl are preferable.

Preferable specific examples of monohydric phenols derived from the aforementioned R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ include phenol, cresol, xylenol, isopropylphenol, butylphenol, and p-cumylphenol, wherein , preferably phenol and 2,6-dimethylphenol.

It should be noted that the monohydric phenol may be substituted with a halogen atom. Specific examples of the phosphate compound having a group derived from the monohydric phenol include tris(2,4,6-tribromophenyl) phosphate and phosphoric acid tris(2,4,6-tribromophenyl) Tris(2,4-dibromophenyl) ester, tris(4-bromophenyl) phosphate, etc.

On the other hand, as specific examples of phosphate ester compounds that are not substituted with halogen atoms, monophosphate ester compounds such as triphenyl phosphate and tris(2,6-xylyl) phosphate, and resorcinol bis( Bis(2,6-xylyl) phosphate)-based phosphate oligomers, 4,4-dihydroxydiphenyl bis(diphenyl phosphate)-based phosphate oligomers, and Bisphenol A bis(diphenyl phosphate)-based phosphate oligomer.

The amount of the organophosphorus-based flame retardant is preferably 3 to 30 parts by weight, more preferably 3 to 25 parts by weight, and still more preferably 5 to 20 parts by weight, based on 100 parts by weight of the total of components A and B. When the content is less than 3 parts by weight, the flame retardancy is insufficient, and when it is more than 30 parts by weight, the heat resistance is greatly reduced, which is not preferable.

In addition, this organophosphorus-based flame retardant can also be used in combination with other flame retardants such as organometallic salt-based flame retardants and silicon-based flame retardants. As a specific example of an organic metal salt-based flame retardant, potassium perfluorobutanesulfonate (manufactured by Dainippon Ink Chemical Industry Co., Ltd., MEGAFAC F-114P (trade name)) is preferred. As a specific example of a silicon-based flame retardant, An organosiloxane-based flame retardant (manufactured by Shin-Etsu Chemical Co., Ltd., X-40-2600J (trade name)) containing a Si—H group, a methyl group, and a phenyl group is preferable.

Based on 100 parts by weight of the total of components A and B, the compounding amount of the organometallic salt-based flame retardant and the silicon-based flame retardant is preferably 0.005 to 1 part by weight, more preferably 0.01 to 0.7 parts by weight, and even more preferably 0.02 to 0.5 parts by weight.

(Component E: fluorine-containing anti-dripping agent)

The fluorine-containing anti-dripping agent used in the present invention is used to prevent molten dripping during combustion and to further improve flame retardancy, and it is preferable to use polytetrafluoroethylene having fibril-forming ability. Hereinafter, polytetrafluoroethylene may be simply referred to as PTFE. The molecular weight of PTFE having fibril-forming ability is extremely high, and PTFE tends to be bonded to each other by external action such as shear force to form a fibrous form. The molecular weight is 1 million to 10 million, more preferably 2 million to 9 million, in terms of the number average molecular weight obtained from the standard specific gravity. In addition to the solid form of this PTFE, PTFE in the form of an aqueous dispersion can also be used. In addition, in order to improve the dispersibility of the fibril-forming PTFE in the resin and obtain better flame retardancy and mechanical properties, a PTFE mixture in the form of being mixed with other resins may also be used.

Commercially available products of the PTFE having fibril-forming ability include, for example, Teflon (registered trademark) 6J from Dupont-Mitsui Fluorochemicals, Polyflon MPA FA500 and F-201L from DAIKIN Chemical Industry Co., Ltd., and the like. Representative examples of commercially available products of aqueous dispersions of PTFE include FLUON AD-1 and AD-936 manufactured by Asahi-ICI Fluoropolymers, and FLUON D-1 and D-2 manufactured by DAIKIN Chemical Industry Co., Ltd. Teflon (registered trademark) 30J manufactured by Mitsui Fluorochemicals Co., Ltd. and the like.

As the PTFE in the mixed form, the mixed form PTFE obtained by the following method can be used: (1) the aqueous dispersion of PTFE is mixed with the aqueous dispersion or solution of the organic polymer, and the co-precipitation is carried out to obtain the method of the co-agglomerated mixture (Japan Unexamined Patent No. 60-258263, Japanese Unexamined No. 63-154744 etc.); (2) the method of mixing the aqueous dispersion of PTFE with dried organic polymer particles (Japanese Unexamined Patent Publication 4- 272957 communique); (3) uniformly mixing the aqueous dispersion of PTFE and the organic polymer particle solution, and simultaneously removing the respective media from the mixture (Japanese Patent Laid-Open Publication No. 06-220210, Japanese Patent Application Laid-Open No. (methods described in Kokai Hei No. 08-188653, etc.); (4) a method of polymerizing monomers that form organic polymers in an aqueous dispersion of PTFE (the method described in Japanese Patent Laid-Open No. Hei 9-95583); and (5) After uniformly mixing the aqueous dispersion of PTFE and the organic polymer dispersion, the vinyl monomer is polymerized in the mixed dispersion, and then the method of obtaining the mixture (described in Japanese Patent Application Laid-Open No. 11-29679, etc. Methods). Commercially available products of these mixed forms of PTFE include "METABLEN A3800" from MITSUBISHI RAYON, and the like.

The proportion of PTFE in the mixed form is preferably 1 to 60% by weight, more preferably 5 to 55% by weight, based on 100% by weight of the PTFE mixture. When the ratio of PTFE is within this range, good dispersibility of PTFE can be achieved.

The content of the fluorine-containing anti-dripping agent is preferably 0.01 to 2 parts by weight, more preferably 0.05 to 1 part by weight, and even more preferably 0.1 to 0.6 parts by weight based on 100 parts by weight of the total of components A and B. When the content is less than 0.01 parts by weight, dripping occurs during combustion, and when it exceeds 2 parts by weight, the molding processability is lowered, which is not preferable.

(Component F: inorganic filler)

In the present invention, various inorganic fillers can be contained as the F component. Examples of the inorganic filler include talc, wollastonite, mica, clay, montmorillonite, smectite, kaolin, calcium carbonate, glass fiber, glass beads, glass balls, ground glass fiber, glass flakes, carbon fiber , carbon flakes, carbon beads, milled carbon fibers, metal flakes, metal fibers, metal-clad glass fibers, metal-clad carbon fibers, metal-clad glass flakes, silica, ceramic particles, ceramic fibers, ceramic balls, aramid particles, Various whiskers such as aramid fiber, polyarylate fiber, graphite, potassium titanate whisker, aluminum borate whisker, basic magnesium sulfate, etc. Among them, silicate-based fillers such as talc, wollastonite, mica, glass fiber, and milled glass fiber are preferably used. Among them, talc, wollastonite, and mica are particularly preferable. These reinforcement fillers may contain 1 type or may contain 2 or more types together.

As wollastonite preferable in the present invention, wollastonite having a number average fiber diameter of 0.5 to 5 μm is preferable. The number-average fiber diameter is obtained by measuring the fiber diameters of a total of 1000 randomly sampled fibers from images observed with electron micrographs and calculating the arithmetic mean value thereof. In addition, the aspect ratio L/D (L: number average fiber length, D: number average fiber diameter) is preferably 5 or more, more preferably 6 or more. It should be noted that the number-average fiber length can be calculated by observing wollastonite with an optical microscope or an electron microscope at a magnification at which the overall image of wollastonite can be observed almost completely, inputting the image into an image analysis device, and calculating the number average fiber length. average fiber length. As an image analysis apparatus, the PIAS-III system etc. which are manufactured by PIAS company are mentioned, for example. The wollastonite used in the present invention has a loss on ignition at 1000° C. of preferably 2% by weight or less, more preferably 1.5% by weight or less, even more preferably 1% by weight or less.

Furthermore, talc with an average particle diameter of 5 micrometers or less is mentioned as preferable talc in this invention. Further, talc having an average particle diameter of preferably 3 μm or less, particularly preferably 2 μm or less, is mentioned. As a lower limit, 0.05 micrometer is mentioned. Here, the average particle diameter of talc means D50 (median particle diameter of particle diameter distribution) measured by the X-ray transmission method which is a kind of liquid-phase sedimentation method. Specific examples of an apparatus for performing this measurement include Sedigraph 5100 manufactured by Micromeritics, Inc., and the like.

Talc is preferably used in a granulated form. As a granulation method, there exists a case where a binder is used, and the case where a binder is not used substantially. The case where no binder is used is more preferable. As the granulation method in the case of not using a binder, the method of evacuation compression (for example, the method of performing roll compression with a briquetting machine etc. while evacuating in a vacuum state), and rolling granulation, Agglomeration and granulation methods, etc.

Preferable mica in the present invention includes powdered mica having an average particle diameter of 1 to 80 μm. More preferable ones include mica having an average particle diameter of 2 to 50 μm. The average particle diameter is a value measured by a laser diffraction/scattering method. When the average particle size is 1 to 80 μm, it imparts a more favorable effect on the flame retardancy, and also satisfies the microdispersion conditions in the resin, so that heat and humidity resistance can also be maintained favorably. As the thickness of the mica, mica having a thickness of 0.01 to 1 μm actually measured by electron microscope observation can be used. The preferred thickness is 0.03 to 3 μm. The mica can be further surface-treated with a silane coupling agent, etc., and can also be granulated with an epoxy-based, polyurethane-based, acrylic-based adhesive, etc., to make it into a granular form.

When blending inorganic fillers, in order to suppress the breakage of the inorganic fillers and improve the thermal stability of the resin composition, the resin composition of the present invention may contain silane compounds such as alkylalkoxysilane or alkylhydrosilane, carboxyl, etc. ; Lubricants for surface coatings such as olefinic waxes containing acidic groups such as carboxylic acid anhydride groups and sulfonic acid groups.

The content of the (F) inorganic filler in the present invention is preferably 0.1 to 50 parts by weight, more preferably 0.5 to 40 parts by weight, and even more preferably 1 to 30 parts by weight, based on 100 parts by weight of the total of components A and B. . If the compounding amount is less than 0.1 parts by weight, there will be no reinforcing effect of the filler, and if it exceeds 50 parts by weight, the impact strength will be significantly lowered, which is not preferable.

(about content of each ingredient)

Regarding the ratio of the A component and the B component in the aromatic polycarbonate resin composition of the present invention, based on 100 parts by weight of the A component and the B component in total, the A component is 10 to 95 parts by weight, and the B component is 5 to 5 parts by weight. 90 parts by weight. Component A is preferably 50 to 95 parts by weight, more preferably 60 to 93 parts by weight, and component B is preferably 5 to 50 parts by weight, more preferably 7 to 40 parts by weight.

When component B is less than 5 parts by weight or component A exceeds 95 parts by weight, fluidity is insufficient, and when component B exceeds 90 parts by weight or component A is less than 10 parts by weight, heat resistance and impact strength are lowered, which is not preferable.

The content of the C component is 0.1 to 20 parts by weight, preferably 0.5 to 15 parts by weight, and more preferably 1 to 10 parts by weight, based on 100 parts by weight of the total of the A component and the B component. When the C component is less than 0.1 parts by weight, the impact improvement effect is insufficient, and when it exceeds 20 parts by weight, heat resistance, heat and humidity resistance, and flame retardancy will fall, which is not preferable.

(About other additives)

In the aromatic polycarbonate resin composition of the present invention, various stabilizers and colorants may be used in order to stabilize the molecular weight and color tone during molding processing. Examples of the stabilizer include phosphorus-based stabilizers, hindered phenol-based stabilizers, ultraviolet absorbers, light stabilizers, and the like.

(i) Phosphorus stabilizer

Phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, these esters, and tertiary phosphine etc. are illustrated as a phosphorus stabilizer.

Specific examples of phosphite compounds include triphenyl phosphite, tris(nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, tris(octadecyl) phosphite, ester, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, phosphorous acid Monooctyl diphenyl ester, tris (diethylphenyl) phosphite, tris (diisopropylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2 , 4-di-tert-butylphenyl) ester, tris(2,6-di-tert-butylphenyl) phosphite, pentaerythritol distearoyl diphosphite, bis(2,4-di-tert- Butylphenyl) pentaerythritol ester, diphosphite bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol ester, diphosphite bis(2,6-di-tert-butyl-4-ethyl Phenyl) pentaerythritol ester, bis[2,4-bis(1-methyl-1-phenylethyl) phenyl] pentaerythritol diphosphite, phenyl bisphenol A pentaerythritol diphosphite, bisphosphite (Nonylphenyl) pentaerythritol ester, dicyclohexyl pentaerythritol diphosphite, etc.

Furthermore, as another phosphite compound, the phosphite compound which has a ring structure which reacts with a dihydric phenol can also be used. For example, 2,2'-methylene bis(4,6-di-tert-butylphenyl)(2,4-di-tert-butylphenyl)phosphite, 2,2'-methylene phosphite Bis(4,6-di-tert-butylphenyl)(2-tert-butyl-4-methylphenyl)ester, and 2,2-methylene bis(4,6-di-tert-butyl phosphite Phenyl) octyl ester, etc.

Phosphate ester compounds include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl Mono-o-biphenyl ester, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, etc., preferably triphenyl phosphate and trimethyl phosphate.

Examples of phosphonite compounds include tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphinate, tetrakis(2,4-di-tert-diphosphonite) Butylphenyl)-4,3'-biphenylene ester, tetrakis(2,4-di-tert-butylphenyl)-3,3'-diphenylene diphosphinate, tetrakis diphosphonite ( 2,6-di-tert-butylphenyl)-4,4'-biphenylene ester, tetrakis(2,6-di-tert-butylphenyl)-4,3'-biphenylene diphosphinate, Tetrakis(2,6-di-tert-butylphenyl)-3,3'-biphenylene diphosphonite, bis(2,4-di-tert-butylphenyl)-4-phenylene- Phenyl ester, bis(2,4-di-tert-butylphenyl)-3-phenyl-phenyl phosphonite, bis(2,6-di-n-butylphenyl)-3-phenyl- Phenyl ester, bis(2,6-di-tert-butylphenyl)-4-phenyl-phenyl phosphonite, bis(2,6-di-tert-butylphenyl)-3-phenyl- Phenyl esters, etc., preferably tetrakis(di-tert-butylphenyl)-biphenylene diphosphonite, bis(di-tert-butylphenyl)-phenyl-phenyl phosphonite, more preferably tetrakis-diphosphonite (2,4-di-tert-butylphenyl)biphenylene ester, bis(2,4-di-tert-butylphenyl)-phenyl-phenyl phosphonite. It is preferable that this phosphonous acid compound can be used together with the said phosphite compound which has the aryl group which substituted two or more alkyl groups.

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

Examples of tertiary phosphine include triethylphosphine, tripropylphosphine, tributylphosphine, trioctylphosphine, tripentylphosphine, dimethylphenylphosphine, dibutylphenylphosphine, and diphenylmethylphosphine. Phosphine, diphenyloctylphosphine, triphenylphosphine, tri-p-tolylphosphine, trinaphthylphosphine, diphenylbenzylphosphine, and the like. A particularly preferred tertiary phosphine is triphenylphosphine.

The above-mentioned phosphorus-based stabilizers may be used not only alone but in combination of two or more. Among the above-mentioned phosphorus-based stabilizers, a phosphonite compound or a phosphite compound represented by the following general formula (2) is preferable.

(In formula (2), 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 as or different from each other.)

As the phosphonite compound, preferred diphosphonite tetrakis (2,4-di-tert-butylphenyl)-biphenylene ester, the stabilizer with this phosphonite as the main component is used as Sandostab P-EPQ ( (trademark, manufactured by Clariant Corporation) and Irgafos P-EPQ (trademark, manufactured by CIBA SPECIALTYCHEMICALS Corporation) are commercially available and can be used.

In addition, in the above formula (2), more preferable phosphite compounds are distearyl diphosphite pentaerythritol ester, diphosphite bis(2,4-di-tert-butylphenyl) pentaerythritol ester, diphosphite Bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol ester, and bis[2,4-bis(1-methyl-1-phenylethyl)phenyl]pentaerythritol diphosphite .

Pentaerythritol distearyl diphosphite is commercially available as ADK STAB PEP-8 (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.) and JPP681S (trademark, manufactured by Johoku Chemical Co., Ltd.), and any of them can be used. Bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite as ADK STAB PEP-24G (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.), Alkanox P-24 (trademark, manufactured by Great Lakes Corporation), Ultranox P 626 (trademark, manufactured by GE Specialty Chemicals), Doverphos S-9432 (trademark, manufactured by Dover Chemical), and Irgaofos 126 and 126FF (trademark, manufactured by CIBA SPECIALTY CHEMICALS) are commercially available and can be used. Bis(2,6-di-t-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. In addition, bis[2,4-bis(1-methyl-1-phenylethyl)phenyl]pentaerythritol diphosphite is used as ADK STAB PEP-45 (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.), and Doverphos S- 9228 (trademark, manufactured by Dover Chemical Co., Ltd.) is commercially available, and all of them can be used.

(ii) Hindered phenolic antioxidants

As the hindered phenolic compound, various compounds usually compounded in resins can be used. Examples of the hindered phenol compound include α-tocopherol, butylhydroxytoluene, sinapyl alcohol, vitamin E, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propane Ester, 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-hydroxybenzylphosphonic acid diethyl ester, 2,2'-methylenebis(4-methyl base-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-methylenebis(2,6-di-tert-butyl phenylphenol), 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-dimethylene-bis(6-α-methyl-benzyl-p-methyl phenol), 2,2'-ethylene-bis(4,6-di-tert-butylphenol), 2,2'-butylene-bis(4-methyl-6-tert-butylphenol), 4, 4'-butylenebis(3-methyl-6-tert-butylphenol), triethylene glycol-N-bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propane ester, 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], bis[2-tert-butyl-4-methyl-6- (3-tert-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 base-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-thiodiethylenebis-[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-hydroxyhydrogenated cinnamamide), 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)isocyanurate Ester, 1,3,5-tri-2[3(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]ethylisocyanurate, tetrakis[methylene -3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, triethylene glycol-N-bis-3-(3-tert-butyl-4-hydroxy-5-methanol phenyl)propionate, triethylene glycol-N-bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)acetate, 3,9-bis[2-[ 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)acetoxy]-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-4-hydroxy-5-methylbenzyl)benzene, and tris(3-tert-butyl-4-hydroxy-5-methylbenzyl)isocyanurate Esters etc.

Among the above-mentioned compounds, tetrakis[methylene-3-(3-tert-butyl-4-hydroxyl-5-methylphenyl)propionate]methane, octadecyl-3-( 3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and 3,9-bis[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate Acyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane. Particular preference is given to 3,9-bis[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2, 4,8,10-tetraoxaspiro[5,5]undecane. The said hindered phenolic antioxidant can be used individually or in combination of 2 or more types.

It is preferable to mix any one of a phosphorus-based stabilizer and a hindered phenol-based antioxidant. In particular, it is preferable to blend a phosphorus-based stabilizer, and it is more preferable to blend a triorganophosphate compound. Based on 100 parts by weight of the total of components A and B, the amounts of the phosphorus-based stabilizer and the hindered phenol-based antioxidant are preferably 0.005 to 1 part by weight, more preferably 0.01 to 0.3 parts by weight.

(iii) Release agent

In the aromatic polycarbonate resin composition of the present invention, it is preferable to further compound a mold release agent for the purpose of improving productivity during molding and reducing deformation of molded articles. As the release agent, a known release agent can be used. Examples include saturated fatty acid esters, unsaturated fatty acid esters, polyolefin waxes (polyethylene waxes, 1-alkene polymers, etc. Waxes modified with functional group-containing compounds such as acid modification can also be used), Silicon compounds, fluorine compounds (fluorine oil represented by polyfluoroalkyl ethers, etc.), paraffin wax, beeswax, etc.

Among these, fatty acid esters are mentioned as a preferable mold release agent. The fatty acid ester is an ester of an aliphatic alcohol and an aliphatic carboxylic acid. The aliphatic alcohol may be a monohydric alcohol or a dihydric or higher polyhydric alcohol. Moreover, the carbon number of this alcohol is the range of 3-32, More preferably, it is the range of 5-30. Examples of the monohydric alcohol include dodecanol, myristyl alcohol, cetyl alcohol, stearyl alcohol, eicosanol, tetracosanol, hexacosyl alcohol, and triacontanol. . Examples of the polyhydric alcohol include pentaerythritol, dipentaerythritol, tripentaerythritol, polyglycerol (triglycerol to hexaglycerol), di(trimethylol)propane, xylitol, sorbitol, and mannitol. Polyhydric alcohols are more preferred among the fatty acid esters of the present invention.

On the other hand, the aliphatic carboxylic acid is preferably an aliphatic carboxylic acid having 3 to 32 carbon atoms, particularly preferably having 10 to 22 carbon atoms. Examples of the aliphatic carboxylic acid include capric acid, undecanoic acid, dodecanoic acid, tridecanoic acid, myristic acid, pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecane Saturated aliphatic carboxylic acids such as octadecanoic acid (stearic acid), nonadecanoic acid, behenic acid, eicosanoic acid, and behenic acid, as well as palmitoleic acid, oleic acid, and linoleic acid , linolenic acid, eicosaenoic acid, eicosapentaenoic acid, and cetenoic acid and other unsaturated aliphatic carboxylic acids. Among them, the aliphatic carboxylic acid is preferably an aliphatic carboxylic acid having 14 to 20 carbon atoms. Among them, saturated aliphatic carboxylic acids are preferred. Stearic acid and palmitic acid are particularly preferred.

The above-mentioned aliphatic carboxylic acids such as stearic acid and palmitic acid are usually produced from natural oils and fats such as animal fats represented by tallow and lard, and vegetable fats represented by palm oil and sunflower oil. Therefore, these aliphatic carboxylic acids Carboxylic acids are generally mixtures containing other carboxylic acid components varying in the number of carbon atoms. Therefore, fatty acid carboxylic acids, especially stearic acid and palmitic acid, which are produced from the natural oils and fats and are in the form of a mixture containing other carboxylic acid components are also preferably used in the production of the fatty acid ester of the present invention.

Fatty acid ester of the present invention can be any in partial ester and full ester (full ester). However, if it is a partial ester, the hydroxyl value will generally become high, and resin decomposition at high temperature will be easily induced, etc. Therefore, it is more preferable that it is a full ester. The acid value in the fatty acid ester of the present invention is preferably 20 or less, more preferably in the range of 4-20, and still more preferably in the range of 4-12 from the viewpoint of thermal stability. It should be noted that the acid value can be substantially zero. Moreover, it is more preferable that the hydroxyl value of fatty acid ester is the range of 0.1-30. Furthermore, the iodine value is preferably 10 or less. In addition, the iodine value can take 0 substantially. These properties can be obtained by the method specified in JIS K 0070.

The content of the release agent is preferably 0.005 to 2 parts by weight, more preferably 0.01 to 1 part by weight, and even more preferably 0.05 to 0.5 parts by weight, based on 100 parts by weight of the total of components A and B. Within this range, the aromatic polycarbonate resin composition has good mold release properties and roll release properties. In particular, this amount of fatty acid ester provides an aromatic polycarbonate resin composition having good mold release properties and roll release properties without impairing good color tone.

(iv) UV absorber

The aromatic polycarbonate resin composition of the present invention may contain an ultraviolet absorber. The resin composition of the present invention may have poor weather resistance due to the influence of rubber components and flame retardants. Therefore, in order to prevent this deterioration, it is effective to blend an ultraviolet absorber.

As the ultraviolet absorber of the present invention, specifically, as benzophenone series, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy- 4-octyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2-hydroxy-4- Methoxy-5-sulfoxybenzophenone trihydrate, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone Ketone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sulfonate sodium benzophenone Ketone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2-hydroxy-4-n-dodecyloxybenzophenone, and 2-hydroxy-4-methoxy Base-2'-carboxybenzophenone, etc.

嗪-4-酮)、及2-[2-羟基-3-(3，4，5，6-四氢化邻苯二甲酰亚胺甲基)-5-甲基苯基]苯并三唑、以及2-(2’-羟基-5-甲基丙烯酰氧基乙基苯基)-2H-苯并三唑和能与该单体共聚的乙烯系单体的共聚物、2-(2’-羟基-5-丙烯酰氧基乙基苯基)-2H-苯并三唑和能与该单体共聚的乙烯系单体的共聚物等具有2-羟基苯基-2H-苯并三唑骨架的聚合物等。Examples of benzotriazoles include 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-chlorobenzo Triazole, 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol], 2- (2-Hydroxy-3,5-di-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzotriazole, 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-octyloxyphenyl)benzotriazole, 2,2'-methylenebis(4-cumyl-6-benzene Triazole benzene), 2,2'-p-phenylene bis(1,3-benzo

oxazin-4-one), and 2-[2-hydroxy-3-(3,4,5,6-tetrahydrophthalimidemethyl)-5-methylphenyl]benzotriazole , and a copolymer of 2-(2'-hydroxyl-5-methacryloxyethylphenyl)-2H-benzotriazole and a vinylic monomer that can be copolymerized with the monomer, 2-(2 Copolymers of '-hydroxy-5-acryloyloxyethylphenyl)-2H-benzotriazole and vinyl monomers that can be copolymerized with this monomer have 2-hydroxyphenyl-2H-benzotriazole Azole skeleton polymers, etc.

As the hydroxyphenyl triazine series, for example, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxyphenol, 2-(4,6- Diphenyl-1,3,5-triazin-2-yl)-5-methoxyphenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)- 5-ethoxyphenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-propoxyphenol, and 2-(4,6-diphenyl -1,3,5-triazin-2-yl)-5-butoxyphenol and the like. Furthermore, benzene of the above-mentioned exemplified compounds such as 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-hexyloxyphenol can be exemplified. The group becomes the compound of 2,4-dimethylphenyl.

嗪-4-酮)、2，2’-(4，4-二亚苯基)双(3，1-苯并

嗪-4-酮)、及2，2’-(2，6-萘)双(3，1-苯并

嗪-4-酮)等。As the ultraviolet absorber, specifically, as the cyclic imidate series, for example, 2,2'-p-phenylene bis(3,1-benzo

oxazin-4-one), 2,2'-(4,4-diphenylene)bis(3,1-benzo

oxazin-4-one), and 2,2'-(2,6-naphthalene)bis(3,1-benzo

oxazin-4-one) and so on.

Examples of cyanoacrylates include 1,3-bis[(2'-cyano-3',3'-diphenylacryloyl)oxy]-2,2-bis[(2-cyano -3,3-diphenylacryloyl)oxy]methyl)propane, 1,3-bis-[(2-cyano-3,3-diphenylacryloyl)oxy]benzene, and the like.

Furthermore, the above-mentioned ultraviolet absorber may be formed by combining the ultraviolet absorbing monomer and/or the photostable monomer having a hindered amine structure with a (meth)acrylic acid alkyl group by taking the structure of a monomer compound capable of radical polymerization Polymer UV absorber formed by copolymerization of ester and other monomers. As the above-mentioned ultraviolet absorbing monomer, preferably, ester substituents of (meth)acrylates containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic imidate skeleton, and a cyano group are exemplified. Compounds with an acrylate backbone.

Among the above-mentioned ultraviolet absorbers, benzotriazole-based and hydroxyphenyltriazine-based are preferable from the viewpoint of ultraviolet absorbing ability, and cyclic imide-based and cyanocyanide-based are preferable from the viewpoint of heat resistance and color tone (transparency). based acrylates. The above ultraviolet absorbers may be used alone or as a mixture of two or more.

Based on 100 parts by weight of the total of components A and B, the content of the ultraviolet absorber is preferably 0.01 to 2 parts by weight, more preferably 0.02 to 2 parts by weight, even more preferably 0.03 to 1 part by weight, particularly preferably 0.05 to 1 part by weight. 0.5 parts by weight.

(v) Dyed pigment

The aromatic polycarbonate resin composition of the present invention can provide molded articles that further contain various dyes and pigments and exhibit various design properties.

Examples of fluorescent dyes (including fluorescent whitening agents) used in the present invention include coumarin-based fluorescent dyes, benzopyran-based fluorescent dyes, perylene-based fluorescent dyes, anthraquinone-based fluorescent dyes, sulfur Indigo fluorescent dyes, xanthene fluorescent dyes, xanthone fluorescent dyes, thioxanthene fluorescent dyes, thioxanthone fluorescent dyes, thiazine fluorescent dyes, and diamino-1,2-stilbene fluorescent dyes Dyes etc. Among these fluorescent dyes, coumarin-based fluorescent dyes, benzopyran-based fluorescent dyes, and perylene-based fluorescent dyes, which have good heat resistance and little deterioration during molding of polycarbonate resins, are preferable.

嗪系染料、异吲哚啉酮系染料、及酞菁系染料等。进而，本发明的树脂组合物也可与金属颜料配合而得到更良好的金属色彩。作为金属颜料，优选在各种板状填充剂上具有金属包膜或者金属氧化物包膜的金属颜料。Examples of dyes other than the above-mentioned bluing agents and fluorescent dyes include perylene-based dyes, coumarin-based dyes, thioindigo-based dyes, anthraquinone-based dyes, thioxanthone-based dyes, and ferrocyanine such as Prussian blue. Compounds, pyrene dyes, quinoline dyes, quinacridone dyes, di

Azine-based dyes, isoindolinone-based dyes, and phthalocyanine-based dyes. Furthermore, the resin composition of the present invention can also be blended with metallic pigments to obtain better metallic colors. As the metallic pigment, those having a metal coating or a metal oxide coating on various platy fillers are preferable.

The content of the dye pigment is preferably 0.00001 to 1 part by weight, more preferably 0.00005 to 0.5 part by weight, based on 100 parts by weight of the total of the components A and B.

(vi) Other heat stabilizers

In the aromatic polycarbonate resin composition of the present invention, other thermal stabilizers other than the above-mentioned phosphorus-based stabilizer and hindered phenol-based antioxidant may be blended. The other heat stabilizer is preferably used in combination with any one of the aforementioned stabilizers and antioxidants, particularly preferably used in combination with both. As the other heat stabilizer, for example, a lactone-based stabilizer represented by a reaction product of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene (the stabilizer's Details are described in Japanese Patent Application Laid-Open No. 7-233160). This compound is marketed as Irganox HP-136 (trademark, manufactured by CIBA SPECIALTY CHEMICALS), and this compound can be used. Furthermore, a stabilizer obtained by mixing this compound with various phosphite compounds and hindered phenol compounds is commercially available. Preferable example is, for example, Irganox HP-2921 manufactured by the aforementioned company. Premixed stabilizers can also be utilized in the present invention. The compounding amount of the lactone-based 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 components A and B.

In addition, as other stabilizers, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-lauryl thiopropionate), glycerol-3-stearyl thiopropionate, etc. are exemplified. Sulfur stabilizer. This stabilizer is particularly effective when the resin composition is suitable for 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 100 parts by weight of the total of components A and B.

Examples of thermoplastic resins other than components A to C include aromatic polyester resins (polyethylene terephthalate resin (PET resin), polybutylene terephthalate resin (PBT resin), cyclo Hexane dimethanol copolymerized polyethylene terephthalate resin (so-called PET-G resin), polyethylene naphthalate resin, polybutylene naphthalate resin, etc.), polymethacrylic acid Methyl ester resins (PMMA resins), cyclic polyolefin resins, polylactic acid resins, polycaprolactone resins, thermoplastic fluororesins (represented by, for example, polyvinylidene fluoride resins), and polyolefin resins (such as polyethylene resins, ethylene - (α-olefin) copolymer resin, polypropylene resin, propylene-(α-olefin) copolymer resin, etc.). The content of 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 components A and B.

(Manufacture of aromatic polycarbonate resin composition)

In order to manufacture the aromatic polycarbonate resin composition of this invention, arbitrary methods can be employ|adopted. For example, the following method can be enumerated: After fully mixing component A, component B, component C and any other additives with premixing means such as a V-type blender, Henschel mixer, mechanochemical device, extrusion mixer, etc., If necessary, the premix is granulated with an extrusion granulator, a briquetting machine, etc., then melt-kneaded with a melt-kneader typified by a vented twin-screw extruder, and then granulated with a granulator.

In addition, there is also a method in which each component is independently supplied to a melt kneader represented by a vented twin-screw extruder; after a part of each component is pre-mixed, it is separately supplied to a melt kneader with the remaining components. method in a kneader, etc. As a method of premixing a part of each component, after premixing components other than A component, the method of mixing with the aromatic polycarbonate resin of A component or directly supplying to an extruder is mentioned.

As a method of premixing, for example, the following method can also be mentioned: when a substance having a powder form is included as the A component, a part of the powder is mixed with the compounded additive, and a master batch of the additive diluted with the powder is produced, and the master batch is used. material. Furthermore, a method of independently supplying one component from the middle of the melt extruder, etc. are also mentioned. In addition, when there is a liquid substance in the compounded component, a liquid injection device or a liquid addition device can be used for supplying to the melt extruder.

As the extruder, an extruder having a ventilation hole capable of discharging moisture in the raw material and volatilized gas generated by melt-kneading the resin can be preferably used. It is preferable to provide a vacuum pump for efficiently discharging generated moisture and volatile gas from the vent holes to the outside of the extruder. In addition, a screen for removing foreign matter and the like mixed in the extrusion raw material may be installed in the area before the die part of the extruder to remove foreign matter from the resin composition. As this screen, a wire mesh, a screen changer, a sintered metal plate (disk filter etc.), etc. are mentioned.

Examples of the melt kneader include a Banbury mixer, a kneading roll, a single-screw extruder, a multi-screw extruder having three or more shafts, and the like in addition to a twin-screw extruder.

The resin extruded as described above is directly cut and pelletized, or the strand is cut and pelletized by a pelletizer after forming strands. When it is necessary to reduce the influence of external dust and the like during granulation, it is preferable to purify the atmosphere around the extruder. Furthermore, during the manufacture of the pellets, various methods proposed in polycarbonate resins for optical discs can be used to suitably narrow the shape distribution of the pellets, reduce missed cuts, and reduce the occurrence of accidents during transportation or transportation. fine powder, and reduce air bubbles (vacuum bubbles) generated inside strands or grains. Through these processing methods, it is possible to perform high-cycle molding and reduce the occurrence rate of defects such as silver color. In addition, the shape of the particles can take general shapes such as cylinders, prisms, and spheres, and is more preferably a cylinder. The diameter of the cylinder is preferably 1 to 5 mm, more preferably 1.5 to 4 mm, even more preferably 2 to 3.3 mm. On the other hand, the length of the column is preferably 1 to 30 mm, more preferably 2 to 5 mm, even more preferably 2.5 to 3.5 mm.

(manufacture of moldings)

The molded article of the present invention is obtained by injection molding the above-mentioned aromatic polycarbonate resin composition under molding conditions satisfying the conditions of the following formula (1), preferably the following formula (2).

Tg-30≤mold temperature (℃)≤Tg+50...(1)

Tg-25≤mold temperature (℃)≤Tg+30...(2)

(In the formula, Tg is the glass transition temperature of the aromatic polycarbonate resin composition.)

When the mold temperature is lower than Tg by more than 30° C., since the mold temperature is low, many flow marks are generated in the molded product, which is not preferable. Also, when the mold temperature is higher than Tg by more than 50° C., the cooling time becomes too long and the molding cycle becomes long, which is not preferable.

The glass transition temperature of formula (1) and formula (2) in the present invention is the glass transition temperature obtained by measuring each resin composition according to ISO3146, and when there are multiple glass transition temperatures, use the glass transition temperature of the lower temperature ,Calculation.

It should be noted that the time for making the mold temperature satisfy the temperatures shown in formulas (1) and (2) may be any period from when the aromatic polycarbonate resin composition is injected into the mold to when the filling is completed. , the mold temperature at other times is not particularly limited.

As the method of heating the mold, there are conventionally proposed methods of circulating a heating medium such as hot water, steam, and heated hot water through pipes for mold temperature adjustment, methods of irradiating the surface of the mold cavity with radiant heat from a halogen lamp, The method of embedding an electric heater or the like in the mold, the method of providing a heat insulating layer with low thermal conductivity on the surface of the mold cavity, etc. Among them, it is preferable to circulate a heating medium such as hot water, steam, and hot water through the piping for mold temperature adjustment Methods. These methods may be used alone or in combination.

Specific examples of molded articles using the resin composition of the present invention include covers for office automation equipment, home electric appliances, and vehicle parts. Examples of these products include personal computers, notebook computers, flat panel displays, printers, portable terminals, mobile phones, copiers, facsimile machines, car navigation parts, car audio parts, etc., and can be used in various parts such as their casings. A resin article formed from the thermoplastic resin composition of the present invention. Among them, covers for flat panel displays and notebook computers are preferred.

[Invention effect]

The aromatic polycarbonate resin composition of the present invention maintains the original molding processability and mechanical properties such as surface impact strength of the aromatic polycarbonate resin and the graft copolymer represented by ABS resin, and at the same time improves As mentioned above, the appearance of white mist generated during injection molding of the mold is poor, and it is widely used in office automation, electrical and electronic equipment, automobiles, and other various fields. Therefore, the industrial effects obtained by the present invention are extremely large.

Description of drawings

FIG. 1 is a schematic side view of a molded product imitating a notebook computer case used in an example (length 250 mm x width 300 mm x edge height 10 mm, thickness 1.5 mm).

Fig. 2 is a schematic front view of the surface side of the molded article used in the examples, showing the position where a white mist-like appearance defect occurs.

Fig. 3 is a schematic front view of the rear side of the molded article used in the examples, showing the case of the mouth position and the ribbed boss.

[Symbol Description]

1. The main body of the molded product imitating the case of a notebook computer

2 mirror faces

3 Approximate occurrence location of white mist defect

4 ports (straight gate 5mmφ, 1 place)

5 hubs

6 ribs

Detailed ways

The inventors of the present invention think that the best aspect of the present invention is a combination of the preferred ranges of the above-mentioned requirements, and for example, representative examples thereof are described in the following examples. Of course, the present invention is not limited to these forms.

Example

<Evaluation of aromatic polycarbonate resin composition>

(i) Glass transition temperature

According to ISO3146, the glass transition temperature of each resin composition described in Table 1 and Table 2 was measured with a DSC apparatus.

(ii) Charpy impact strength

According to ISO 179, the determination of the notched Charpy impact strength is carried out.

(iii) Load deflection temperature

Determination of deflection temperature under load according to ISO 75-1 and 75-2. It should be noted that it was implemented under a measurement load of 1.80 MPa.

(iv) Liquidity

An Archimedes-type spiral flow length with a channel thickness of 2 mm and a channel width of 8 mm was measured with an injection molding machine "SG150U manufactured by Sumitomo Heavy Industries, Ltd.". It should be noted that the molding conditions were implemented under the conditions of a cylinder temperature of 260° C., a mold temperature of 70° C., and an injection pressure of 98 MPa.

(v) Surface impact strength

Under the following molding conditions, a square plate of 150 mm x 150 mm x 2 mmt was produced, and the energy required for failure (destruction energy: E1) and the failure state were measured with a high-speed surface impact tester. It should be noted that ductile failure is the preferred result. The test machine uses a high-speed surface impact tester Hydro Shot HTM-1 (manufactured by Shimadzu Corporation). The test conditions are: the impact speed of the core is 7m/s, the front end is semicircular, and the radius is 6.35mm. The hole diameter of the stand is 25.4mm.

[Molding conditions] Cylinder temperature 260°C, mold temperature 60°C, injection speed 30mm/s

(vi) Flame retardancy

According to UL standard 94V, the combustion test was carried out at a thickness of 1.5mm.

(vii) Moisture and heat resistance (surface impact strength)

Under the above molding conditions, a square plate of 150mm x 150mm x 2mmt was produced, and after being treated in a constant temperature and humidity chamber [PSL-2FPH manufactured by TABAI ESPEC Co., Ltd.] for 500 hours at 65°C and 85% RH, high-speed surface impact was performed. experiment. In the high-speed surface impact test, the breaking energy (E2) was measured by the same method as (v), and the measurement result (E1) of (v) was used as the value before the wet heat treatment, and the retention rate was calculated according to the following formula. Among them, from a practical point of view, the retention rate of the breaking energy is preferably 70% or more, particularly preferably 75% or more.

Destruction energy retention rate (%) = (E2/E1) × 100

(viii) Appearance

[use equipment]

[Injection Molding Machine] MITSUBISHI HEAVY INDUSTRIES PLASTICTECHNOLOGY 450ME II-50U

[Molding conditions] Cylinder temperature 260°C, injection speed 20mm/s

The mold temperature is recorded in Table 1 and Table 2

Cooldown 40 seconds

1) White mist

Molded products imitating notebook computer cases shown in FIGS. 1 to 3 were produced under the above-mentioned molding conditions, and the state of appearance defects such as white fog generated on the surface of the molded products was evaluated by visual comparison.

[Judgement method] The appearance of the molded product was judged by visual inspection. (○: no white fog, ×: white fog)

2) flow marks

The molded article molded in 1) was visually observed for the presence or absence of flow marks around the boss portion.

[Judgement method] The appearance of the molded product was judged by visual inspection. (○: no flow marks, ×: flow marks)

[Examples 1-16, Comparative Examples 1-10]

A mixture composed of components other than component D (phosphate ester of FR-1) and component F (reinforcing filler) among the compositions shown in Tables 1 to 2 was supplied from the first supply port of the extruder. This mixture is obtained by mixing the premix of (i) below with other ingredients in a V-blender. Here, the premix (i) is a mixture of component E (fluorine-containing anti-dripping agent) and aromatic polycarbonate component A, and the bag is vibrated in a polyethylene bag so that component F accounts for 2.5% by weight of the mixture. The mixture obtained by uniformly mixing the whole. In addition, all the F components were supplied by the side feeder from the 3rd supply port. Furthermore, FR-1 of the C component was heated to 80°C with a liquid injection device (HYM-JS-08 manufactured by Fuji Techno Industries Co., Ltd.) from the second supply port in the middle of the cylinder (between the first supply port and the second supply port). The positions between the supply ports) are supplied to the extruder at a predetermined ratio. The liquid injection device was set to supply a certain amount, and the supply amount of other raw materials was precisely measured with a meter (CWF manufactured by Kubota Corporation). Extrusion uses a ventilated twin-screw extruder with a diameter of 30mmφ (TEX30α-38.5BW-3V of Japan Steel Works Co., Ltd.), under the conditions that the screw speed is 150rpm, the discharge rate is 20kg/h, and the vacuum degree of the ventilation hole is 3kPa. Melt kneading under low pressure to obtain granules. In addition, about extrusion temperature, it implemented at 260 degreeC from the 1st supply port to a die part.

A part of the particles obtained was dried at 80 to 90°C for 5 hours in the case of Examples 12 to 16 with a hot air circulation dryer, and at 100 to 110°C in the cases of Examples 1 to 11 and Comparative Examples 1 to 10. After drying for 5 hours, a test piece for evaluation was molded using an injection molding machine.

The components indicated by the symbols in Tables 1 to 2 are as follows.

(A component)

PC-1: Aromatic polycarbonate resin [Polycarbonate resin powder with a viscosity average molecular weight of 22,500 produced by a conventional method from bisphenol A and phosgene, manufactured by Teijin Chemicals, Panlite L-1225WP]

PC-2: Aromatic polycarbonate resin [Polycarbonate resin powder with a viscosity average molecular weight of 19,700 produced from bisphenol A and phosgene by a conventional method, manufactured by Teijin Chemicals, Panlite L-1225WX]

(B component)

ABS-1: ABS resin [manufactured by Japan A&L Corporation, KRALASTIC SXH-330 (trade name), butadiene rubber component is about 17.5% by weight, weight average rubber particle size is 0.40 μm, manufactured by emulsion polymerization]

ABS-2: ABS resin [GT-A-250 (trade name) manufactured by Denka Co., Ltd., the butadiene rubber component is about 18% by weight, and the weight average rubber particle size is 0.30 μm, produced by emulsion polymerization]

(C component)

MBS-1: MBS [Manufactured by Rohm and Haas: Paraloid EXL2620 (trade name); produced by emulsion polymerization, the core is 70% by weight of polybutadiene, the shell is styrene and graft copolymerization of methyl methacrylate material, the sodium content is 15ppm, and the phosphorus content is 235ppm]

MBS-2: MBS [Manufactured by Rohm and Haas: Paraloid EXL2678 (trade name); produced by emulsion polymerization, the core is 60% by weight of polybutadiene, the shell is styrene and graft copolymerization of methyl methacrylate material, the sodium content is 10ppm, and the phosphorus content is 350ppm]

MBS-3: core-shell graft copolymer [manufactured by emulsion polymerization, the core is a 70% by weight butadiene rubber component, the shell is a graft copolymer of styrene and methyl methacrylate, the sodium content is 40ppm, phosphorus content is 310ppm]

MBS-4: MBS [manufactured by MITSUBISHI RAYON Co., Ltd.: METABLEN C-223A (trade name); produced by emulsion polymerization, the core is 70% by weight of polybutadiene, the shell is grafted with styrene and methyl methacrylate Copolymer with 83 ppm sodium and 5 ppm phosphorus]

MBS-5: MBS [manufactured by KANEKA: Kane Ace M-901 (trade name); produced by emulsion polymerization, the core is 70% by weight of polybutadiene, the shell is grafted with styrene and methyl methacrylate Copolymer with 46 ppm sodium and 8 ppm phosphorus]

MBS-6: core-shell type graft copolymer [manufactured by emulsion polymerization, the core is a 70% by weight butadiene rubber component, the shell is a graft copolymer of styrene and methyl methacrylate, the sodium content is 40ppm with a phosphorus content of 1,100ppm]

MBS-7: core-shell graft copolymer [manufactured by emulsion polymerization, the core is a 70% by weight butadiene rubber component, the shell is a graft copolymer of styrene and methyl methacrylate, the sodium content is 20ppm, phosphorus content is 90ppm]

(Component D)

FR-1: Phosphate ester mainly composed of bisphenol A bis(diphenyl phosphate) (manufactured by Daihachi Chemical Industry Co., Ltd.: CR-741 (trade name))

FR-2: Phosphate ester mainly composed of resorcinol (diphenyl phosphate) (manufactured by Daihachi Chemical Industry Co., Ltd.: CR-733S (trade name))

(Component E)

PTFE: Polytetrafluoroethylene [Polyflon MP FA500 (trade name) manufactured by Daikin Industry Co., Ltd.]

(F component)

WSN: Wollastonite (manufactured by Shimizu Industry Co., Ltd.: H-1250F (trade name))

Talc: Talc (manufactured by Hayashi Kasei Co., Ltd.: HST 0.8 (trade name))

(other ingredients)

DC30M: Olefin-based wax obtained by copolymerization of α-olefin and maleic anhydride (manufactured by Mitsubishi Chemical Corporation: Diacarna 30M (trade name))

SL: Fatty acid ester-based release agent (manufactured by RIKEN VITAMIN: Rikemal SL900 (trade name))

IRGX: Phenolic heat stabilizer (manufactured by Ciba Specialty Chemicals K.K.: IRGANOX1076 (trade name))

[Table 1]

[Table 2]

As can be seen from the above table, by applying the rubber-modified polymer with a specific residual metal content of the present invention, it is possible to perform injection molding in a mold heated to a high temperature without impairing impact strength, heat and humidity resistance, flame retardancy, and fluidity. The appearance of white mist generated during molding is poor.

Claims (5)

1. products formed is by with condition of molding hemostasis molded obtain of aromatic copolycarbonate resin composition in the condition that satisfies following formula (1),

In the described aromatic copolycarbonate resin composition, with respect to (A) aromatic polycarbonate resin, be that A composition 10～95 weight parts, (B) make vinyl cyanide monomer and aromatic vinyl monomer and rubber polymer graft copolymerization and the graft copolymer that obtains, be total 100 weight parts of B composition 5～90 weight parts, contain (C) rubber modified polymers, be C composition 0.1～20 weight part

Described C composition is with (methyl) alkyl acrylate monomer or (methyl) alkyl acrylate monomer with can obtain by the emulsion polymerization copolymerization with the mixture of the monomer of its copolymerization in the presence of rubber constituent, and sodium content is 0～50ppm, phosphorus content is 100～1000ppm

Tg-30≤die temperature (℃)≤Tg+50 ... (1)

In the formula, Tg is the second-order transition temperature of aromatic copolycarbonate resin composition.

2. products formed according to claim 1, wherein, the rubber constituent of C composition is divinyl.

3. products formed according to claim 1 and 2, wherein, described resin combination contain with respect to total 100 weight parts of A composition and B composition be 3～30 weight parts (D) organic phosphorus flame retardant, be D composition and 0.01～2 weight part (E) fluorine-containing anti-dripping agent, be the E composition.

4. each described products formed according to claim 1～3, wherein, described resin combination contain with respect to total 100 weight parts of A composition and B composition be 0.1～50 weight part (F) inorganic filling material, be the F composition.

5. each described products formed according to claim 1～4, wherein, products formed is the case of flat-panel monitor, notebook computer.

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