CN101519528A - Polycarbonate resin composition with superior appearance - Google Patents

Abstract

An object of the present invention is to provide a polycarbonate resin composition which does not generate flow marks at a welded portion or a portion with uneven thickness, and which has both excellent impact characteristics and moldability. The resin composition of the present invention contains 0.1 to 10 parts by weight of a core-shell graft based on a total of 100 parts by weight of 99 to 1% by weight of an aromatic polycarbonate resin and 1 to 99% by weight of a graft copolymer. A copolymer, wherein the graft copolymer contains a rubbery polymer with a weight-average particle diameter of 0.20-2.0 μm, a vinyl cyanide monomer, and an aromatic vinyl monomer; the core-shell graft The copolymer is, in the presence of a diene rubber component with a weight average particle diameter of 0.30-0.50 μm, by emulsion polymerization, (meth)acrylic acid alkyl ester monomer or can be combined with (meth)acrylic acid alkyl It is obtained by copolymerizing a mixture of monomers in which ester monomers are copolymerized.

Description

Polycarbonate resin composition excellent in appearance

technical field

The present invention relates to a polycarbonate resin composition with excellent appearance and its molded article. More specifically, it relates to a resin composition containing a polycarbonate resin and a specific graft copolymer and a specific core-shell type graft copolymer, which not only has unevenness in welds or thickness A resin composition and a molded article thereof having an excellent appearance without causing flow lines in some cases, and also having excellent impact properties and moldability.

Background technique

Polymer alloys with graft copolymers represented by aromatic polycarbonate resins and ABS resins have excellent formability and high impact properties, and are therefore widely used in office machines, electrical and electronic machines, and automobiles. Among them, the shells of office machines such as laser printers, copiers, notebook computers or projectors, or electrical and electronic equipment are strongly required to have high impact and excellent moldability. The aromatic polycarbonate resin and graft copolymer formed Polymer alloys have become mainstream.

In particular, recently, for the purpose of weight reduction or cost reduction, thinning and non-painting (painting) of the case molded products have been developed. Due to this influence, it has been used for cases with high appearance and high impact. Material requirements are getting higher and higher.

As the material for the shell, many methods of adding a core-shell type graft copolymer to a polymer alloy of a graft copolymer represented by an aromatic polycarbonate resin and an ABS resin have been proposed, and knowledge related to it It is well known.

For example, it is known that in a resin composition composed of an aromatic polycarbonate, an AS resin, an ABS resin, and an oligomer of an organic phosphorus compound, MBS resin is blended as a core-shell graft copolymer to obtain fluidity. , a flame-retardant resin composition excellent in impact resistance and heat resistance (Patent Document 1, Patent Document 2, and Patent Document 3). However, in this flame-retardant resin composition, by blending MBS resin as a core-shell type graft copolymer, high impact strength can be obtained while maintaining high fluidity, but the welded part or rib of the molded product In the parts with uneven thickness such as bosses and bosses, linear color unevenness due to the flow pattern during injection molding occurs, which becomes a big problem in terms of appearance. The reason is that the shape of the molded article formed from the polycarbonate-based flame-retardant resin composition is different in the part where the flow pattern changes, such as the welded part or the uneven thickness part, and many improvements have been proposed. Ester resins and ABS resins are representative graft copolymer compatibility methods.

For example, it is known that in a composition composed of polycarbonate resin and styrene-based resin represented by ABS resin and HIPS resin, terpene-based resin is added as a phase solvent, thereby obtaining strength of welded part, appearance of welded part, A polycarbonate-based thermoplastic resin excellent in melt fluidity (Patent Document 4). However, when such a compatibilizer typified by terpene-based resins is used, it has little effect as a countermeasure against appearance defects such as uneven color caused by flow patterns during injection molding, and there are problems such as lowering flammability.

As mentioned above, it is necessary to develop a resin material with a higher level of appearance and impact properties, but it has not yet been obtained.

Patent document 1: WO2000/001839 publication

Patent Document 2: JP Unexamined Publication No. 2003-41114

Patent Document 3: JP Unexamined Publication No. 2001-302898

Patent Document 4: JP Unexamined Publication No. 2000-63651

Contents of the invention

An object of the present invention is to provide a polycarbonate resin composition having improved appearance and high impact to a higher level while maintaining the original flame retardancy, heat resistance, and fluidity.

In order to solve the above-mentioned problems, the inventors of the present invention conducted intensive studies and found that by blending a core- The shell-type graft copolymer can solve the problem of poor appearance caused by the morphology of the graft copolymer polymer alloy typified by aromatic polycarbonate resin and ABS resin, thereby completing the present invention.

The above-mentioned subject of the present invention is achieved by the following means.

ビニル)单体以及芳香族乙烯单体；所述核-壳型接枝共聚物(C成分)是，在重均粒径为0.30～0.50μm的二烯类橡胶成分的存在下，通过乳液聚合法，将(甲基)丙烯酸烷基酯单体或(甲基)丙烯酸烷基酯单体和能够与(甲基)丙烯酸烷基酯单体进行共聚合的单体的混合物加以共聚合而得到。(1) There is provided a resin composition characterized by comprising an aromatic polycarbonate resin (component A), a graft copolymer (component B), and a core-shell type graft copolymer (component C), and Contains 0.1 to 10 parts by weight of core-shell-type A graft copolymer (component C), wherein the graft copolymer (component B) contains a rubbery polymer with a weight-average particle diameter of rubber particles of 0.20 to 2.0 μm, vinyl cyanide (Cian

ビニル) monomer and an aromatic vinyl monomer; the core-shell graft copolymer (component C) is obtained by emulsion polymerization in the presence of a diene rubber component with a weight average particle diameter of 0.30 to 0.50 μm. method, by copolymerizing an alkyl (meth)acrylate monomer or a mixture of an alkyl (meth)acrylate monomer and a monomer capable of copolymerizing with an alkyl (meth)acrylate monomer to obtain .

(2) The resin composition according to (1), wherein the graft copolymer (component B) is obtained by emulsion polymerization and contains 1 to 40% by weight of a diene rubber as a rubbery polymer. .

(3) The resin composition according to (1) or (2) above, wherein the core-shell graft copolymer (component C) is a core containing a diene rubber component in an amount of 40 to 90% by weight. - Shell graft copolymers.

(4) The resin composition according to any one of the above (1) to (3), wherein 0.1 to 50 parts by weight of the inorganic filler (D Element).

(5) The resin composition according to (4) above, wherein the inorganic filler (component D) is one or more fillers selected from the group consisting of talc, mica, and wollastonite.

(6) The resin composition according to any one of the above (1) to (5), wherein 0.001 to 25 parts by weight of a flame retardant (E component) and 0.05 to 2 parts by weight of a fluorine-containing anti-dripping agent (component F), and the flame retardant (component E) is selected from the group consisting of phosphoric acid esters, sulfonic acid alkali (alkaline earth) metal salts, and silicon compounds One or more flame retardants.

(7) The resin composition according to any one of the above (1) to (6), wherein the flame retardant (component E) is a phosphoric acid ester represented by the following formula (I):

In formula (I), X is a divalent phenol residue derived from a dihydroxy compound selected from the group consisting of hydroquinone, resorcinol, bis(4-hydroxydiphenyl)methane, bisphenol A , dihydroxydiphenyl, dihydroxynaphthalene, bis(4-hydroxyphenyl) sulfone, bis(4-hydroxyphenyl) ketone and bis(4-hydroxyphenyl) sulfide in the group consisting of dihydroxy compounds; n is an integer of 0 to 5, or, when it is a mixture of phosphate esters with different n numbers, n is their average value; R ⁴ , R ⁵ , R ⁶ and R ⁷ independently represent a monovalent group derived from an aryl group. A phenol residue, the aryl group being an aryl group selected from the group consisting of phenol, cresol, xylenol, isopropylphenol, butylphenol and p-cumylphenol.

Description of drawings

Fig. 1 is a schematic perspective view of the surface of a molded product imitating a notebook computer case used in an example (length 178 mm x width 245 mm x side height 10 mm, thickness 2.0 mm). The gates of this molded article were two side gates (length 5 mm x width 8 mm, thickness 1.5 mm).

Fig. 2 is a schematic front view of the surface of a molded product used in an example, showing the position of a gate, the position where a flow line occurs, and the expected fusion position.

Fig. 3 is a schematic front view of the back side of a molded product used in an example, showing a state having a ribbed boss (boss shape: outer diameter 6.5 mm, inner diameter 2.5 mm, height 10 mm).

Explanation of reference signs

1 The molded product body imitating the case of a laptop computer

2 mirror faces

3 matte surface part

4 gates (two side gates, length 5mm×width 8mm, thickness 1.5mm)

5 fusion expected position

6 Merge streak A (line-shaped color unevenness starting from the part considered to be the fusion zone)

7 Merging pattern B (linear color unevenness generated in the flow direction of the resin starting from the boss)

8 ribbed boss (outer diameter 6.5mm, inner diameter 2.5mm, height 10mm)

Detailed ways

Next, the present invention will be described in detail.

(Component A: aromatic polycarbonate resin)

The polycarbonate resin used as component A in the present invention is an aromatic polycarbonate resin obtained by reacting a dihydric phenol and a carbonate precursor. Examples of the reaction method include interfacial polymerization, melting Transesterification, solid-phase transesterification of carbonate prepolymers, ring-opening polymerization of cyclic carbonate compounds, etc.

Representative examples of dihydric phenols include hydroquinone, resorcinol, 4,4'-bisphenol, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4 -Hydroxyphenyl) propane (commonly referred to 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)diphenol, 4, 4'-(m-phenylene diisopropylidene)diphenol, 1,1-bis(4-hydroxyphenyl)-4-isopropylcyclohexane, bis(4-hydroxyphenyl)oxide, Bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)ketone, bis(4-hydroxyphenyl) Esters, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane, bis(3,5-dibromo-4-hydroxyphenyl)sulfone, bis(4-hydroxy-3-methyl Phenyl)sulfide, 9,9-bis(4-hydroxyphenyl)fluorene and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, etc. Preferred dihydric phenols are bis(4-hydroxyphenyl)alkanes, and among them, bisphenol A is particularly preferred from the viewpoint of impact resistance.

As the carbonate precursor, acyl halide (Carbonyl halide), carbonate ester or haloformate (Haro Holmette) etc. are used, specifically, phosgene (Phosgene), diphenyl carbonate or diphenyl carbonate are used. Dihaloformic acid esters of phenol, etc.

When the polycarbonate resin is produced from the above-mentioned dihydric phenol and carbonate precursor by the interfacial polymerization method, catalysts, terminal stoppers, antioxidants, etc. may be used as necessary. Antioxidants are used to prevent oxidation of the dihydric phenol. In addition, the aromatic polycarbonate resin of the present invention includes: a branched polycarbonate resin in which a polyfunctional aromatic compound having a trifunctionality or higher is copolymerized; an aromatic or aliphatic (including alicyclic) bifunctional A polyester carbonate resin in which a carboxylic acid is copolymerized; a polycarbonate resin in which a difunctional alcohol (including alicyclic) is copolymerized; and a resin in which the difunctional carboxylic acid and a difunctional alcohol are copolymerized Polyester carbonate resin. In addition, a mixture obtained by mixing two or more types of the obtained polycarbonate resins may also be used.

As polyfunctional aromatic compounds having a trifunctionality or higher, 1,1,1-tris(4-hydroxyphenyl)ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyl) Phenyl)ethane, etc.

When a polyfunctional compound capable of producing branched polycarbonate is contained, the content ratio of the polyfunctional compound is 0.001 to 1 mol%, preferably 0.005 to 0.9 mol%, and particularly preferably 0.005 to 0.9 mol% in the total amount of aromatic polycarbonate. 0.01 to 0.8 mol%. In addition, especially when the melt transesterification method is used, a branched chain structure may be generated as a side reaction, and the content of the branched chain structure is also 0.001 to 1 mol %, preferably 0.005 to 0.9 mol %, in the total amount of the aromatic polycarbonate. mol%, particularly preferably 0.01 to 0.8 mol%. In addition, the content of the above branched structure can be calculated by ¹ H-NMR measurement.

Preferred aliphatic difunctional carboxylic acids are α,ω-dicarboxylic acids. Examples of the aliphatic difunctional carboxylic acid preferably include sebacic acid (sebacic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, eicosanedioic acid, etc. straight saturated aliphatic dicarboxylic acids; and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. The difunctional alcohol is preferably an alicyclic diol, and examples thereof include cyclohexanedimethanol, cyclohexanediol, and tricyclodecane dimethanol.

Furthermore, polycarbonate-polyorganosiloxane copolymers obtained by copolymerizing polyorganosiloxane units can also be used.

The aromatic polycarbonate resin may be polycarbonate different from the above-mentioned dihydric phenol, polycarbonate containing branched chain components, various polyester carbonates, polycarbonate-polyorganosiloxane copolymers, etc. A resin in which two or more types of aromatic polycarbonates are mixed. Further, various resins such as polycarbonates having different production methods described below and polycarbonates having different terminal stoppers may be used in which two or more types are mixed.

Reaction methods such as interfacial polymerization method, melt transesterification method, carbonate prepolymer solid-phase transesterification method, and ring-opening polymerization method of cyclic polycarbonate compounds, which are production methods of polycarbonate resins, are described in various documents. And known methods such as patent publications.

The molecular weight of the aromatic polycarbonate resin is not particularly limited, but when the molecular weight is less than 1.0×10 ⁴ , it is difficult to obtain sufficient strength as a molded product, and when it exceeds 5.0×10 ⁴ , moldability decreases. Therefore, when represented by the viscosity average molecular weight, it is preferably 1.0×10 ⁴ to 5.0×10 ⁴ , more preferably 1.4×10 ⁴ to 3×10 ⁴ , and still more preferably 1.4×10 ⁴ to 2.4×10 ⁴ . In addition, two or more aromatic polycarbonate resins may be mixed. In this case, of course, it may be mixed with an aromatic polycarbonate resin having a viscosity average molecular weight outside the above-mentioned range.

In particular, mixtures with aromatic polycarbonate resins having a viscosity-average molecular weight of more than 5.0×10 ⁴ have high entropy elasticity, and are characterized by poor appearance of molded products due to rheological behavior such as injection Difficult to produce. This is an appropriate method in view of suppressing appearance defects. Furthermore, in gas injection molding, etc., the gas injection amount is stable, and in foam molding, foam cells are stable, and fine and uniform cells can be easily formed, which is advantageous in the present invention.

A mixture with a polycarbonate resin having a viscosity average molecular weight of 8.0×10 ⁴ or more is more preferable, and a mixture with a polycarbonate resin having a viscosity average molecular weight of 1.0×10 ⁵ or more is further preferable. That is, those in which a molecular weight distribution of two or more peaks can be observed in a measurement method such as GPC (gel permeation chromatography) can be preferably used.

The viscosity-average molecular weight referred to in the present invention can be calculated by the following method. First, from a solution obtained by dissolving 0.7 g of polycarbonate in 100 ml of methylene chloride at 20° C., the specific viscosity was obtained by the following formula using an Ostwald viscometer:

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

[t ₀ is the dripping second of dichloromethane, t is the dripping second of sample solution];

According to the obtained specific viscosity (η _sp ), calculate the viscosity average molecular weight M by the following formula:

η _sp /c=[η]+0.45×[η] ² c ([η] is the limit viscosity)

[η]=1.23×10 ^-4 M ^0.83

c=0.7.

(Component B: graft copolymer)

The graft copolymer (component B) of the present invention refers to a graft copolymer containing a rubbery polymer having a weight-average particle diameter of rubber particles of 0.20 to 2.0 μm, a vinyl cyanide monomer, and an aromatic vinyl monomer.

As the rubbery polymer of the present invention, polybutadiene, diene copolymers (for example, random copolymers and block copolymers of styrene/butadiene, acrylonitrile/butadiene copolymers, etc.) , copolymers of alkyl (meth)acrylate and butadiene, etc.), polyisoprene, copolymers of styrene and α-olefins (for example, ethylene/propylene random copolymers and block copolymers, Random copolymers and block copolymers of ethylene/butylene, etc.), copolymers of ethylene and unsaturated carboxylic acid esters (for example, ethylene/methacrylate copolymers, and ethylene/butyl acrylate copolymers, etc.) , copolymers of ethylene and aliphatic ethylene (for example, ethylene/vinyl acetate copolymer, etc.), non-conjugated diene terpolymers of ethylene and propylene (for example, ethylene/propylene/hexadiene copolymer, etc.), Acrylic rubbers (for example, polybutyl acrylate, poly(2-ethylhexyl acrylate), and copolymers of butyl acrylate and 2-ethylhexyl acrylate, etc.), and silicone rubbers (for example, polysilicone Oxane rubber, an IPN type rubber formed of a polyorganosiloxane rubber component and a polyalkyl(meth)acrylate rubber component, that is, a rubber having a mutual complex structure so that the two rubber components cannot be separated, and a rubber composed of IPN type rubber composed of polyorganosiloxane rubber component and polyisobutylene rubber component, etc.). Among them, polybutadiene, diene-based copolymers, polyisoprene, acrylic rubber, and non-conjugated diene terpolymers of ethylene and propylene, which can express their effects more easily, are particularly preferred. For polybutadiene, diene copolymer.

The rubber particles of the rubbery polymer have a weight average particle diameter of 0.20 to 2.0 μm, preferably 0.25 to 1.5 μm, more preferably 0.28 to 1.3 μm. When the weight-average particle diameter of the rubber particles is less than 0.2 μm, the impact improvement effect by adding the graft polymer is low, which is not preferable. Moreover, when it exceeds 2.0 micrometers, since the dispersion|distribution state with polycarbonate resin will worsen and the impact characteristic will fall, it is unpreferable.

The weight-average particle diameter of the rubber particles in the present invention is a value measured by a transmission electron microscope. Specifically, a drop of emulsion-like rubber-like polymer is placed in a transmission electron microscope measurement mesh, and stained with vapor of osmium tetroxide or ruthenium tetroxide. Then, use a transmission electron microscope (TECNAI G2, accelerating voltage 120kv, manufactured by FEI Company) to photograph the rubbery polymer sample after dyeing, and by image processing software (NexusNewQube), from the 200 images taken The weight-average particle diameter of the rubber particles was calculated.

Acrylonitrile, methacrylonitrile, etc. are mentioned as a vinyl cyanide monomer in this invention, Acrylonitrile is especially preferable.

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

The rubber component content of the graft copolymer (component B) of the present invention is 1 to 40% by weight, preferably 5 to 30% by weight, more preferably 10 to 25% by weight. When the content exceeds 40% by weight, the effect of improving fluidity is not sufficient, which is not preferable. In addition, when the content of the rubber component is less than 1% by weight, the impact improvement effect is insufficient, which is not preferable.

The method for producing the graft copolymer (component B) of the present invention is not particularly limited, but a graft copolymer produced by an emulsion polymerization method is preferably used.

As the graft copolymer (B component) of this invention, ABS resin, AES resin, ASA resin etc. are mentioned specifically, and these are all easy to obtain, for example. Among them, ADS resin is more preferable.

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

In addition, here, the ABS resin refers to a graft copolymer mainly composed of acrylonitrile, butadiene rubber, and styrene, and the AES resin refers to a graft copolymer mainly composed of acrylonitrile, ethylene-propylene rubber, and styrene. ASA resin refers to a graft copolymer mainly composed of acrylonitrile, styrene, and acrylic rubber.

The graft copolymer (B component) of this invention may be used individually or in combination of 2 or more types. For example, ABS resin and ASA resin, ABS resin and AES resin, etc. can be used together. When a plurality of graft copolymers are used in combination, the content of the rubber component is 1 to 40% by weight, preferably 5 to 30% by weight, more preferably 10 to 25% by weight. When the content of the rubber component exceeds 40% by weight, the effect of improving fluidity is not sufficient, which is not preferable. In addition, when the content of the rubber component is less than 1% by weight, the impact improvement effect is insufficient, which is not preferable.

ABS resin refers to a thermoplastic graft copolymer (ABS copolymer) formed by graft-copolymerizing a vinyl cyanide compound and an aromatic vinyl compound on a diene rubber component, and the graft copolymer and a vinyl cyanide compound A mixture with a copolymer of an aromatic vinyl compound (AS copolymer). In addition, the copolymer of the vinyl cyanide compound and the aromatic vinyl compound may be a copolymer derived during the manufacture of a resin composed of a thermoplastic graft copolymer (wherein the thermoplastic graft copolymer is derived from a diene A thermoplastic graft copolymer obtained by graft-copolymerizing a vinyl cyanide compound and an aromatic vinyl compound in the rubber component), or a vinyl compound copolymer obtained by separately copolymerizing an aromatic vinyl compound and a vinyl cyanide compound substances that are mixed together. Among values measured in terms of standard polystyrene by the GPC (gel permeation chromatography) method, the weight average molecular weight of the copolymer formed of the vinyl cyanide compound and the aromatic vinyl compound is preferably 3.0×10 ⁴ to 2.0× 10 ⁵ , more preferably 6.0×10 ⁴ to 1.4×10 ⁵ , still more preferably 9.0×10 ⁴ to 1.2×10 ⁵ . In addition, the proportion of the AS copolymer can be obtained by dissolving the ABS resin in a good solvent of the AS copolymer such as acetone, and collecting the soluble components by centrifugation or the like. In addition, its insoluble component (gel) is the real ABS copolymer.

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

As the diene-based rubber component of the ABS resin, rubber components having a glass transition temperature of -10° C. or lower, such as polybutadiene, polyisoprene, and styrene-butadiene copolymer, can be used, for example.

Examples of the aromatic vinyl compound in the ABS resin include the above-mentioned compounds, and styrene is particularly preferable. Examples of the vinyl cyanide compound in the ABS resin include the above-mentioned compounds, for example, acrylonitrile, methacrylonitrile, etc., and acrylonitrile is particularly preferable.

In the ABS resin used in the present invention, the proportion of the diene rubber component in 100% by weight of the ABS resin component is preferably 1 to 40% by weight, more preferably 5 to 30% by weight, and even more preferably 10 to 25% by weight. , particularly preferably 12 to 22% by weight. In 100% by weight of the ABS resin component, the ratio of the copolymer of the vinyl cyanide compound and the aromatic vinyl compound other than the diene rubber component is preferably 99 to 60% by weight, more preferably 95 to 70% by weight, and even more preferably It is 90 to 75% by weight, particularly preferably 88 to 78% by weight. Furthermore, the vinyl cyanide compound is preferably 5 to 50% by weight (more preferably 15 to 35% by weight) relative to 100% by weight of the vinyl cyanide compound and the total of 100% by weight of the aromatic vinyl compound, and the aromatic vinyl compound It is preferably 95 to 50% by weight (more preferably 65 to 85% by weight). Furthermore, methyl (meth)acrylate, ethyl acrylate, maleic anhydride, N-substituted maleic anhydride imide, etc. may be used in combination with a part of the grafted component grafted into the above-mentioned diene rubber component, Their content ratio is preferably 15% by weight or less in the ABS resin. Furthermore, as the initiator, chain transfer agent, emulsifier, etc. used in the reaction, conventionally known various substances can be used as needed.

In the ABS resin, the weight-average particle diameter of the rubber particle diameter is preferably 0.20 to 2.0 μm, more preferably 0.25 to 1.5 μm, and especially preferably 0.28 to 1.3 μm. The rubber particle diameter distribution may be a material having a single distribution or a material having two or more peaks, and further, in its form, a material in which the rubber particles form a single phase may be used, or a material around the rubber particles may be used. A substance that contains an occluded phase and has a salami structure.

The method for producing the ABS resin is not particularly limited, but an ABS resin produced by an emulsion polymerization method is more preferable.

(Component C: core-shell graft copolymer)

In the core-shell type graft copolymer (component C) of the present invention, a diene rubber component having a weight-average particle diameter of rubber particles of 0.30 to 0.50 μm and an alkyl (meth)acrylate monomer or (meth)acrylate base) a core-shell graft copolymer formed by copolymerizing a mixture of alkyl acrylate and other monomers that can be copolymerized with it, preferably mainly methyl methacrylate or methyl methacrylate and a monomer that can be copolymerized with it A copolymer obtained by graft-copolymerizing a mixture of other polymerized monomers to a diene rubber typified by butadiene-styrene.

The diene rubber component mentioned in the present invention refers to adjusting 1,3-butadiene as the main structural unit to 50 to 100% by weight, preferably 65 to 100% by weight, more preferably 75% by emulsion polymerization. ~100% by weight, the vinyl monomer represented by styrene, which can be copolymerized with the main structural unit, is adjusted to 50-0% by weight, preferably 35-0% by weight, more preferably 25-0% by weight obtained copolymers. When 1,3-butadiene as a main structural unit is less than 50% by weight, sufficient impact properties cannot be obtained, which is not preferable.

The particle diameter of the diene rubber component of the present invention is 0.30 to 0.50 μm, preferably 0.30 to 0.40 μm, and more preferably 0.32 to 0.38 μm in terms of weight average particle diameter. When the particle size of the diene rubber is less than 0.30 μm, the flow lines generated on the welded part or the uneven thickness part are very thick, and when it exceeds 0.50 μm, it causes poor dispersion and loses the effect as an impact modifier, so it is not suitable preferred.

The weight-average particle diameter of the rubber particles of the present invention is a numerical value measured by the same method as the method for measuring the weight-average particle diameter of the rubbery polymer of the B component, and is the value of the rubber particles photographed by a transmission electron microscope. Value calculated based on the image.

Examples of vinylic monomers represented by styrene used in the formation of the diene rubber component include styrene, α-methylstyrene, p-methylstyrene, chlorostyrene, dibromo Aromatic vinyl monomers such as styrene and tribromostyrene; alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate; methyl acrylate , ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and other alkyl acrylates. In addition to the above-mentioned monomers, vinyl ether-based monomers, halogenated vinylidene monomers, glycidyl acrylate and other vinyl-based monomers having a glycidyl group are also mentioned.

Moreover, among the above-mentioned vinyl monomers, those that can also be used as crosslinkable monomers are monomers that can be copolymerized with butadiene or vinyl monomers, and have two or more independent C=C bonds in the molecule. Compounds, for example, aromatic polyfunctional vinyl compounds such as divinylbenzene and divinyltoluene; polyhydric alcohols such as ethylene glycol dimethacrylate and 1,3-butanediol diacrylate α,β-Unsaturated carboxylic acid esters; trimethacrylates or allyl esters of α,β-unsaturated carboxylic acids of triacrylates, allyl acrylates, allyl methacrylates, etc.; ortho Diallyl or triallyl compounds such as diallyl phthalate, diallyl sebacate, and diallyltriazine.

The above vinylic monomers and crosslinkable monomers may be used alone or in combination of two or more.

In addition, when forming the diene rubber component, a chain transfer agent (initiator) such as t-dodecyl mercaptan may be used as necessary during the polymerization reaction. To this diene rubber component, when preparing the latex, a bulking agent is added to suppress the weight average particle diameter of the diene rubber component. Examples of the hypertrophic agent include inorganic salts such as sodium chloride, potassium chloride, sodium sulfate, magnesium sulfate, and aluminum sulfate; organic salts such as calcium acetate and magnesium acetate; inorganic acids such as sulfuric acid and hydrochloric acid; acetic acid, Organic acids such as succinic acid; and their organic acid anhydrides, and further, carboxylic acid-containing polymer latex, etc.

The core-shell type graft copolymer (component C) used in the present invention can be obtained by making (meth)acrylic acid alkyl ester monomer or (meth) ) A mixture of alkyl acrylate and other monomers that can be copolymerized with it, and it is prepared by one or more stages of graft copolymerization.

That is, as monomers used in the above-mentioned graft copolymerization, alkyl (meth)acrylates such as methyl methacrylate and ethyl methacrylate as essential components; and methyl acrylate, ethyl acrylate, etc. In addition to alkyl acrylates such as esters and butyl acrylate, styrene, α-methylstyrene, or various halogen-substituted and/or alkyl-substituted styrenes and other styrenes; glycidyl acrylate Vinyl monomers having a glycidyl group such as ester, glycidyl methacrylate, allyl glycidyl ether, etc. Furthermore, you may use together the said vinylic monomer used as a crosslinkable monomer, and the said vinylic monomer. These vinylic monomers and crosslinkable monomers may be used alone or in combination with an alkyl (meth)acrylate which is an essential component, or two or more of them.

In graft polymerization, the latex of the diene rubber component is adjusted to 40 to 90% by weight, preferably 42 to 85% by weight, and more preferably 45 to 80% by weight. Or the usage-amount of a monomer mixture is adjusted to 60-10 weight%, Preferably it is 58-15 weight%, More preferably, it is 55-20 weight%. In addition, when a monomer mixture is used, the content of the alkyl (meth)acrylate monomer as an essential component is at least 25% by weight, preferably 40% by weight or more in the total amount of the monomer mixture.

In addition, the graft copolymer (component C) can be polymerized in one stage by adding the monomer or the monomer mixture at one time, or can divide the monomer or the monomer mixture into two or more times, so that it can be divided into multiple stages. Carry out graft polymerization.

As the method of graft copolymerization, the 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 Organic peroxides such as hydrogen peroxide, lauric acid peroxide, and diisopropylbenzene hydroperoxide; azo compounds such as azobisisobutyronitrile and azoisovaleronitrile, etc. In addition, the above-mentioned oxidant compound is mixed with sulfite, bisulfite, thiosulfate, metalloid, sodium formaldehyde sulfoxylate, dextrose, etc., and used as a redox type initiator.

The reaction temperature in the graft copolymer can be appropriately selected in the range of, for example, 40 to 80° C. according to the kind of the polymerization initiator to be used. Moreover, when carrying out emulsion polymerization, a well-known emulsifier can be used suitably as an emulsifier with respect to the butadiene rubber polymer latex.

For the obtained core-shell graft copolymer (component C), add an appropriate antioxidant to the reaction solution or add additives as needed, or spray dry (directly powderize) without adding, or , A coagulant (such as sulfuric acid, hydrochloric acid, phosphoric acid, etc., or salts such as calcium chloride, sodium chloride, etc.) is appropriately added to the reaction solution to coagulate, and further heat-treated to solidify. Then, after dehydration, washing, final drying and powdering, it is put into use.

(Component D: inorganic filler)

In the present invention, various inorganic fillers may be contained as the D component. For example, talc, wollastonite, mica, clay, montmorillonite, smectite, kaolin, calcium carbonate, carbon fibers, carbon flakes, carbon beads, ground carbon fibers, metal flakes, Metal fibers, metal coated glass fibers, metal coated carbon fibers, metal coated glass flakes, silica, ceramic particles, ceramic fibers, ceramic balls, aramid particles, aramid fibers, polyarylate fibers, Various whiskers such as graphite, potassium titanate whiskers, aluminum borate whiskers, basic magnesium sulfate, etc. Among them, silicate-based fillers such as talc, wollastonite, and mica are preferably used. These inorganic fillers may be used alone or in combination.

(D-1 ingredient: talc)

The talc (component D-1) used in the present invention includes talc having an average particle diameter of 5 μm or less. Talc having an average particle diameter of 3 μm or less is more preferred, and talc having an average particle diameter of 2 μm or less is particularly preferred. 0.05 micrometer is mentioned as a lower limit. The average particle diameter of talc mentioned here means D50 (median diameter of particle diameter distribution) measured by the X-ray transmission method which is one of liquid-phase precipitation methods. As a specific example of an apparatus for carrying out this measurement, Sedigraph 5100 manufactured by Micromeritics, etc. can be mentioned.

Talc is preferably used in a granulated state. As a granulation method, there are cases where a binder is used and cases where it is not actually used. Talc in which no binder is used is more preferred. As the granulation method when no binder is used, the method of degassing compression (for example, the method of performing roll compression with a dough maker while degassing in a vacuum state) and rotary granulation or agglomeration particle method, etc.

(D-2 component: mica)

Examples of mica (component D-2) used in the present invention include powdered mica having an average particle diameter of 1 to 80 μm. Mica having an average particle diameter of 2 to 50 μm is more preferable. The average particle diameter is a value measured by a laser diffraction scattering method. When the average particle diameter is 1-80 μm, it can exert a more favorable effect on the flame retardancy and also satisfy the condition of microdispersion in the resin, therefore, it can also maintain good heat and humidity resistance. As the thickness of the mica, mica having a thickness of 0.01 to 1 μm actually measured by observation with an electron microscope can be used. A preferable thickness is 0.03 to 3 μm. Furthermore, the mica may be surface-treated with a silane coupling agent or the like, and further, may be granulated with an epoxy-based, polyurethane-based, acrylic-based or other binder to obtain a granular form.

(D-3 component: wollastonite)

Wollastonite (component D-3) used in the present invention is preferably wollastonite having a number average fiber diameter of 0.5 to 5 μm. The number-average fiber diameter refers to a numerical value obtained by randomly extracting a total of 1000 samples from images observed by electron micrographs, measuring the fiber diameters, and calculating the number average. The wollastonite preferably has an aspect ratio L/D (L: number average fiber length, D: number average fiber diameter) of 5 or more, more preferably 6 or more. The number-average fiber length is obtained by observing wollastonite with an optical microscope or an electron microscope at a magnification that can almost completely observe the entire image of wollastonite, inputting the image to an image analysis device, and calculating the number-average fiber length. length. Examples of the image analysis device include the PIAS-III system manufactured by Byass, and the like. The wollastonite used in the present invention preferably has a heat loss at 1000° C. of 2% by weight or less, more preferably 1.5% by weight or less, and still more preferably 1% by weight or less.

The resin composition of the present invention may contain a fracture preventing agent for suppressing fracture of the reinforcing filler. The anti-fragmentation agent inhibits the adhesion between the matrix resin and the reinforcing filler, reduces the stress acting on the reinforcing filler during melt kneading, and suppresses fracture of the filler. As the effect of the anti-fragmentation agent, it can be cited (1) to improve the rigidity (the aspect ratio of the filling material becomes larger); Carbonate resin is effective when used as the main body); (3) Improve conductivity (when it is a conductive filling material), etc. Specifically, the anti-fragmentation agent is a compound as follows: (i) a compound having a low affinity with resin is directly coated on the surface of the reinforcing filler; (ii) has a low affinity with resin A compound with a functional group capable of reacting with the surface of the reinforcing filler material.

Typical examples of compounds having low affinity with resins include various lubricants. Examples of lubricants include mineral oil, synthetic oil, higher fatty acid ester, higher fatty acid amide, polyorganosiloxane (silicone oil, silicone rubber, etc.), olefin wax (paraffin wax, polyolefin wax, etc.), Fluorine oils such as alkyl glycol, fluorinated fatty acid ester, chlorotrifluoroethylene, polyhexafluoropropylene glycol, etc.

As a method of directly coating the surface of the reinforcing filler with a compound having a low affinity with the resin, there are (1) a method of directly impregnating the compound into the reinforcing filler or impregnating a solution or emulsion of the compound into the reinforcing filler. (2) the method of passing the reinforced filling material through the steam or powder of the compound; (3) the method of irradiating the powder of the compound to the reinforced filling material at high speed; (4) making the reinforced filling material The chemical kinetic method of friction with the compound, etc.

Examples of the compound having a structure having a low affinity with resin and a functional group capable of reacting with the surface of the reinforcing filler include the aforementioned lubricants modified with various functional groups. As this functional group, a carboxyl group, a carboxylic anhydride group, an epoxy group, an oxazoline group, an isocyanate group, an ester group, an amino group, an alkoxysilyl group etc. are mentioned, for example.

More preferably, the anti-fragmentation agent is a polyolefin wax having at least one functional group selected from carboxyl groups and carboxylic anhydride groups. As a molecular weight, it is preferable that it is 500-20000 in weight average molecular weight, and it is more preferable that it is 1000-15000. In this polyolefin wax, with respect to 1 g of lubricants having at least one functional group selected from carboxyl groups and carboxylic anhydride groups, the amount of carboxyl groups and carboxylic anhydride groups is preferably 0.05 to 10 meq/g, more preferably 0.1 to 6 meq/g. g is more preferably 0.5 to 4 meq/g. In the case of other functional groups, it is preferable to contain the same amount as the carboxyl group.

Particularly preferably, the anti-cracking agent is a copolymer of α-olefin and maleic anhydride. The copolymer can be produced by melt polymerization or bulk polymerization in the presence of a radical catalyst according to a conventional method. Here, examples of the α-olefin preferably include α-olefins having an average number of carbon atoms of 10 to 60. As the α-olefin, an α-olefin having an average number of carbon atoms of 16 to 60 is more preferable, and an α-olefin having 25 to 55 carbon atoms is still more preferable. In 100% by weight of the resin composition of the present invention, the anti-fragmentation agent is preferably 0.01 to 2% by weight, more preferably 0.05 to 1.5% by weight, and even more preferably 0.1 to 0.8% by weight.

(E component: flame retardant)

For the resin composition of the present invention, various flame retardants (component E) known as flame retardants for aromatic polycarbonate resins can be used. More preferably as E component (i) organophosphorus flame retardant (for example, monophosphate compound, phosphate oligomer, phosphonate oligomer, phosphazene oligomer and phosphonic acid amide compound etc.); (ii ) organic metal salt flame retardants (for example, organic sulfonic acid alkali (alkaline earth) metal salts, boric acid metal salt flame retardants and stannate metal salt flame retardants, etc.) (iii) silicon-based flame retardants formed of silicon compounds Fuel. By blending compounds used as flame retardants, not only can flame retardancy be improved, but also antistatic properties, fluidity, rigidity, and thermal stability can be improved, for example, based on the properties of each compound.

(E-1) Organophosphorous flame retardants

As the organophosphorus flame retardant that can be used in the present invention, phosphoric acid ester compounds are preferred, and aryl phosphoric acid ester compounds are particularly preferred. The phosphoric acid ester compound is effective in improving flame retardancy, and since the phosphoric acid ester compound has a plasticity effect, it is advantageous in improving the molding processability of the resin composition of the present invention although there is a decrease in heat resistance. As the phosphoric acid ester compound, various phosphoric acid ester compounds conventionally known as flame retardants can be used, but more preferably one or more phosphoric acid ester compounds represented by the following general formula (I) .

(In formula (I), X is a divalent phenol residue derived from a dihydroxy compound selected from the group consisting of hydroquinone, resorcinol, bis(4-hydroxydiphenyl)methane, bisphenol A, dihydroxyl compounds in the group consisting of dihydroxydiphenyl, dihydroxynaphthalene, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)ketone and bis(4-hydroxyphenyl)sulfide; n is an integer from 0 to 5, or, when it is a mixture of phosphate esters with different n numbers, n is their average value; R ⁴ , R ⁵ , R ⁶ and R ⁷ independently represent a group derived from an aryl group. Valence phenol residue, the aryl group is an aryl group selected from the group consisting of phenol, cresol, xylenol, isopropylphenol, butylphenol and p-cumylphenol.)

The phosphate ester compound of the above formula (I) may also be a mixture of compounds with different n values. When it is the mixture, the average value of n is preferably 0.5 to 1.5, more preferably 0.8 to 1.2, and even more preferably 0.95 to 1.15, particularly preferably in the range of 1 to 1.14.

Preferable specific examples of the dihydric phenol derived from X of the above formula (I) include resorcinol, bisphenol A and dihydroxydiphenyl, among which resorcinol and bisphenol A are preferable.

Preferred specific examples of monovalent phenols derived from R ⁴ , R ⁵ , R ⁶ and R ⁷ of the above formula (I) include phenol, cresol, xylenol, and 2,6-xylenol, wherein , preferably phenol and 2,6-dimethylphenol.

As specific examples of the phosphate ester compound of the above formula (I), monophosphate ester compounds such as triphenyl phosphate and tris (2,6-dimethylphenyl) phosphate can be preferably mentioned; and resorcinol Phosphate oligomer with bis(2,6-dimethylphenyl) phosphate as the main body; phosphate oligomer with 4,4-dihydroxydiphenylbis(diphenyl phosphate) as the main body and bisphenol A bis(diphenyl phosphate) as the main phosphoric acid ester oligomer, wherein, preferably resorcinol bis(2,6-dimethylphenyl) phosphate as the main phosphoric acid Ester oligomers; phosphate oligomers based on 4,4-dihydroxydiphenyl bis(diphenyl phosphate); and phosphate esters based on bisphenol A bis(diphenyl phosphate) Oligomer.

When an organophosphorus flame retardant is used as a flame retardant, its compounding amount is preferably 1 to 25 parts by weight, more preferably 2 to 25 parts by weight, and even more preferably 3 to 20 parts by weight. The effect (for example, flame retardancy, etc.) exerted by the compounding of the organic phosphorus flame retardant becomes better when the compounding amount is in a more preferable range.

(E-2) Organometallic salt flame retardants

Organometallic salt-based flame retardants are advantageous in maintaining heat resistance. The most preferred organometallic salt flame retardants in the present invention are alkali (alkaline earth) metal organosulfonates. Among them, alkali (alkaline earth) metal salts of fluorine-substituted organic sulfonic acids are preferred, and alkali (alkaline earth) metal salts of sulfonic acids having a perfluoroalkyl group are particularly preferred. In this case, the number of carbon atoms in the perfluoroalkyl group is preferably in the range of 1-18, more preferably in the range of 1-10, and still more preferably in the range of 1-8.

The metal that constitutes the metal ion of the fluorine-substituted organic sulfonic acid alkali (alkaline earth) metal salt is an alkali metal or an alkaline earth metal, and lithium, sodium, potassium, rubidium, and cesium can be mentioned as the alkali metal; Magnesium, calcium, strontium and barium. More preferred are alkali metals. Therefore, the preferred organometallic salt-based flame retardants are alkali metal perfluoroalkyl sulfonates. Among the alkali metals, rubidium and cesium are preferably used when higher transparency is required, but on the other hand, since these are not commonly used and are difficult to refine, they may be disadvantageous in terms of cost. In addition, lithium and sodium are advantageous in terms of cost and flame retardancy, but may be disadvantageous in transparency. Alkali metals in alkali metal salts of perfluoroalkane sulfonates can be used differently depending on the above circumstances, but potassium salts of perfluoroalkane sulfonates with an excellent balance of properties are most suitable for use regardless of the point of view. It is also possible to use this potassium salt in combination with an alkali metal salt of perfluoroalkylsulfonic acid formed from another alkali metal.

Specific examples of the perfluoroalkanesulfonate alkali metal salts include potassium trifluoromethanesulfonate, potassium perfluorobutanesulfonate, potassium perfluorohexanesulfonate, potassium perfluorooctanesulfonate, Sodium fluoroethane sulfonate, sodium perfluorobutane sulfonate, sodium perfluorooctane sulfonate, lithium trifluoromethane sulfonate, lithium perfluorobutane sulfonate, lithium perfluoroheptane sulfonate, trifluoromethane sulfonate cesium perfluorobutanesulfonate, cesium perfluorobutanesulfonate, cesium perfluorooctanesulfonate, cesium perfluorohexanesulfonate, rubidium perfluorobutanesulfonate and rubidium perfluorohexanesulfonate, etc. These may be used alone or in combination of two or more. Among them, potassium perfluorobutanesulfonate is particularly preferable.

In the above-mentioned organometallic salt-based flame retardant, the content of fluoride ions measured by ion chromatography is preferably 50 ppm or less, more preferably 20 ppm or less, even more preferably 10 ppm or less. The lower the content of fluoride ions, the better the flame retardancy or light resistance. Actually, the lower limit of the content of fluoride ions can be adjusted to 0, but in consideration of the number of steps and the effect of the refining process, the lower limit is practically preferably about 0.2 ppm. The perfluoroalkylsulfonate alkali metal salt having this fluoride ion content can be purified, for example, by the following method. That is, at 40 to 90°C (more preferably 60 to 85°C), the alkali metal salt of perfluoroalkanesulfonic acid is dissolved in ion-exchanged water that is 2 to 10 times the weight of the metal salt. The alkali metal salt of perfluoroalkane sulfonate is neutralized by neutralizing perfluoroalkane sulfonic acid in alkali metal carbonate or hydroxide, or by adding perfluoroalkane sulfonyl fluoride (パ-フルオロアルキルスルリルフルオライライド) is produced by neutralizing an alkali metal carbonate or hydroxide (preferably the latter method). In addition, as the ion-exchanged water, it is particularly preferable to use water having a resistance value of 18 MΩ·cm or more. The solution in which the metal salt is dissolved is stirred at the above temperature for 0.1 to 3 hours, preferably for 0.5 to 2.5 hours. Then, the solution is cooled to 0-40°C, preferably to 10-35°C. Crystallization occurs by cooling. The precipitated crystals were taken out by filtration. Thus, an ideal purified alkali metal perfluoroalkanesulfonate is produced.

When a fluorine-substituted organic sulfonic acid alkali (alkaline earth) metal salt is used as a flame retardant, the compounding amount is preferably 0.01 to 1.0 parts by weight, more preferably 0.05 to 0.8 parts by weight, based on 100 parts by weight of the total of components A and B. , and more preferably 0.08 to 0.6 parts by weight. The effect (for example, flame retardancy, antistatic property, etc.) exerted by the addition of the fluorine-substituted organic sulfonic acid alkali (alkaline earth) metal is more favorable when the compounding amount is in a more preferable range.

As the organic metal salt-based flame retardant other than the alkali (alkaline earth) metal salt of a fluorine-substituted organic sulfonic acid, a metal salt of an organic sulfonic acid not containing a fluorine atom is preferable. As the metal salt, for example, alkali metal salts of aliphatic sulfonic acids, alkaline earth metal salts of aliphatic sulfonic acids, alkali metal salts of aromatic sulfonic acids, and alkaline earth metal salts of aromatic sulfonic acids (all containing no fluorine atoms) )wait.

Preferable examples of metal salts of aliphatic sulfonic acids include alkali (alkaline earth) metal salts of alkylsulfonic acids, and these may be used alone or in combination of two or more (here, the notation of alkali (alkaline earth) metal salts Indicates any of alkali metal salts and alkaline earth metal salts). Preferable examples of the paraffinsulfonic acid used in the alkali (alkaline earth) metal salt of the alkylsulfonic acid include methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, methylbutanesulfonic acid, hexanesulfonic acid, and acid, heptansulfonic acid, octanesulfonic acid, etc. These may be used alone or in combination of two or more.

Examples of the aromatic sulfonic acid used for the alkali (alkaline earth) metal salt of an aromatic sulfonic acid include sulfonic acids of monomeric or polymeric aromatic sulfides, sulfonic acids of aromatic carboxylic acids and esters, monomeric Aromatic or polymeric aromatic ether sulfonic acid, aromatic sulfonic ester sulfonic acid, monomeric or polymeric aromatic sulfonic acid, monomeric or polymeric aromatic sulfone sulfonic acid, aromatic At least one acid selected from the group consisting of sulfonic acids of aromatic ketones, heterocyclic sulfonic acids, sulfonic acids of aromatic sulfoxides, and condensates formed through alkylene bonds of aromatic sulfonic acids. These may be used alone or in combination of two or more.

ポリスルホン

ポリナトリウム)、1—甲氧基萘—4—磺酸钙、4—月桂基苯基醚二磺酸二钠、聚(2，6—二甲基亚苯基氧化物)多磺酸多钠(ポリ(2，6—ジメチルフエ二レンオキシド)ポリスルホン

ポリナトリウム)、聚(1，3—亚苯基氧化物)多磺酸多钠(ポリ(1，3—フエ二レンオキシド)ポリスルホン

ポリナトリウム)、聚(1，4—亚苯基氧化物)多磺酸多钠(ポリ(1，4—フ_エ二レンオキシド)ポリスルホン

ポリナトリウム)、聚(2，6—二苯基亚苯基氧化物)多磺酸多钾(ポリ(2，6—ジフ_エ二ルフ_エ二レンオキシド)ポリスルホン

ポリカリウム)、聚(2—氟代—6—丁基亚苯基氧化物)聚磺酸锂、苯磺酸酯的磺酸钾、苯磺酸钠、苯磺酸锶、苯磺酸镁、对苯二磺酸二钾、萘—2，6—二磺酸二钾、联苯—3，3’—二磺酸钙、二苯基砜—3—磺酸钠、二苯基砜—3—磺酸钾、二苯基砜—3，3’—二磺酸二钾、二苯基砜—3，4’—二磺酸二钾、α，α，α—三氟苯乙酮—4—磺酸钠、二苯甲酮—3，3’—二磺酸二钾、噻吩—2，5—二磺酸二钠、噻吩—2，5—二磺酸二钾、噻吩—2，5—二磺酸钙、苯并噻吩磺酸钠、二苯基亚砜—4—磺酸钾、萘磺酸钠的福尔马林缩合物、以及蒽磺酸钠的福尔马林缩合物等。As specific examples of aromatic sulfonic acid alkali (alkaline earth) metal salts, for example, diphenylsulfide-4,4'-disodium disulfonate, diphenylsulfide-4,4'-disulfonate Dipotassium dipotassium acid, potassium 5-sulfoisophthalate, sodium 5-sulfoisophthalate, polysodium polyethylene terephthalate polysulfonate

Polysilhon

Polynatrium), 1-methoxynaphthalene-4-calcium sulfonate, disodium 4-lauryl phenyl ether disulfonate, poly(2,6-dimethylphenylene oxide) polysulfonate polysodium (ポリ(2,6—ジメチルフエレンオキキシャド)ポリスルホン

Polynatrium), poly(1,3-phenylene oxide) polysulfonate polysodium

Polynatrium), poly(1,4- _phenylene oxide) polysulfonate polysodium

Polynatrium), poly(2,6- _{diphenylphenylene oxide} ) polypotassium polysulfonate

Polycarium), poly(2-fluoro-6-butylphenylene oxide) lithium polysulfonate, potassium sulfonate of benzenesulfonate, sodium benzenesulfonate, strontium benzenesulfonate, magnesium benzenesulfonate, Dipotassium terephthalate, dipotassium naphthalene-2,6-disulfonate, calcium biphenyl-3,3'-disulfonate, sodium diphenylsulfone-3-sulfonate, diphenylsulfone-3 —Potassium sulfonate, diphenylsulfone-3,3'-dipotassium disulfonate, diphenylsulfone-3,4'-dipotassium disulfonate, α,α,α-trifluoroacetophenone-4 -Sodium sulfonate, benzophenone-3,3'-dipotassium disulfonate, thiophene-2,5-disodium disulfonate, thiophene-2,5-dipotassium disulfonate, thiophene-2,5 - Calcium disulfonate, sodium benzothiophene sulfonate, potassium diphenylsulfoxide-4-sulfonate, formalin condensate of sodium naphthalene sulfonate, formalin condensate of sodium anthracene sulfonate, etc. .

Among the metal salts of organic sulfonic acids not containing fluorine atoms, alkali (alkaline earth) metal salts of aromatic sulfonic acids are preferred, and potassium salts are particularly preferred. When blending an aromatic sulfonic acid alkali (alkaline earth) metal salt as a flame retardant, the compounding amount is preferably 0.01 to 1.0 parts by weight, more preferably 0.05 to 0.8 parts by weight, based on 100 parts by weight of the total of components A and B. , and more preferably 0.08 to 0.6 parts by weight.

(E-3) Silicon flame retardant

In the present invention, the silicon compound used as a silicon-based flame retardant refers to a compound that improves flame retardancy through a chemical reaction during combustion. As the compound, various compounds conventionally proposed as flame retardants for aromatic polycarbonate resins can be used. It is considered that the silicon compound imparts a flame-retardant effect to the polycarbonate resin by combining itself or with components derived from the resin to form a structure during combustion, or by a reduction reaction when forming the structure. Therefore, it is preferable to contain a group having high activity in the above reaction. More specifically, it is preferable to contain a predetermined amount of at least one group selected from an alkoxy group and a hydrogen group (ie Si-H group). The content ratio of the group (alkoxy group, Si-H group) is preferably in the range of 0.1-1.2 mol/100g, more preferably in the range of 0.12-1 mol/100g, and still more preferably in the range of 0.15-0.6 mol/100g. This content ratio can be obtained by measuring the amount of hydrogen or alcohol generated per unit weight of the silicon compound by the alkali decomposition method. In addition, the alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, particularly preferably a methoxy group.

In general, the structure of a silicon compound is constituted by arbitrarily combining the following four siloxane units. Right now,

M unit: (CH ₃ ) ₃ SiO _1/2 , H(CH ₃ ) ₂ SiO _1/2 , H ₂ (CH ₃ )SiO _1/2 , (CH ₃ ) ₂ (CH ₂ ＝CH)SiO _1/2 , (CH ₃ ) ₂ (C ₆ H ₅ )SiO _1/2 , (CH ₃ )(C ₆ H ₅ )(CH ₂ =CH)SiO _1/2 and other monofunctional siloxane units;

Unit D: (CH ₃ ) ₂ SiO, H(CH ₃ )SiO, H ₂ SiO, H(C ₆ H ₅ )SiO, (CH ₃ )(CH ₂ =CH)SiO, (C ₆ H ₅ ) ₂ SiO and other difunctional siloxane units;

T unit: (CH ₃ )SiO _3/2 , (C ₃ H ₇ )SiO _3/2 , HSiO _3/2 , (CH ₂ =CH)SiO _3/2 , (C ₆ H ₅ )SiO _{3/2 ,} etc. of trifunctional siloxane units;

Q unit: a tetrafunctional siloxane unit represented by SiO ₂ .

The structures of silicon compounds used in silicon-based flame retardants specifically include structures represented by the following schematic formulas, namely, D _n , T _p , M _m D _n , M _m T _p , M _m Q _q , M _m D _n T _p , M _m D _n Q _q , M _m T _p Q _q , M _m D _n T _p Q _q , D _n T _p , D _n Q _q , D _n T _p Q _q . Among them, the preferred structure of the silicon compound is M _m D _n , M _m T _p , M _m D _n T _p , M _m D _n Q _q , and the more preferred structure is M _m D _n or M _m D _n T _p .

Here, the coefficients m, n, p, and q in the above schematic formulas are integers of 1 or more representing the degree of polymerization of each siloxane unit, and the sum of the coefficients in each schematic formula is the average degree of polymerization of the silicon compound. The average degree of polymerization is preferably in the range of 3-150, more preferably in the range of 3-80, still more preferably in the range of 3-60, particularly preferably in the range of 4-40. The more preferable the average degree of polymerization is in the range, the more excellent the flame retardancy is. Furthermore, a silicon compound containing a predetermined amount of aromatic groups as described later is also excellent in transparency and color.

In addition, when any one of m, n, p, and q is a value of 2 or more, the siloxane unit with this coefficient may be two or more siloxane units with different hydrogen atoms or organic residues to be bonded. alkane unit.

The silicon compound may have either a linear structure or a silicon compound having a branched structure. In addition, the organic residue bonded to a silicon atom is preferably an organic residue having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms. Specific examples of the organic residue include alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, and decyl; cycloalkyl groups such as cyclohexyl; aryl groups such as phenyl; and tolyl groups. Aralkyl etc. More preferred is an alkyl group, alkenyl group or aryl group having 1 to 8 carbon atoms. As the alkyl group, an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, and a propyl group is particularly preferable.

Furthermore, the silicon compound used as the silicon-based flame retardant preferably contains an aryl group. More preferable is a silicon compound having an aromatic group content ratio (aromatic group amount) represented by the following general formula (II) of 10 to 70% by weight (more preferably 15 to 60% by weight).

(In formula (II), X independently represent OH groups and monovalent organic residues with 1 to 20 carbon atoms; n represents an integer of 0 to 5. And in formula (II), when n is 2 or more , different types of X can be taken respectively.)

Silicon compounds used as silicon-based flame retardants may contain reactive groups in addition to the above-mentioned Si-H groups and alkoxy groups. Examples of such reactive groups include amino groups, carboxyl groups, epoxy groups, vinyl groups, Mercapto, and methacryloxy, etc.

As a silicon compound having a Si-H group, preferably, a silicon compound containing at least one of structural units represented by the following general formulas (III) and (IV):

(In formula (III) and formula (IV), Z ¹ to Z ³ independently represent a hydrogen atom, a monovalent organic residue with 1 to 20 carbon atoms, or a compound represented by the following general formula (V) ; α1～α3 independently represent 0 or 1; m1 represents an integer of 0 or more than 1; and, in formula (III), when m1 is more than 2, its repeating unit can respectively take a plurality of repeating units different from each other .)

(In formula (V), Z ⁴ to Z ⁸ each independently represent a hydrogen atom and a monovalent organic residue with 1 to 20 carbon atoms; α4 to α8 each independently represent 0 or 1; m2 represents 0 or more than 1 Integer; and, in formula (V), when m2 is more than 2, its repeating unit can take respectively a plurality of repeating units different from each other.)

Among the silicon compounds used in silicon-based flame retardants, as the silicon compound having an alkoxy group, for example, at least one compound selected from the compounds represented by the general formula (VI) and the general formula (VII):

(In formula (VI), ^β1 represents a vinyl group, an alkyl group with 1 to 6 carbon atoms, a cycloalkyl group with 3 to 6 carbon atoms, an aryl group and an aralkyl group with 6 to 12 carbon atoms ; γ ¹ , γ ² , γ ³ , γ ⁴ , γ ⁵ and γ ⁶ represent alkyl groups and cycloalkyl groups with 1 to 6 carbon atoms, and aryl and aralkyl groups with 6 to 12 carbon atoms, Wherein at least one group is an aryl group or an aralkyl group; δ ¹ , δ ² and δ ³ represent an alkoxy group with 1 to 4 carbon atoms.)

(In formula (VII), β ² and β ³ represent a vinyl group, an alkyl group with 1 to 6 carbon atoms, a cycloalkyl group with 3 to 6 carbon atoms, and an aryl group with 6 to 12 carbon atoms and aralkyl groups; γ ⁷ , γ ⁸ , γ ⁹ , γ ¹⁰ , γ ¹¹ , γ ¹² , γ ¹³ and γ ¹⁴ represent alkyl groups with 1 to 6 carbon atoms and cycloalkanes with 3 to 6 carbon atoms group, aryl group and aralkyl group with 6 to 12 carbon atoms, at least one of which is aryl or aralkyl group; δ ⁴ , δ ⁵ , δ ⁶ and δ ⁷ represent C alkoxy.)

When a silicon-based flame retardant is used as a flame retardant, the compounding amount of the silicon-based flame retardant is preferably 0.1 to 5 parts by weight, more preferably 0.2 to 4 parts by weight, based on 100 parts by weight of the total of components A and B. More preferably, it is 0.3-3 weight part.

The above-mentioned flame retardants (E-1), (E-2) and (E-3) may be used alone or in combination of two or more.

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

The fluorine-containing anti-dripping agent (component F) used in the present invention is a fluorine-containing compound that can prevent solution dripping during combustion and further improve flame retardancy. Representative examples include fibril-forming of polytetrafluoroethylene. In addition, polytetrafluoroethylene may be abbreviated as "PTFE" below sometimes. PTFE having fibril-forming ability has an extremely high molecular weight, and tends to bond PTFE to form fibers by external action such as shear force. As the molecular weight, the number average molecular weight determined from the standard specific gravity is 1 million to 10 million, preferably 2 million to 9 million. In addition to using the PTFE in a solid form, PTFE in the form of an aqueous dispersion can also be used. In addition, in order to improve the dispersibility in the resin, and in order to obtain more excellent flame retardancy and mechanical properties, the PTFE having the fibril-forming ability can also be used as a mixed form of PTFE mixed with other resins.

Commercially available products of the PTFE having fibril-forming ability include, for example, Teflon (registered trademark) 6J of DUPONT-MITSUI FLUOROCHEMICALS COMPANY, LTD, Polyflon MPA FA500 and F-201L manufactured by DAIKIN Industry Co., Ltd. As a commercial product of an aqueous dispersion of PTFE, representative examples include Fluon AD-1 and AD-936 manufactured by Asahi-ICI Fluoropolymers Co., Ltd., and Fluon D-1 and D-2 manufactured by DAIKIN Industry Co., Ltd. , Teflon (registered trademark) 30J manufactured by DUPONT-MITSUI FLUOROCHEMICALS COMPANY, LTD.

As PTFE in a mixed form, PTFE in a mixed form obtained by the following method can be used: (1) an aqueous dispersion of PTFE and an aqueous dispersion or solution of an organic polymer are mixed and co-precipitated to obtain a co-agglomerated mixture Method (the method described in JP Unexamined No. 60-258263 communique, JP Unexamined No. 63-154744 communique, etc.); (2) the method of mixing the aqueous dispersion of PTFE with the dried organic polymer particles (JP (3) the method of uniformly mixing the aqueous dispersion of PTFE and the organic polymer particle solution, and simultaneously removing the respective media from the mixture (JP Patent Application Publication No. 06-220210 , the methods described in JP Patent Publication No. 08-188653 etc.); (4) the method of polymerizing monomers for forming organic polymers in an aqueous dispersion of PTFE (recorded in JP Patent Publication No. 9-95583 method); and (5) after uniformly mixing the aqueous dispersion of PTFE and the organic polymer dispersion, further polymerizing vinyl monomers in the mixed dispersion, and then obtaining the method of the mixture (JP Patent Publication No. 11-29679 method described in et al.). Commercially available products of these mixed forms of PTFE include [metablen A3800] (trade name) manufactured by Mitsubishi Rayon Co. Ltd., [BLENDEX B449] (trade name) manufactured by GE Specialty Chemicals, and the like.

As the ratio of PTFE in the mixed form, the content ratio of PTFE in 100% by weight of the PTFE mixture is preferably 1 to 60% by weight, more preferably 5 to 55% by weight. When the content ratio of PTFE is within this range, good dispersibility of PTFE can be realized.

(about content of each ingredient)

The resin composition of the present invention has a component A content of 99 to 1% by weight, preferably 98 to 20% by weight, more preferably 97 to 40% by weight, and particularly preferably 95 to 60% by weight, and the component B content is 1 to 99% by weight, preferably 2 to 80% by weight, more preferably 3 to 60% by weight, particularly preferably 5 to 40% by weight.

When the content of component A is less than 1% by weight, the mechanical strength such as impact strength and heat resistance are insufficient, and when it exceeds 99% by weight, the formability decreases, which is not preferable.

Content of C component is 0.1-10 weight part with respect to the total 100 weight part of A component and B component, Preferably it is 0.5-9 weight part, More preferably, it is 1-8 weight part. When it is less than 0.1 parts by weight, flow lines or impact properties are insufficient, and when it exceeds 10 parts by weight, heat resistance or flame retardancy will remarkably decrease, which is not preferable.

The content of D component is preferably 0.1 to 50 parts by weight, more preferably 0.5 to 40 parts by weight, and still more preferably 1 to 30 parts by weight, based on 100 parts by weight of the total of A component and B component. When the content of component D exceeds 50 parts by weight, it is not preferable because a decrease in fluidity or a significant decrease in impact strength will occur.

The content of the E component is preferably 0.001 to 25 parts by weight, more preferably 0.05 to 23 parts by weight, and still more preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the total of the A component and the B component. When it is less than 0.001 parts by weight, the flame retardancy is insufficient, and when it exceeds 25 parts by weight, heat resistance or mechanical strength will remarkably decrease, which is not preferable.

The content of component F is preferably 0.05 to 2 parts by weight, more preferably 0.07 to 1.5 parts by weight, and still more preferably 0.1 to 1 part by weight, based on 100 parts by weight of the total of components A and B. When the content of the F component is less than 0.05 parts by weight, the flame retardancy is insufficient, and when it exceeds 2 parts by weight, mechanical properties such as impact strength will fall, which is not preferable.

(about other additives)

(i) Phosphorus stabilizer

Examples of the phosphorus-based stabilizer include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, esters thereof, tertiary phosphine, and the like.

Specific phosphite compounds include, for example, triphenyl phosphite, tris(nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, tris(decyl) Octyl) phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, mono Decyl diphenyl phosphite, monooctyl diphenyl phosphite, tris (diethylphenyl) phosphite, tris (diisopropylphenyl) phosphite, tris (di-n-butyl Phenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, tris(2,6-di-tert-butylphenyl) phosphite, distearyl pentaerythritol diphosphite , bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis(2,6- Di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, bis{2,4-bis(1-methyl-1-phenylethyl)phenyl} pentaerythritol diphosphite, phenyl bis Phenol A pentaerythritol diphosphite, bis(nonylphenyl)pentaerythritol diphosphite, dicyclohexylpentaerythritol diphosphite, and the like.

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

Examples of the phosphate compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, Diphenyl mono-o-biphenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, etc., preferably triphenyl phosphate and trimethyl phosphate.

As the phosphonite compound (phosphonite), tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite, tetrakis(2,4-di-tert-butylphenyl) Butylphenyl)-4,3'-biphenylene diphosphonite, tetrakis(2,4-di-tert-butylphenyl)-3,3'-biphenylene diphosphonite, Four (2,6-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite, four (2,6-di-tert-butylphenyl)-4,3'-biphenylene Phenyl diphosphonite, tetrakis(2,6-di-tert-butylphenyl)-3,3'-biphenylene diphosphonite, bis(2,4-di-tert-butylphenyl) —4-phenyl-phenylphosphonite, bis(2,4-di-tert-butylphenyl)-3-phenyl-phenylphosphonite, bis(2,6-di-n-butylphenyl base)-3-phenyl-phenylphosphonite, bis(2,6-di-tert-butylphenyl)-4-phenyl-phenylphosphonite, bis(2,6-di-tert-butyl phenyl)-3-phenyl-phenylphosphonite, etc. Among them, preferred tetrakis(di-tert-butylphenyl)-biphenylene diphosphonite, bis(di-tert-butylphenyl)-phenyl-phenylphosphonite, more preferably tetrakis(2,4 -di-tert-butylphenyl)-biphenylene diphosphonite, bis(2,4-di-tert-butylphenyl)-phenyl-phenylphosphonite. The phosphonite compound can be used in combination with the above-mentioned phosphite compound having two or more aryl group substitutions in the alkyl group, and this method is preferably used.

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

Examples of tertiary phosphine include triethylphosphine, tripropylphosphine, tributylphosphine, trioctylphosphine, tripentylphosphine, dimethylphenylphosphine, dibutylphenylphosphine, diphenylmethane Base phosphine, diphenyl octyl phosphine, triphenyl phosphine, tri-p-tolyl phosphine, trinaphthyl phosphine and diphenyl benzyl phosphine, etc. A particularly preferred tertiary phosphine is triphenylphosphine.

Not only one kind of the above-mentioned phosphorus stabilizers may be used, but two or more kinds may be used in combination. Among the above-mentioned phosphorus stabilizers, phosphonite compounds or phosphite compounds represented by the following general formula (VIII) are preferable.

(In formula (VIII), R and R' represent an alkyl group having 6 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, which may be the same as or different from each other).

As described above, tetrakis(2,4-di-tert-butylphenyl)-biphenylene diphosphonite is preferable as the phosphonite compound. As a stabilizer mainly composed of this phosphonite, Sandostab P-EPQ (trademark, manufactured by Clariant) and Irgafos P-EPQ (trademark, manufactured by CIBASPECIALTY CHEMICALS) are commercially available, and both can be used.

In addition, in the above formula (VIII), more preferred phosphite compounds are distearoyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2 , 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, and bis{2,4-bis(1-methyl-1-phenylethyl)phenyl}pentaerythritol diphosphite .

As the distearoyl pentaerythritol diphosphite, there are commercially available Adecastab PEP-8 (trademark, manufactured by Asahi Denka Co., Ltd.) and JPP681S (trademark, manufactured by Johoku Chemical Co., Ltd.), and all of them can be used. Commercially available bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite includes Adecastab PEP-24G (trademark, manufactured by Asahi Denka Co., Ltd.), AlkanoxP-24 (trademark, manufactured by Great Lakes Co., Ltd. ), Ultranox P626 (trademark, manufactured by GE Specialty Chemicals), Doverphos S-9432 (trademark, manufactured by Dover Chemical), and Irgaofos 126 and 126FF (trademark, manufactured by CIBA SPECIALTYCHEMICALS), etc., can be used. As bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, Adecastab PEP-36 (trademark, manufactured by Asahi Denka Co., Ltd.) is commercially available, and it can be used easily. In addition, commercially available as bis{2,4-bis(1-methyl-1-phenylethyl)phenyl}pentaerythritol diphosphite is Adecastab PEP-45 (trademark, manufactured by Asahi Denka Co., Ltd. ), and Doverphos S-9228 (trademark, manufactured by Dover Chemical Company), can be used.

(ii) Hindered phenolic antioxidants

As the hindered phenol 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 -6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-methylenebis(2,6-di-tert-butyl phenol), 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-dimethylbenzyl-bis(6-α-methylbenzyl-p-cresol) , 2,2'-ethylene-bis(4,6-di-tert-butylphenol), 2,2'-butylene-bis(4-methyl-6-tert-butylphenol), 4,4' -Butylene-bis(3-methyl-6-tert-butylphenol), triethylene glycol-N-bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid Esters, 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 -6-tert-butylphenol), bis(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4,4'-dithiobis(2,6-di-tert-butylphenol), 4,4'-Trithiobis(2,6-di-tert-butylphenol), 2,2-thiodivinylbis[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' -Hexamethylene bis-(3,5-di-tert-butyl-4-hydroxyhydrocinnamamide), 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 Base-4-hydroxybenzyl) isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 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-hydroxy5-methylbenzene base) 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, etc.

Among the above-mentioned compounds, the present invention preferably uses 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) propionyl oxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5,5]undecane. Especially preferred is the use of 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 above-mentioned hindered phenolic antioxidants can be used alone or in combination of two or more.

It is preferable to mix any one of a phosphorus stabilizer and a hindered phenolic antioxidant. It is especially preferable to use them in combination. The amount of the phosphorus stabilizer and the hindered phenolic antioxidant is 0.001 to 3 parts by weight, preferably 0.005 to 2 parts by weight, more preferably 0.01 to 1 part by weight, based on 100 parts by weight of the total of components A and B. . When used in combination, 0.01 to 0.3 parts by weight of a phosphorus-based stabilizer and 0.01 to 03 parts by weight of a hindered phenolic antioxidant are preferably blended with respect to a total of 100 parts by weight of components A and B.

(iii) Release agent

In the resin composition of the present invention, it is preferable to further compound a mold release agent in order to improve productivity during molding or reduce deformation of molded articles. A known mold release agent can be used as the mold release agent. Examples include saturated fatty acid esters, unsaturated fatty acid esters, polyolefin waxes (polyethylene waxes, 1-olefin polymers, etc., and those 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 esters are esters of aliphatic alcohols and aliphatic carboxylic acids. 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 dodecyl alcohol, tetradecyl alcohol, cetyl alcohol, octadecyl alcohol, eicosyl alcohol, tetracyl alcohol, hexadecanyl alcohol, and triacyl alcohol. wait. Examples of the polyhydric alcohol include pentaerythritol, dipentaerythritol, tripentaerythritol, polyglycerol (triglycerol to hexaglycerol), di(trimethylol)propane, xylitol, sorbitol, and mannitol. Among the fatty acid esters of the present invention, polyhydric alcohols are more preferred.

On the other hand, the aliphatic carboxylic acid preferably has 3 to 32 carbon atoms, particularly preferably an aliphatic carboxylic acid having 10 to 22 carbon atoms. Examples of the aliphatic carboxylic acid include capric acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid ( Stearic acid), nonadecanic acid, behenic acid, eicosanic acid and behenic acid and other saturated aliphatic carboxylic acids and palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, di Unsaturated aliphatic carboxylic acids such as decapentaenoic acid and cetenoic acid. Among the above, the aliphatic carboxylic acid having 14 to 20 carbon atoms is preferable as the aliphatic carboxylic acid. Among them, saturated aliphatic carboxylic acids are preferred. Stearic acid and palmitic acid are particularly preferred.

Since the above-mentioned aliphatic carboxylic acids such as stearic acid and palmitic acid are usually made of animal fats represented by tallow or lard, and natural oils such as vegetable fats represented by palm oil or sunflower oil, etc. Class production, so these aliphatic carboxylic acids are usually mixtures containing other carboxylic acid components with different numbers of carbon atoms. Therefore, in the production of the fatty acid ester of the present invention, also from these natural oils and fats, it is preferable to use an aliphatic carboxylic acid in the form of a mixture containing other carboxylic acid components, and it is particularly preferable to use stearic acid or palmitic acid.

Fatty acid esters may be any of partial esters and full esters (full esters). However, in partial esters, the hydroxyl value is generally high, and it is easy to induce decomposition of the resin at high temperature, so full fat is more preferable. The acid value in the fatty acid ester of the present invention is preferably 20 or less, more preferably 4-20, and still more preferably 4-12 from the viewpoint of thermal stability. In addition, the acid value can actually be 0. Moreover, it is preferable that the hydroxyl value of a fatty acid ester is 0.1-30. Furthermore, the iodine value is preferably 10 or less. The iodine value can actually be 0. These properties can be obtained according to the method stipulated in JIS K 0070.

The content of the mold release agent is preferably 0.005 to 2 parts by weight, more preferably 0.01 to 1 part by weight, and still 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 polycarbonate resin composition has good mold release properties and roll release properties. In particular, the fatty acid ester in this content can provide a polycarbonate resin composition having excellent mold release properties and roll-off type without impairing good color.

(iv) UV absorber

The resin composition of the present invention may further contain an ultraviolet absorber. Since the resin composition of this invention has excellent transparency, it is very suitable for the use which transmits light.

Specific examples of the ultraviolet absorber include benzophenones, such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4 -octyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methyl Oxygen-5-sulfoxy trihydrogen compound benzophenone (2-hidrokishi-4-metokish-5-sulhokishitrihidridereittobenzophenone), 2,2'-dihydroxy-4-methoxydiphenone Benzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy -4,4'-dimethoxy-5-sodium sulphonate benzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2-hydroxy-4- n-dodecyloxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, etc.

Benzotriazoles as ultraviolet absorbers include, for example, 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzene Triazole, 2-(2-hydroxy-3,5-dicumylphenyl)phenylbenzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5 -Chlorobenzotriazole, 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol ], 2-(2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzotriazole Azole, 2-(2-hydroxy-3,5-di-tert-pentylphenyl) 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-benzotriazole phenyl), 2,2'-p-phenylene bis(1,3-benzoxazin-4-one), 2-[2-hydroxyl-3-(3,4,5 , 6-tetrahydrophthalamidomethyl)-5-methylphenyl]benzotriazole, 2-(2'-hydroxy-5-methacryloyloxyethylphenyl)-2H-benzene A copolymer of triazole and a vinyl monomer that can be copolymerized with the monomer or 2-(2'-hydroxyl-5-acryloyloxyethylphenyl)-2H-benzotriazole and a monomer that can be copolymerized with the monomer Polymers having a 2-hydroxyphenyl-2H-benzotriazole skeleton, such as copolymers of vinyl monomers that can be copolymerized.

Hydroxyphenyl triazines as ultraviolet absorbers include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxyphenol, 2-(4 , 6-diphenyl-1,3,5-triazin-2-yl)-5-methyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazin-2- base)-5-ethyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-propyloxyphenol and 2-(4,6-di Phenyl-1,3,5-triazin-2-yl)-5-butyloxyphenol, etc. Further, among the above-mentioned exemplary compounds such as 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-hexyloxyphenol, etc. The phenyl group becomes 2,4-dimethylphenyl compound.

Cyclic imino esters as ultraviolet absorbers include, for example, 2,2'-p-phenylene bis(3,1-benzoxazin-4-one), 2,2'-(4, 4'-diphenylene)bis(3,1-benzoxazin-4-one) and 2,2'-(2,6-naphthalene)bis(3,1-benzoxazin-4-one) )wait.

In addition, as cyanoacrylates as ultraviolet absorbers, specific examples include 1,3-bis-[(2'-cyano-3',3'-diphenylacryloyl)oxy]-2, 2-bis-[(2-cyano-3,3-diphenylacryloyl)oxy]methylpropane and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl) Oxygen] benzene, etc.

Furthermore, the above-mentioned ultraviolet absorber may also be obtained by using a monomer compound structure capable of free radical polymerization, and the ultraviolet absorbing monomer and/or light-stable monomer having a hindered amine structure and (meth)acrylic alkyl Polymerized ultraviolet absorbers obtained by copolymerizing monomers such as base esters. Preferred examples of the above-mentioned ultraviolet absorbing monomer include (meth)acrylic acid esters containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic imidate skeleton, and cyanoacrylic acid ester substituents. Compounds with an ester backbone.

Among the above, benzotriazoles and hydroxyphenyl triazines are preferably used in consideration of ultraviolet absorbing ability, and cyclic imide esters and cyanides are preferably used in consideration of heat resistance and color (transparency). base acrylates. The above ultraviolet absorbers may be used alone or in combination of two or more.

The content of the ultraviolet absorber is 0.01 to 2 parts by weight, preferably 0.02 to 2 parts by weight, more preferably 0.03 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. .

(v) Dyed pigment

The resin composition of the present invention may further contain various dyes and pigments to provide molded articles exhibiting various appearances. Since the resin composition of this invention has excellent transparency, it is very suitable for the use which transmits light. Therefore, for example, by blending a fluorescent whitening agent, higher light transmittance or natural transparency can be imparted to the resin composition of the present invention, and by blending a fluorescent whitening agent or other luminescent fluorescent dyes, it is possible to impart More excellent appearance effect of luminous color. In addition, an extremely small amount of dye pigment can provide a resin composition with subtle coloring and higher transparency.

Fluorescent dyes (including fluorescent whitening agents) used in the present invention include, for example, coumarin-based fluorescent dyes, benzopyran-based fluorescent dyes, perylene-based fluorescent dyes, anthraquinone-based fluorescent dyes, thioindigo-based fluorescent dyes, etc. dyes, xanthene-based fluorescent dyes, xanthone-based fluorescent dyes, thioxanthene-based fluorescent dyes, thioxanthone-based fluorescent dyes, thiazide-based fluorescent dyes, diaminostilbene-based fluorescent dyes, and the like. Among them, coumarin-based fluorescent dyes, benzopyran-based fluorescent dyes, and perylene-based fluorescent dyes, which have good heat resistance and are less deteriorated during molding processing of polycarbonate resins, are preferable.

Examples of dyes other than the above-mentioned bluing agent and fluorescent dye include ferrocyanides such as perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, and Prussian blue. Perionone-based dyes, quinoline-based dyes, quinacridone-based dyes, dioxazine-based dyes, isoindolinone-based dyes, phthalocyanine-based dyes, and the like. Furthermore, the resin composition of the present invention can obtain a better metallic color by mixing a metallic pigment. Among various platy fillers, those having a metal coating or a metal oxide coating are preferable as the metal pigment.

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 resin composition of the present invention, in addition to the above-mentioned phosphorus stabilizer and hindered phenolic antioxidant, other heat stabilizers may also be blended. The other heat stabilizers are preferably used in combination with any one of these stabilizers and antioxidants, and are particularly preferably used in combination with both. As this other thermal stabilizer, for example, a lactone stabilizer represented by a reaction product of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene (about The details of this stabilizer are described in JP-A-7-233160). This compound is commercially available as Irganox HP-136 (trademark, manufactured by CIBA SPECIALTY CHEMICALS), and this compound can be used. In addition, there are commercially available stabilizers in which this compound is mixed with various phosphite compounds and hindered phenolic compounds. For example, Irganox HP-2921 of the company mentioned above is preferably mentioned. In the present invention, the previously mixed stabilizer can also be used. The content of the lactone stabilizer is preferably 0.0005 to 0.05 parts by weight, more preferably 0.001 to 0.03 parts by weight, based on 100 parts by weight of the total of components A and B.

In addition, examples of other stabilizers include pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-laurylthiopropionate), glycerol-3-stearylthiopropionate, and the like. sulfur-containing stabilizers. This stabilizer is particularly effective when the resin composition is used 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.

(vii) White pigments for high light reflection

In the resin composition of the present invention, a light reflection effect can be imparted by blending a white pigment for high light reflection. As the white pigment, titanium dioxide (especially titanium dioxide treated with an organic surface treatment agent such as organosiloxane) pigment is preferable. The content of the white pigment for high light reflection is preferably 3 to 30 parts by weight, more preferably 8 to 25 parts by weight, based on 100 parts by weight of the total of A component and B component. In addition, it is preferable to use two or more kinds of white pigments for high light reflection in combination.

(viii) Other additives

The resin composition of the present invention may contain thermoplastic resins other than components A and B, other flow modifiers, antibacterial agents, dispersants such as liquid paraffin, photocatalytic antifouling agents, heat absorbers, and photochromic agent etc.

Examples of thermoplastic resins other than components A and B include polymethyl methacrylate resins (PMMA resins), cyclic polyolefin resins, polylactic acid resins, polycaprolactone resins, thermoplastic fluororesins (for example, Polyvinylidene fluoride resin is a representative), and polyolefin resin (polyethylene resin, polypropylene resin, etc.).

(Manufacture of resin composition)

When producing the resin composition of this invention, arbitrary methods can be employ|adopted. For example, pre-mixing devices such as V-type mixers, Henschel mixers, chemical power devices, and extrusion mixers can be used to fully mix components from A to F and any other additives, and then use extrusion as needed. A method in which the pre-mixture is granulated by a granulator or an agglomerator, melt-kneaded by a melt-kneader typified by a vented twin-screw extruder, and then granulated by a granulator or the like. .

In addition, a method of separately supplying each component to a melt-kneader typified by a vented twin-screw extruder, or a method of premixing a part of each component and then separately mixing it with the remaining components can also be mentioned. The method of supplying to the melt kneader etc. As a method of premixing a part of each component, the method of mixing with the polycarbonate resin of A component or directly supplying to an extruder after premixing components other than A component is mentioned, for example.

As a pre-mixing method, for example, when a powdery substance is contained as the A component, a part of the powder is mixed with the additive to prepare a master compound (Master) of the additive diluted by the powder.バッチ), the method of reusing the master compound. Moreover, the method etc. which supply one component independently from the middle of a melt extruder are also mentioned. Furthermore, when there is a liquid substance in the compounded component, what is called a liquid injection device or a liquid addition device can be used for supply to a melt extruder.

As the extruder, it is preferable to use an extruder having a vent that can remove moisture in the raw material or volatile gas generated by melting and kneading the resin. Preferably, a vacuum pump is provided at the exhaust port to efficiently exhaust the generated moisture or volatile gas to the outside of the extruder. In addition, a filter for removing impurities and the like mixed in the extruded raw material is provided in the area before the die part of the extruder, whereby impurities can also be removed from the resin composition. As this filter screen, a metal screen, a screen changer, a sintered metal plate (disc filter, etc.), etc. are mentioned.

Examples of the melt-kneading machine include a Banbury kneader, 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 may be directly cut and pelletized, or after being formed into strands, the strands may be cut and pelletized by a pelletizer. In addition, when pelletizing, if it is necessary to reduce the influence of external factors such as dust, it is preferable to clean the ambient air around the extruder. Furthermore, in the production of the particles, the narrowing of the particle shape distribution, the reduction of short cuts (miscuts), and the transport or delivery can be appropriately performed by various methods that have been proposed for polycarbonate resins for optical discs. The reduction of tiny powder particles generated during the process and the reduction of air bubbles (vacuum bubbles) generated inside strands or particles. According to these methods, it is possible to realize high-cycle molding and reduce the rate of occurrence of defects such as silver spots. In addition, the particle shape may be a general shape such as a cylinder, a prism, and a sphere, and is more preferably a cylinder. Preferably, the diameter of the cylinder is 1-5 mm, more preferably 1.5-4 mm, even more preferably 2-3.3 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.

In addition, in the form of containing the E component of the present invention at a high concentration in advance, the A component and the B component are melt-kneaded with a melt kneader, and pelletized to produce a master compound, and the master rubber The method of mixing the ingredients with the remaining A component and other additives, and granulating them with a melt kneader.

(Molded article formed from the resin composition of the present invention)

The resin composition of the present invention is usually molded by injection molding the pellets produced as above to produce various products. In the injection molding, not only ordinary molding methods but also injection compression molding, injection press molding, gas-assisted injection molding, foam molding (including molding by supercritical fluid injection), insert molding, etc. , In-Mold Coating molding, thermal insulation mold molding, rapid heating and cooling mold molding, two-color molding, sandwich molding, and ultra-high-speed injection molding, etc. The advantages of these various forming methods are well known. In addition, molding can choose any one of the cold runner method and the hot runner method.

The resin composition of the present invention can be utilized in the form of various extrusion moldings, sheets, films, etc. by extrusion molding. In addition, blow molding, calendering, casting, and the like can also be used for sheet or film molding. Moreover, it can also be molded into a heat-shrinkable tube by performing a specific stretching operation. In addition, the resin composition of the present invention can also be produced as a molded article by rotational molding, blow molding, or the like.

As a specific example of a molded article using the resin composition of the present invention, it is suitably used in applications such as internal parts or casings of OA equipment and home electric appliances. Examples of these products include computers, notebook computers, CRT monitors, printers, portable terminals, mobile phones, copiers, facsimile machines, recording media (CD, CD-ROM, DVD, PD, FDD, etc.) drives, parabolic antennas ( parabola antenna), electric tools, VTR, TV, iron, hair dryer, rice cooker, microwave oven, audio equipment, audio equipment such as audio/laserdisc/CD, lighting equipment, refrigerator, air conditioner, typewriter, word processor, etc. The resin product formed from the flame-retardant resin composition of this invention can be used for various members, such as these frames. In addition, examples of other resin products include automobile parts such as guide plate parts, car navigation parts, and car audio parts.

The inventors of the present invention currently believe that the best embodiment of the present invention is an embodiment in which the preferred ranges of the above-mentioned requirements are combined. For example, representative examples thereof are described in the following Examples. Of course, the present invention is not limited to these embodiments.

Example

Next, the present invention will be described in more detail by way of examples. Unless otherwise specified, "parts" in the examples represent "parts by weight", and "%" represents "% by weight". In addition, evaluation was performed by the following method.

(Evaluation of resin composition)

(i) Flame retardancy: A flame test was performed according to UL Standard 94 using a test piece having a thickness of 1.5 mm.

In addition, the grade of flame retardancy is preferably V-1 grade or higher.

(ii) Charpy impact strength:

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

(iii) heat resistance

Determination of deflection temperature under load according to ISO 75-1 and 75-2. In addition, the measurement was implemented with a load of 1.80 MPa.

(iv) Liquidity

Using an injection molding machine (SG150U, manufactured by Sumitomo Heavy Industries, Ltd.), the flow length of the Archimedes spiral with a channel thickness of 2 mm and a channel width of 8 mm was measured. It is carried out under the conditions that the cylinder temperature is 260°C, the mold temperature is 70°C, and the injection pressure is 98MPa.

(v) Appearance

Mold the notebook computer frame moldings shown in Figures 1 to 3, and check whether there is linear color unevenness (merge line A) on the extension line of the welded part and whether there is linear color from the boss as the starting point Uneven (confluence pattern B).

○: No uneven color

×: Color unevenness occurs

Examples 1-19, Comparative Examples 1-10

According to the compositions shown in Table 1 to Table 3, the mixture is supplied from the first supply port of the extruder, and the mixture is composed of FR-1 (phosphate ester) except E component, D component (reinforcing filler) and B component (ABS- 1. Ingredients other than ABS-2, ABS-3, ABS-4). The mixture is obtained by mixing the following premix of (i) and other ingredients in a V-blender. That is, (i) is a mixture of component F (fluorine-containing anti-dripping agent) and an aromatic polycarbonate component A, wherein the components F and A are added so that the component F content becomes 2.5% by weight Put the mixture in a polyethylene bag and shake the bag as a whole to mix it evenly. When component B (ABS-1, ABS-2, ABS-3, ABS-4) and component D (reinforcing filler) are contained, use a side feeder and supply from the second supply port. Furthermore, when adding FR-1 of E component, in the state of heating to 80°C, use a liquid injection device (HYM-JS-08, manufactured by Fuji Technology Industries Co., Ltd.), from the third supply port in the middle of the cylinder (located between the first supply port and the exhaust port), supply to the extruder and adjust to a predetermined ratio. The liquid injection device was set to quantitative supply, and the supply of other raw materials was precisely measured by a meter (CWF, manufactured by Kubota Corporation). Extrude using a vented twin-screw extruder (5BW-3V, (strain) Japan Steel Works TEX30α-38) with a diameter of 30mmΦ, and the number of rotations of the screw is 150rpm, the extrusion rate is 20kg/h, exhaust Particles were obtained by melt-kneading at a vacuum degree of 3 kPa. In addition, the extrusion temperature was 260° C. from the first supply port to the die portion.

The obtained granules were dried by a hot air circulation dryer at 80-90°C for 6 hours, and then passed through an injection molding machine to form test pieces for evaluation (according to UL94, ISO179, ISO75-1 and ISO 75-2).

In addition, the content of each component represented by the code|symbol in Tables 1-3 is as follows.

(A component)

PC-1: Aromatic polycarbonate resin (パンライト L-1225WP, polycarbonate resin powder with a viscosity average molecular weight of 22,500 produced from bisphenol A and phosgene by a common method, manufactured by Teijin Chemicals Co., Ltd.)

PC2: Aromatic polycarbonate resin (パンライト L-1225WX, a polycarbonate resin powder with a viscosity average molecular weight of 19,700 produced from bisphenol A and phosgene by a common method, manufactured by Teijin Chemicals Co., Ltd.)

(B component)

ABS-1: ABS resin (CLARAS _CHICK SXH-330 (trade name), butadiene rubber component about 17.5% by weight, rubber weight-average particle size 0.40 μm, manufactured by emulsion polymerization, manufactured by Nippon A&L Co., Ltd.)

ABS-2: ABS resin (UT-61 (trade name), about 14% by weight of butadiene rubber, rubber weight-average particle size of 0.56 μm, manufactured by bulk polymerization, manufactured by Nippon A&L Co., Ltd.)

ABS-5: ABS resin produced by emulsion polymerization (CHT (trade name), rubber component made of polybutadiene about 58% by weight, rubber weight average particle size 0.31 μm, manufactured by CHEIL INDUSTRY INC)

(C component)

MBS-1: core-shell type graft copolymer (a graft copolymer of 70% by weight of butadiene rubber in the core and 30% by weight of styrene and methyl methacrylate in the shell produced by emulsion polymerization, The weight-average particle size of the rubber component is 0.32 μm)

MBS-2: core-shell graft copolymer (a graft copolymer of 70% by weight of butadiene rubber in the core and 30% by weight of styrene and methyl methacrylate in the shell produced by emulsion polymerization, The weight-average particle size of the rubber component is 0.41 μm)

MBS-3: core-shell type graft copolymer (Pararoid EXL-2678 (trade name), the core is 60% by weight of polybutadiene, and the shell is a graft of 40% by weight of styrene and methyl methacrylate Copolymer, the weight average particle diameter of the rubber component is 0.35 μm, manufactured by emulsion polymerization, manufactured by Rohm and Haas)

(Component D)

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

Talc: Talc (HST0.8 (trade name), manufactured by Hayashi Kasei Co., Ltd.)

Mica: Muscovite (A-41 (trade name), manufactured by Yamaguchi Mica Industry Co., Ltd.)

(Component E)

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

FR-2: Potassium perfluorobutane sulfonate (Megafact F-114P (trade name), manufactured by Dainippon Ink & Chemicals Co., Ltd.)

FR-3: Organosiloxane flame retardant containing Si-H group, methyl group and phenyl group (X-40-2600J (trade name), manufactured by Shin-Etsu Chemical Co., Ltd.)

(F component)

PTFE: Polytetrafluoroethylene (polyflon MP FA500 (trade name), manufactured by Daikin Industries, Ltd.)

(other ingredients)

ABS-3: ABS resin produced by emulsion polymerization (the rubber component composed of polybutadiene is about 15% by weight, and the rubber weight average particle size is 0.18 μm)

ABS-4: ABS resin produced by emulsion polymerization (the rubber component composed of polybutadiene is about 21% by weight, and the rubber weight average particle size is 2.2 μm)

MBS-4: core-shell type graft copolymer (metablenC-223A (trade name), the core is 70% by weight of polybutadiene, the shell is a graft copolymerization of 30% by weight of styrene and methyl methacrylate material, the weight average particle diameter of the rubber component is 0.23 μm, manufactured by Mitsubishi Rayon Co.Ltd)

MBS-5: core-shell graft copolymer (a graft copolymer of 70% by weight of butadiene rubber in the core and 30% by weight of styrene and methyl methacrylate in the shell produced by emulsion polymerization, The weight-average particle size of the rubber component is 0.55 μm)

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

SL900: Fatty acid ester mold release agent (Rikama-ru SL900 (trade name), manufactured by Riken Vitamin Co., Ltd.)

IRGX: phenolic heat stabilizer (IRGANOX1076 (trade name), manufactured by Ciba Specialty Chemicals)

TMP: Phosphate ester heat stabilizer (TMP (trade name), manufactured by Daihachi Chemical Industry Co., Ltd.)

As can be seen from the above table, by using the diene-based rubber with a specific weight-average particle size of the present invention, it is possible to obtain an excellent appearance with no flow lines at the welded part or the uneven thickness part, and at the same time have excellent impact characteristics and moldability. permanent polycarbonate resin composition.

Industrial Applicability

Since the resin composition of the present invention does not generate flow lines at welded portions or uneven thickness portions, and has excellent impact properties and moldability, it is widely applicable to OA applications and other various applications. Therefore, the industrial effect achieved by the present invention is very large.

Claims (8)

1. resin combination, it is characterized in that, comprise aromatic polycarbonate resin as the A composition, as the graft copolymer of B composition and as the core-shell grafting copolymer of C composition, and total 100 weight parts with respect to the B composition of the A composition of 99～1 weight % and 1～99 weight %, the C composition that contains 0.1～10 weight part

Wherein, described B composition contains rubber polymer, vinyl cyanide monomer and the aromatic vinyl monomer that the weight average particle diameter of rubber particles is 0.20～2.0 μ m; Described C composition is, at weight average particle diameter be 0.30～0.50 μ m the polydiene composition in the presence of, by emulsion polymerization, with (methyl) alkyl acrylate monomer or (methyl) alkyl acrylate monomer and can with the in addition copolymerization and obtaining of the monomeric mixture of this (methyl) alkyl acrylate monomer copolymerization.

2. resin combination as claimed in claim 1, wherein, described B composition obtains by letex polymerization, and, contain the polydiene of 1～40 weight % as rubber polymer.

3. resin combination as claimed in claim 1 or 2, wherein, described C composition is the core-shell grafting copolymer that contains the polydiene composition of 40～90 weight %.

4. as any described resin combination in the claim 1～3, wherein, contain inorganic filling material, and, contain the D composition of 0.1～50 weight part with respect to total 100 weight parts of A composition and B composition as the D composition.

5. resin combination as claimed in claim 4, wherein, described D composition is more than one the inorganic filling material that is selected from the group of being made up of talcum, mica and wollastonite.

6. as any described resin combination in the claim 1～5, wherein, contain as the fire retardant of E composition and as the fluorine-containing Antidrip agent of F composition, and total 100 weight parts with respect to A composition and B composition, contain the E composition of 0.001～25 weight part and the F composition of 0.05～2 weight part, described E composition is more than one the fire retardant that is selected from the group of being made up of phosphoric acid ester, sulfonic acid alkali metal salts or azochlorosulfonate acid alkali earth metal salt and silicon compounds.

7. as any described resin combination in the claim 1～6, wherein, the E composition is the phosphoric acid ester of following formula (I) expression:

In the formula (I), X is from dihydroxy compound deutero-divalent phenol residue, and described dihydroxy compound is the dihydroxy compound that is selected from the group of being made up of quinhydrones, Resorcinol, two (4-hydroxy diphenyl) methane, dihydroxyphenyl propane, dihydroxyl hexichol, dihydroxy naphthlene, two (4-hydroxy phenyl) sulfone, two (4-hydroxy phenyl) ketone and two (4-hydroxy phenyl) sulfide; N is 0～5 integer, and perhaps when for the mixture of the different phosphoric acid ester of n number, n is their mean value; R ⁴, R ⁵, R ⁶And R ⁷Represent independently respectively that from aryl deutero-one bivalent phenol residue described aryl is the aryl that is selected from the group of forming by phenol, cresols, xylenol, isopropyl-phenol, butylphenol and to cumyl phenol.

8. moulding product, it is to be formed by any described resin combination moulding in the claim 1～7.

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