JP2002220527A - Flame-retardant polycarbonate resin composition and molded part therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame-retardant polycarbonate resin composition excellent in fluidity, solvent resistance, and flame retardancy, and further capable of giving a molded part which is excellent in persistency of antistatic performance so as to avoid the attachment of dust to the part, and to provide the molded part therefrom. SOLUTION: This flame-retardant polycarbonate resin composition comprises (A) 50-97.95 wt.% of a polycarbonate resin, (B) 2-41 wt.% of a thermoplastic resin other than the polycarbonate resin, and (C) 0.05-3 wt.% of an acid-base- containing aromatic vinyl-based resin. The molded part for electrical/electronic equipment is given by molding the resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a flame-retardant polycarbonate resin composition and a molded article thereof. More specifically, the present invention relates to a flame-retardant polycarbonate resin composition having excellent fluidity, solvent resistance, and flame retardancy, and excellent durability of antistatic performance, and a molded product thereof.

[0002]

2. Description of the Related Art Polycarbonate resins are excellent in impact resistance, heat resistance, electrical characteristics, dimensional stability, etc., and are therefore used in office automation (OA) equipment,
It is widely used in various fields such as electric and electronic devices such as communication devices and home appliances, automobiles, and construction. This polycarbonate resin is itself a self-extinguishing resin, but when used as a material for OA equipment, information / communication equipment, electric / electronic equipment, etc., in order to further improve safety, the degree of flame retardancy Is required to be higher.

[0003] As a method of improving the flame retardancy of polycarbonate resins, halogen-based flame retardants such as halogenated bisphenol A and halogenated polycarbonate oligomers are used together with flame retardant aids such as antimony oxide because of their high flame retardant efficiency. Have been. However, in recent years,
Because of the large impact on the environment during safety and incineration of waste, there is a need for a flame retardant method using a halogen-free flame retardant. Therefore, when an organic phosphorus-based flame retardant, particularly an organic phosphate compound is blended as a non-halogen-based flame retardant, the organic phosphate ester compound is used because it has excellent flame retardancy and also acts as a plasticizer. A flame retardant polycarbonate resin composition has been proposed.

By the way, in order to make a polycarbonate resin flame-retardant using this organic phosphate compound,
It is necessary to mix the organic phosphate compound in a relatively large amount. Further, since the polycarbonate resin has a high molding temperature and a high melt viscosity, it is necessary to further increase the molding temperature to increase the fluidity in order to cope with a thinned and large-sized molded product. Therefore, this organic phosphate compound contributes to the flame retardancy, but is not always sufficient in the molding environment and the appearance of the molded product, such as adhering to the mold or generating gas during molding of the polycarbonate resin. There are cases. In addition, molded articles of the flame-retardant polycarbonate resin composition using the organophosphate compound have a problem in that the impact strength is reduced or the color is changed due to a high-temperature history or a high-temperature and high-humidity history.

In order to solve such a problem, Japanese Patent Application Laid-Open No. 50-98546 discloses a method in which a small amount of a metal salt of a polymeric aromatic sulfonic acid, for example, a sodium salt of polystyrene sulfonic acid is blended. It is proposed to make the resin flame-retardant. However,
If the polycarbonate resin is flame-retarded using polystyrene sulfonate sodium salt obtained by sulfonating polystyrene by a usual method and further neutralizing with sodium hydroxide, a material having excellent flame retardancy can be obtained. There is a drawback that poor appearance of a molded article is caused due to poor dispersibility of polystyrenesulfonic acid sodium salt.

In such a flame-retardant polycarbonate resin composition, there is a demand for the development of a flame-retardant molding material which maintains the characteristics of the polycarbonate resin. 8-1764
No. 25 proposes a resin composition in which an organic alkali metal salt or an organic alkaline earth metal salt and an organopolysiloxane are mixed with a polycarbonate resin.
Although this resin composition is excellent in flame retardancy and mechanical strength, a molded article obtained by molding the resin composition has a drawback that dust easily adheres to the surface thereof.

Further, Japanese Patent Application Laid-Open No. 11-172603 proposes a flame-retardant resin composition comprising a mixture of a metal salt of polystyrene sulfonic acid and various thermoplastic resins. As for the resin composition mainly composed of polyphenylene ether, a resin composition excellent in flame retardancy has been described, but the flame retardancy mainly composed of polycarbonate resin maintaining the inherent properties of polycarbonate resin has been shown. No description is given of the conductive resin composition.

For these reasons, the polycarbonate resin maintains the excellent characteristics, and has excellent fluidity, solvent resistance, and flame retardancy, and also has excellent durability of antistatic performance without the attachment of dust. There is a demand for the development of a flame-retardant polycarbonate resin composition capable of obtaining a molded article.

[0009]

According to the present invention, it is possible to obtain a molded article which is excellent in fluidity, solvent resistance and flame retardancy, and which has excellent antistatic performance without adhering dust. An object of the present invention is to provide a flame-retardant polycarbonate resin composition and a molded product thereof.

[0010]

As a result of various studies to solve the above problems, the present inventors have found that (A) a polycarbonate resin, (B) a thermoplastic resin other than a polycarbonate resin, and (C) an acid base. The present inventors have found that a flame-retardant polycarbonate resin composition obtained by blending a contained aromatic vinyl-based resin at a specific composition ratio can achieve the above object, and have completed the present invention based on these findings. Was.

That is, the gist of the present invention is as follows. [1] Polycarbonate resin 50 to 9 as component (A)
Flame-retardant polycarbonate comprising 7.95% by mass, 2-47% by mass of thermoplastic resin other than polycarbonate resin as component (B), and 0.05-3% by mass of acid-base-containing aromatic vinyl resin as component (C) Resin composition. [2] The flame-retardant polycarbonate resin composition according to the above [1], wherein the polycarbonate resin as the component (A) is a polycarbonate copolymer resin having a structural unit derived from an organosiloxane. [3] The above-mentioned [1] or [2], wherein the thermoplastic resin of the component (B) is a styrene resin or a polyester resin.
3. The flame-retardant polycarbonate resin composition according to item 1. [4] The acid-base-containing aromatic vinyl resin of the component (C) is
The above [1] to metal polystyrene sulfonate,
The flame-retardant polycarbonate resin composition according to any one of [3]. [5] The above-mentioned [1], which is obtained by blending 0.02 to 5 parts by mass of a drip inhibitor as a component (D) with respect to a total of 100 parts by mass of the components (A), (B) and (C). ] ~
The flame-retardant polycarbonate resin composition according to any one of [4]. [6] The flame-retardant polycarbonate resin composition according to [5], wherein the drip inhibitor of the component (D) is a fluororesin. [7] The above-mentioned component (E), in which 0.1 to 10 parts by mass of a functional group-containing silicone compound is blended as the component (E) with respect to a total of 100 parts by mass of the components (A), (B) and (C). The flame-retardant polycarbonate resin composition according to any one of [1] to [6]. [8] 0.5 to 10 parts by weight of a core / shell type graft rubber-like elastic body as a component (F) is blended as a component (F) with respect to a total of 100 parts by weight of the components (A), (B) and (C). The flame-retardant polycarbonate resin composition according to any one of the above [1] to [7].

[9] A flame retardant of 0.1 as a component (G) based on a total of 100 parts by mass of the components (A), (B) and (C).
The flame-retardant polycarbonate resin composition according to any one of the above [1] to [8], wherein the composition comprises from 30 to 30 parts by mass. [10] The above [1] to

An electric / electronic device part obtained by molding the flame-retardant polycarbonate resin composition according to any one of [9].

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The flame-retardant polycarbonate resin composition of the present invention comprises a polycarbonate resin 50 (A).
-97.95% by weight, 2-47% by weight of a thermoplastic resin other than the polycarbonate resin as the component (B), and 0.05-3% by weight of an acid-base-containing aromatic vinyl resin as the component (C). It is a polycarbonate resin composition. In addition, the flame-retardant polycarbonate resin composition of the present invention may further comprise, if necessary, a drip inhibitor as a component (D), in addition to the basic components (A), (B), and (C).
(E) a functional group-containing silicone compound as a component, (F)
It is a core-shell type graft rubber-like elastic material as a component or a flame-retardant polycarbonate resin composition obtained by adding a flame retardant as a component (G) at a specific ratio.

Next, the polycarbonate resin of the component (A), the thermoplastic resin other than the polycarbonate resin of the component (B), and the acid-base-containing aromatic component of the component (C) which constitute the flame-retardant polycarbonate resin composition of the present invention. Vinyl resin,
The drip suppressant of the component (D), the functional group-containing silicone compound of the component (E), the core-shell type graft rubber-like elastic material of the component (F), and the flame retardant of the component (G) will be described in detail below. explain.

(A) Polycarbonate Resin The polycarbonate resin of the component (A) used as a raw material of the flame-retardant polycarbonate resin composition of the present invention includes:
There is no particular limitation, and examples thereof include polycarbonate resins having various structural units. Usually, an aromatic polycarbonate produced by reacting a dihydric phenol with a carbonate precursor can be used. That is, a polycarbonate resin produced by reacting a dihydric phenol with a carbonate precursor by a solution method or a melting method is suitably used.

As the dihydric phenol, for example,
4,4′-dihydroxybiphenyl, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3 -Methyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 1,1-
Bis (4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxy Phenyl) ketone,
Hydroquinone, resorcin, catechol and the like can be mentioned. Among these divalent phenols, bis (hydroxyphenyl) alkanes are preferable, and those using 2,2-bis (4-hydroxyphenyl) propane as a main raw material are particularly preferable.

Examples of the carbonate precursor include carbonyl halide, carbonyl ester, haloformate and the like. Specific examples include phosgene, dihaloformate of dihydric phenol, diphenyl carbonate, dimethyl carbonate, diethyl carbonate and the like. Further, the polycarbonate resin may have a branched structure in addition to a polymer having a linear molecular structure. Examples of branching agents for introducing such a branched structure include 1,1,1-tris (4-hydroxyphenyl) ethane and α, α ′, α ″ -tris (4-
(Hydroxyphenyl) -1,3,5-triisopropylbenzene, phloroglucin, trimellitic acid, isatin bis (o-cresol) and the like can be used. In addition, phenol, pt-butylphenol, pt-octylphenol, p-cumylphenol and the like can be used as the molecular weight regulator.

Further, as the polycarbonate resin used in the present invention, in addition to the homopolymer prepared using only the above-mentioned dihydric phenol, a copolymer having a polycarbonate structural unit and a polyorganosiloxane structural unit, or a homopolymer thereof may be used. It may be a resin composition composed of a polymer and a copolymer. Further, it may be a polyester-polycarbonate resin obtained by performing a polymerization reaction of polycarbonate in the presence of a bifunctional carboxylic acid such as terephthalic acid or an ester precursor such as an ester-forming derivative thereof. Further, a resin composition obtained by melt-kneading a polycarbonate resin having various structural units can also be used. In addition, as the polycarbonate resin of the component (A) in the present invention, those having substantially no halogen atom in the structural unit are preferably used.

The polycarbonate resin used as the component (A) has a viscosity average molecular weight of 10,000.
Those which are 0-100,000 are preferable. If the viscosity average molecular weight is less than 10,000, the thermal and mechanical properties of the obtained resin composition are not sufficient, and if the viscosity average molecular weight exceeds 100,000, the obtained resin This is because the moldability of the composition decreases. The viscosity average molecular weight of this polycarbonate resin is
More preferably, it is 11,000 to 40,000, and still more preferably 12,000 to 30,000.

(B) Thermoplastic resin other than polycarbonate resin The thermoplastic resin other than the polycarbonate resin as the component (B) used as a raw material of the flame-retardant polycarbonate resin composition of the present invention includes, for example, general-purpose polystyrene and impact resistance Polystyrene, syndiotactic polystyrene,
Styrene resins such as acrylonitrile-butadiene-styrene resin, acrylonitrile-styrene resin, methyl methacrylate-butadiene-styrene resin, and methyl methacrylate-styrene resin; polyester resins such as polyethylene terephthalate and polybutylene terephthalate; polyethylene and polypropylene Polyolefin resin; polyamide resin such as nylon 6, nylon 66, nylon 12, etc .; heat of styrene-butadiene-styrene-based elastomer, styrene-ethylene-butadiene-styrene-based elastomer, ethylene-propylene-based elastomer, polyester-based elastomer, polyamide-based elastomer, etc. Acrylic resin such as polymethyl methacrylate resin and acrylic acid-olefin copolymer And the like.

Among the thermoplastic resins of the component (B), the styrene resin is particularly excellent in improving the fluidity of the flame-retardant polycarbonate resin composition obtained when the styrene resin is used as the component (B). Therefore, it is a preferable thermoplastic resin to be used as the component (B). Further, the polyester-based resin is particularly effective in improving the solvent resistance of the flame-retardant polycarbonate resin composition obtained when the polyester resin is used as the component (B). It is a particularly preferred thermoplastic resin for production.

(C) Acid-Base-Containing Aromatic Vinyl Resin The acid-base-containing aromatic vinyl resin (C) used as a raw material of the flame-retardant polycarbonate resin composition of the present invention is a polymer of aromatic vinyl resin. An aromatic vinyl resin having a structure in which a part of hydrogen atoms of an aromatic ring in a united chain is substituted with an acid base is preferably used. Examples of the aromatic vinyl resin include polystyrene, rubber-modified polystyrene, styrene-acrylonitrile copolymer, and acrylonitrile-butadiene-styrene copolymer resin having at least a structural unit derived from styrene in a polymer chain. Resin can be used. Among these,
Particularly, a polystyrene resin is preferable.

Examples of the acid base substituted with a hydrogen atom of the aromatic ring in the aromatic vinyl resin include, for example, alkali metal salts such as sulfonic acid group, borate group and phosphate group, alkaline earth salts, and the like. Ammonium salts and the like. The substitution ratio of these acid bases is not particularly limited, and can be appropriately selected, for example, within a range of 10 to 100%.

Next, regarding the acid-base-containing polystyrene resin suitable as the acid-base-containing aromatic vinyl resin, the following general formula (1)

[0024]

Embedded image

[In the formula (1), X represents an acid base, and Y represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. M represents an integer of 1 to 5, n represents a molar fraction of a structural unit derived from styrene substituted with an acid base, and 0 <n
≦ 1. ] Is preferably used. In the general formula (1), the acid base represented by X includes a sulfonic acid group, a borate group,
Phosphate bases are preferred, and alkali metal salts such as sodium and potassium, alkaline earth metal salts such as magnesium and calcium, aluminum salts, zinc salts, tin salts, and ammonium salts of these acids are preferred. Further, as Y in the general formula (1), a hydrogen atom is preferable, and as the hydrocarbon group, a methyl group is particularly preferable.

Next, regarding the method for producing the acid-base-containing aromatic vinyl resin as the component (C), an aromatic vinyl monomer having a sulfone group or the like or another copolymerizable with them. And then neutralizing with a basic substance. Alternatively, a method of sulfonating an aromatic vinyl polymer, an aromatic vinyl copolymer, or a mixture thereof and neutralizing the sulfonated polymer with a basic substance can also be used. In the case where the aromatic vinyl polymer is sulfonated and then neutralized, for example, a polystyrene sulfonic acid is produced by adding sulfuric anhydride to a 1,2-dichloroethane solution of a polystyrene resin and reacting the resulting solution. This is neutralized with a basic substance such as sodium hydroxide or potassium hydroxide and purified to obtain an acid-base-containing aromatic vinyl resin.

Here, as the acid-base-containing aromatic vinyl resin as the component (C), an inorganic metal salt contained in the acid-base-containing aromatic vinyl resin is less than 5% by mass, preferably 3% by mass. What is reduced to less than is more preferably used. If only the aromatic vinyl resin, for example, polystyrene is sulfonated and then neutralized with sodium hydroxide, the by-produced sodium sulfate remains in the sodium polystyrene sulfonate, and the content of the sodium sulfate becomes 5%. If the amount is more than 10% by mass, the mechanical properties, thermal properties, and electrical properties of the flame-retardant polycarbonate resin composition obtained using the composition will be deteriorated, and the appearance of the molded product will be poor. The purification of sodium polystyrene sulfonate can be performed by a method of recrystallization using a solvent, a method of filtering off by-produced sodium sulfate, a treatment with an ion exchanger, a chelating agent, an adsorbent, or the like.

The acid-base-containing aromatic vinyl resin (C) has a weight average molecular weight of 1,000.
Those having a value of 0 to 300,000 are preferably used. If the weight-average molecular weight of the acid-base-containing aromatic vinyl resin is less than 1,000, the physical properties of a resin composition using the same as a compounding component are reduced, and the acid-base-containing aromatic resin is also reduced. Weight average molecular weight of the aromatic vinyl resin is 3
If it exceeds 000, the fluidity of the resin composition using this as a compounding component is deteriorated, leading to a decrease in productivity.

(D) Drip Inhibitor As the drip inhibitor of the component (D) used as a raw material of the flame-retardant polycarbonate resin composition of the present invention, a fluorine resin, a silicone resin or a phenol resin is preferably used. The fluororesin is preferably a fluoroolefin resin, and more preferably a polymer or copolymer having a polymer chain composed of fluoroethylene structural units. Examples of such a fluoroolefin resin include, for example, difluoroethylene resin, tetrafluoroethylene resin, tetrafluoroethylene-hexafluoropropylene copolymer resin, and a copolymer resin of tetrafluoroethylene and an ethylene monomer containing no fluorine atom. No. Among these fluororesins, polytetrafluoroethylene resins are particularly preferably used. These fluororesins may be used alone as the component (D), or two or more of them may be used in combination as the component (D). These fluororesins have an average molecular weight of 500,000 or more,
Those having a molecular weight of 0000 to 10,000,000 are preferred.

When a resin having a fibril forming ability is used among the above-mentioned polytetrafluoroethylene-based resins, a higher effect of suppressing the dripping of the melt can be obtained. Examples of the polytetrafluoroethylene-based resin having such a fibril-forming ability include those classified into Type 3 in the ASTM standard. And this polytetrafluoroethylene-based resin is, for example, tetrafluoroethylene in an aqueous solvent, sodium, potassium, in the presence of ammonium peroxydisulfide,
A polymer obtained by polymerizing at a temperature of 0 to 200 ° C, preferably 20 to 100 ° C under a pressure of 0.01 to 1 MPa is suitably used.

As such a polytetrafluoroethylene-based resin having a fibril-forming ability, Teflon 6-J (manufactured by DuPont-Mitsui Fluorochemical Co., Ltd.) as a commercial product classified into Type 3 of the ASTM standard is available. , Polyflon D-1, polyflon F-103, polyflon F201 (manufactured by Daikin Industries, Ltd.) and CD076 (manufactured by Asahi Glass Fluoropolymers). Also, AST
Other than those classified into Type 3 of the M standard, Algoflon F5 (manufactured by Montefluos), polyflon MPA,
Polyflon FA-100 (manufactured by Daikin Industries, Ltd.) and the like.

As the silicone resin, a polyorganosiloxane resin is preferable. Specifically, polydimethylsiloxane resin, polymethylphenylsiloxane resin, polydiphenylsiloxane resin, polymethylethylsiloxane resin, Mixtures are mentioned. These silicone resins have a number average molecular weight of 2
00 or more, preferably 500 to 5,000,000, and the form is oil-like, varnish-like, gum-like,
Any of a powder form and a pellet form may be used.

Further, as the phenolic resin, those obtained by reacting phenols such as phenol, cresol, xylenol and alkylphenol with aldehydes such as formaldehyde and acetaldehyde in the presence of a catalyst are preferably used. . The phenolic resin may be a resol type or a novolak type.

(E) Functional Group-Containing Silicone Compound Used as a raw material for the flame-retardant polycarbonate resin composition of the present invention.
Component (E) is a functional group-containing silicone compound
Is used. This functional group-containing silicone compound is
(R¹)_a(R^Two)_bSiO_{(4-ab) / 2}[Wherein, R¹Is
Represents a functional group; ^TwoRepresents a hydrocarbon group having 1 to 12 carbon atoms.
You. A and b are respectively 0 <a ≦ 3 and 0 ≦ b <
3, an integer satisfying 0 <a + b ≦ 3. ]
A polymer or copolymer composed of structural units Soshi
This R¹As the functional group represented by, an alkoxy group,
Aryloxy group, polyoxyalkylene group, hydrogen group,
Hydroxyl, carboxyl, silanol, amino,
Examples include a rucapto group, an epoxy group, and a vinyl group.
However, among these, alkoxy groups, hydrogen groups, hydroxyl groups,
Poxy group and vinyl group are preferred, methoxy group and vinyl group
Is more preferred. Also, R ^TwoAs a hydrocarbon group represented by
Represents a methyl group, an ethyl group, a phenyl group, etc.
You.

Among these functional group-containing silicone compounds, those having particularly high utility for use as the component (E) in the present invention include structural units containing a phenyl group as the hydrocarbon group represented by R ² in the above formula. And a functional group-containing silicone compound. The functional group represented by R ¹ in the above formula may be ^one containing one kind of functional group, one containing a plurality of different kinds of functional groups, or a mixture thereof. You may. Then, the value of the functional group (R ¹⁾ / hydrocarbon group (R ²⁾ in the above formula is 0.1 to 3, preferably suitably used those which are 0.3 to 2. Further, the silicone compound containing the functional group may be in a liquid state or a powder state. Among liquids, those having a viscosity at room temperature of about 10 to 500,000 cst are preferable.

(F) Core-shell type graft rubber-like elastic material As the component (F) used as a raw material of the flame-retardant polycarbonate resin composition of the present invention, a core-shell type graft rubber-like elastic material is preferably used. Used. The core-shell type graft rubber-like elastic body has a two-layer structure composed of a core and a shell. And
The core portion is in a soft rubber state, the shell portion on the surface thereof is in a hard resin state, and the rubber-like elastic body itself is preferably a graft rubber-like elastic body in a powder state (particle state). Most of the core-shell type graft rubber-like elastic body retains its original shape even after being melt-blended with a polycarbonate resin. Therefore, the graft rubber-like elastic body is uniformly dispersed in the polycarbonate resin, and is less likely to cause surface layer separation.

The core-shell type graft rubber-like elastic material is, for example, one or more rubber-like polymers obtained from monomers mainly composed of alkyl acrylate, alkyl methacrylate and dimethyl siloxane. Those obtained by polymerizing one or more vinyl monomers such as styrene in the presence are preferably used. As these alkyl acrylates and alkyl methacrylates, those having an alkyl group having 2 to 10 carbon atoms, for example, those obtained using ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, n-octyl methacrylate and the like are preferable. Elastomers obtained by using these monomers mainly composed of alkyl acrylate include 70% by weight or more of alkyl acrylate and a vinyl monomer copolymerizable therewith, such as methyl methacrylate, acrylonitrile, vinyl acetate, and styrene. A copolymer obtained by reacting the above components at a ratio of 30% by weight or less is suitably used. Further, it may be cross-linked with a polyfunctional compound such as divinylbenzene, ethylene dimethacrylate, triallyl cyanurate, triallyl isocyanurate.

Further, in the presence of a rubbery polymer, an aromatic vinyl compound such as styrene and α-methylstyrene,
Those obtained by polymerizing or copolymerizing acrylates such as methyl acrylate and ethyl acrylate, and methacrylates such as methyl methacrylate and ethyl methacrylate may be used. Furthermore, it was obtained by copolymerizing these monomers with other vinyl monomers such as acrylonitrile and vinyl cyanide compounds such as methacrylonitrile, vinyl acetate compounds such as vinyl acetate and vinyl propionate, and the like. It may be something. And these polymers and copolymers are those obtained by various methods such as bulk polymerization, suspension polymerization, and emulsion polymerization, and among them, those obtained by emulsion polymerization are used. Particularly preferably used.

Further, as the core-shell type graft rubber-like elastic material, n-butyl acrylate 60-
80% by mass of styrene and methyl methacrylate in 20 to
An MAS resin elastic material graft-copolymerized at a ratio of 40% by mass is used. In addition, the polysiloxane rubber component 5
95% by mass and poly (meth) acrylate rubber component 5 to 9
A composite rubber obtained by graft copolymerizing at least one vinyl monomer with a composite rubber having an average particle diameter of about 0.01 to 1 μm having a structure entangled with each other so that 5% by mass cannot be separated. A graft copolymer can also be used. Commercially available core-shell type graft rubber-like elastic bodies having these various forms are commercially available as Hybrene B621 (manufactured by Zeon Corporation) and KM-357P.
(Kureha Chemical Industry Co., Ltd.), Metablen W529, Metablen S2001, Metablen C223 (Mitsubishi Rayon Co., Ltd.) and the like.

(G) Flame Retardant As the component (G) used as a raw material of the flame retardant polycarbonate resin composition of the present invention, for example, an organic phosphorus compound,
Known flame retardants such as silicone compounds, nitrogen-containing compounds, metal hydroxides, halogen compounds, red phosphorus, antimony oxide, and expandable graphite can be used alone or in combination of two or more as appropriate. Here, examples of the nitrogen-containing compound include melamine and a melamine compound having an alkyl group or an aromatic group as a substituent, and examples of the metal hydroxide include magnesium hydroxide and aluminum hydroxide. .

As the halogen-based compound, tetrabromobisphenol A, halogenated polycarbonate, decabromodiphenyl ether, tetrabromobisphenol epoxy oligomer, halogenated polystyrene, halogenated polyolefin and the like are excellent in flame retardancy. However, it is preferable to use a non-halogen-containing flame retardant, since these may corrode a mold at the time of molding the resin composition and have a great possibility of adversely affecting the natural environment.

Among the halogen-free flame retardants, organophosphorus compounds are mentioned as having excellent flame retardancy.
Among them, phosphate ester-based flame retardants are preferred. As the phosphoric ester flame retardant, a phosphoric ester compound having one or more esteric oxygen atoms directly bonded to a phosphorus atom is preferably used. Such a phosphate compound is, for example, represented by the following general formula (2)

[0043]

Embedded image

[In the formula (2), R ¹ , R ² , R ³ , R
⁴ independently represents a hydrogen atom or an organic group;
Represents a divalent or higher valent organic group. P represents 0 or 1, q represents an integer of 1 or more, and r represents an integer of 0 or more. ] And a mixture thereof are preferably used. Here, in the general formula (2), R ¹
The organic group to R ⁴ represents respectively optionally substituted alkyl group, a cycloalkyl group, an aryl group. When the compound has a substituent, the substituent is preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an arylthio group, or the like. Further, it may be an arylalkoxyalkyl group which is a group obtained by combining these substituents, or an arylsulfonylaryl group in which these substituents are bonded by an oxygen atom, a nitrogen atom, a sulfur atom or the like. . Further, the divalent or higher valent organic group represented by X in the general formula (2) means a divalent or higher valent group obtained by removing one or more hydrogen atoms bonded to carbon atoms from the above organic group. For example, it may be an alkylene group or a phenylene group which may have a substituent, or a group derived from bisphenols which are polynuclear phenols.

Next, regarding the composition ratio of each component in the flame-retardant polycarbonate resin composition of the present invention,
The polycarbonate resin of the component (A) has a composition ratio of 50 to 97.95% by mass. When the composition ratio of the component (A) is less than 50% by mass, it is difficult to maintain excellent physical properties inherent to the polycarbonate resin in the obtained resin composition. If the content exceeds 97.95% by mass, the resulting resin composition will not have sufficient fluidity and solvent resistance. The composition ratio of the thermoplastic resin other than the polycarbonate resin as the component (B) is set to 2 to 47% by mass.
If the composition ratio of the thermoplastic resin is less than 2% by mass, the effect of improving the fluidity and solvent resistance of the resin composition obtained by blending the component (B) is not sufficient, When the composition ratio exceeds 47% by mass,
This is because in the degree of flame retardancy of the obtained resin composition, high flame retardancy of V-2 or more in UL standard cannot be obtained. Further, the composition ratio of the acid-base-containing aromatic vinyl-based resin as the component (C) is set to 0.05 to 3% by mass.
When the composition ratio of the acid-base-containing aromatic vinyl resin is less than 0.05% by mass, the resin composition obtained by blending the component (C) can maintain the flame retardancy and antistatic performance. The effect of improving the performance is not sufficient,
Also, when the composition ratio exceeds 3% by mass, physical properties such as impact strength of the obtained resin composition are reduced. The more preferable mixing ratio of the component (C) is 0.1 to 2% by mass, and the more preferable mixing ratio is 0.5 to 2% by mass.

The flame-retardant polycarbonate resin composition of the present invention has a practically sufficiently high flame-retardancy and antistatic performance, in the composition having the basic constitution comprising the components (A) to (C) described above. However, in applications where even higher flame retardancy is required, the dripping inhibitor of component (D) is added in an amount of 0.02 to 100 parts by mass of the basic components in total. Flame-retardant polycarbonate resin compositions containing up to 5 parts by weight are suitably used. This (D)
If the compounding ratio of the component is less than 0.02 parts by mass, the effect of the compounding is not sufficiently exhibited, and even if the compounding amount is increased beyond 5 parts by mass, the effect corresponding thereto cannot be obtained. A more preferable mixing ratio of the component (D) is
0.1 to 1 part by mass.

In order to further improve the flame retardancy of the flame retardant polycarbonate resin composition, the functional group-containing silicone compound (E) is added to the total of 100 parts by mass of the above basic components. Is suitably used in an amount of 0.1 to 10 parts by mass. If the compounding ratio of the component (E) is less than 0.1 part by mass, the effect of the compounding is not sufficient, and even if the compounding amount is increased beyond 10 parts by mass, the effect corresponding thereto cannot be obtained. This is because the mechanical strength of the obtained resin composition is reduced. A more preferable mixing ratio of the component (E) is 0.1 to 5 parts by mass.

Further, when the flame-retardant polycarbonate resin composition is required to have higher impact resistance and flame retardancy, the total of the above-mentioned basic components is 10%.
A flame-retardant polycarbonate resin composition obtained by mixing 0.5 to 10 parts by mass of a core / shell type graft rubber-like elastic component (F) with respect to 0 parts by mass is suitably used. If the compounding ratio of the component (E) is less than 0.5 part by mass, the compounding effect is not sufficiently exhibited, and even if the compounding amount is increased beyond 10 parts by mass, the effect corresponding thereto cannot be obtained. Because. A more preferable mixing ratio of the component (F) is 0.5 to 5 parts by mass.

Further, in order to further improve the flame retardancy of the flame retardant polycarbonate resin composition, the flame retardant of the component (G) is added in an amount of 0.1 part by mass based on 100 parts by mass of the above-mentioned basic constituent components. A flame-retardant polycarbonate resin composition blended with 1 to 30 parts by mass is suitably used. If the compounding ratio of the component (G) is less than 0.1 part by mass, the compounding effect is not sufficiently exhibited, and even if the compounding amount is increased beyond 30 parts by mass, the effect corresponding thereto cannot be obtained. is there.

Next, the method for producing the flame-retardant polycarbonate resin composition of the present invention will be described with reference to the above (A) to (A).
What is necessary is just to mix | blend and melt-knead each component of (C) by the said mixing ratio, and also mix | blending the components (D)-(G) suitably as needed. The compounding and kneading of each component here is performed by using a commonly used device, for example, a premix with a ribbon blender or a drum tumbler, and then a Banbury mixer, a single screw extruder, a twin screw extruder,
Melt kneading can be performed by a multi-screw extruder, a kneader, or the like. The temperature during melt-kneading may be appropriately selected usually in the range of 240 to 300 ° C. The melt-kneaded product is preferably formed by extruding into a strand with an extruder, particularly a vent-type extruder, and then cooling, cutting and pelletizing.

Using the pellets of the flame-retardant polycarbonate resin composition obtained in this manner, various molded articles are formed by injection molding, injection compression molding, extrusion molding, blow molding, press molding, or the like. Can be manufactured. The molded article of the present invention thus obtained has excellent properties such as excellent flame retardancy and solvent resistance, and excellent durability of antistatic performance without dust being attached to the surface. Electronic and electrical equipment, such as copiers, facsimiles, televisions, radios, tape recorders, VCRs, personal computers, printers, telephones, information terminals, refrigerators, microwave ovens and other housing and internal parts In addition, it is highly useful in fields such as automobile parts.

[0052]

[Examples 1 to 9]

[1] Production of Flame-Retardant Polycarbonate Resin Composition The components (A) to (G) of the raw materials were mixed in the proportions shown in Table 1 [provided that the components (A) to (C) in the table are mass %, And each of the components (D) to (G) represents 10% of the components (A) to (C).
The parts by mass of each component relative to 0 parts by mass are shown. And a vent-type twin screw extruder (manufactured by Toshiba Machine Co., Ltd .: TEM
35) and melt-kneaded at 280 ° C. The kneaded product was extruded into a strand, cooled, and cut to obtain pellets of the flame-retardant polycarbonate resin composition. Next, the obtained pellet was heated at 120 ° C.
After drying for 12 hours at a molding temperature of 270 ° C. and a mold temperature of 8
Injection molding was performed at 0 ° C. to obtain various test pieces. Here, the following components were used as the components (A) to (G) of the raw material.

(A) Polycarbonate resin (A-1) 2,2-bis (4-hydroxyphenyl)
A polycarbonate resin having a structural unit derived from propane, a linear structure, and a viscosity average molecular weight of 19,500. (A-2) 4% by mass of a block having 30 structural units derived from dimethylsiloxane, and the other is composed of structural units derived from 2,2-bis (4-hydroxyphenyl) propane, and has a linear structure. A polycarbonate resin having a viscosity average molecular weight of 15,000.

(B) Thermoplastic resins other than polycarbonate resin (B-1) A temperature of 20 according to JIS K-7210.
An impact-resistant polystyrene resin having a melt flow rate of 8 g / 10 min and a polybutadiene rubber content of 10% by mass measured under the conditions of 0 ° C. and a load of 5 kg [IT44, manufactured by Idemitsu Petrochemical Co., Ltd.]. (B-2) Acrylonitrile-butadiene-styrene copolymer resin [DP611 manufactured by Technopolymer Co., Ltd.]. (B-3) Acrylonitrile-styrene copolymer resin [manufactured by Technopolymer: 290]. (B-4) Polyethylene terephthalate resin (manufactured by Mitsubishi Rayon Co., Ltd .: Diamondite MA523).

(C) Acid-base-containing aromatic vinyl resin (C-1) Sodium polystyrene sulfonate having a weight average molecular weight of 20,000 and a sulfonation ratio of 100%. (C-2) Potassium polystyrene sulfonate having a weight average molecular weight of 20,000 and a sulfonation ratio of 40%.

(D) Drip inhibitor (D-1) Polytetrafluoroethylene resin [CD076: manufactured by Asahi Glass Co., Ltd.]

(E) Functional Group-Containing Silicone Compound (E-1) Methylphenylsilicone containing a vinyl group and a methoxy group as a functional group [K: manufactured by Shin-Etsu Chemical Co., Ltd.
R219]. (E-2) Methylphenyl silicone containing a methoxy group as a functional group [manufactured by Toray Dow Corning: DC3
037].

(F) Core-shell type graft rubber-like elastic material (F-1) Methyl methacrylate-butyl acrylate-styrene copolymer resin [KM357 manufactured by Kureha Chemical Industry Co., Ltd.]
P]. (G) Flame retardant (G-1) Resorcinol bis (diphenyl phosphate) [Adeka Stab PFR manufactured by Asahi Denka Kogyo KK]. (G-2) Tetrabromobisphenol A oligomer [FG7500 by Teijin Chemicals Ltd.].

[2] Evaluation of Flame-Retardant Polycarbonate Resin Composition Using the test pieces of the flame-retardant polycarbonate resin composition obtained in the above [1], the performance of the following items was evaluated. The results are shown in Table 1. (1) Melt fluidity The melt flow rate was measured at a temperature of 280 ° C and a load of 2.16 kg in accordance with JIS K7210. (2) Izod impact strength According to ASTM D256, the test piece had a thickness of 3.1.
It measured at 23 degreeC using the thing of 8 mm. (3) Grease resistance The grease resistance was measured in accordance with the chemical resistance evaluation method (critical distortion due to 1/4 ellipse). That is, a test piece (thickness = 3 mm) was fixed to the 1/4 elliptical surface of the jig shown in FIG. 1, and Albania grease (manufactured by Showa Shell Sekiyu KK) was applied to the test piece.
Hold for 48 hours. Then, the minimum length (X) at which cracks occurred was read, and the critical strain (%) was determined by the following equation (1).

[0060]

(Equation 1)

(4) Half-life of charged voltage As a test piece, a square plate having a size of 25 × 35 mm and a thickness of 3 mm was charged for 1 minute at an applied voltage of 9 kv. The halving time (seconds) was measured. (5) Half-life of charged voltage after washing with water After the test piece used in (4) above was washed with water at 23 ° C. for 1 minute, the adhering water was wiped off, and the sample was charged at an applied voltage of 9 kv for 1 minute. The time (second) at which the potential after the discharge was interrupted was reduced by half with respect to the charged voltage. (6) Flame retardancy A test piece having a thickness of 1.5 mm was used according to Underwriters Laboratory Subject 94.
A vertical burn test was performed.

[Comparative Examples 1 to 7] [1] Production of Flame-Retardant Polycarbonate Resin Composition The components of the raw materials were blended in the blending ratio shown in Table 2 (each numerical value in the table is the same as in the examples). Supplied to a vent-type twin-screw extruder (manufactured by Toshiba Machine Co., Ltd .: TEM35).
The mixture was melt-kneaded at ℃. Subsequently, the kneaded material was extruded into a strand, cooled, and cut to obtain pellets of the flame-retardant polycarbonate resin composition.

Next, the obtained pellets were dried at 120 ° C. for 12 hours, and then a molding temperature of 270 ° C. and a mold temperature of 80 ° C.
Injection molding was performed at ℃ to obtain a test piece and a molded product. Here, the following were used as each component of a raw material and an additive. (A) Polycarbonate resin The same polycarbonate resin as (A-1) in Examples 1 to 9. (B) Thermoplastic resin other than polycarbonate resin The same thermoplastic resin as (B-1) and (B-3) in Examples 1 to 9. (C) Acid-base-containing aromatic vinyl-based resin The same acid-base-containing aromatic vinyl-based resin as (C-1) and (C-2) in Examples 1 to 9, and the following metal salts. (C-3) Sodium dodecylbenzenesulfonate [Takemoto Yushi Co., Ltd .: Elecut S412-2].

(D) Drip inhibitor The same polytetrafluoroethylene resin as (D-1) in Examples 1 to 9. (E) Functional group-containing silicone compound The same silicone compound as (E-2) in Examples 1 to 9 and the following silicone compound. (E-3) Dimethyl silicone [SH200 manufactured by Dow Corning Toray Co., Ltd.]. (F) Core-shell type graft rubber-like elastic body The same methyl methacrylate-styrene copolymer resin as (F-1) in Examples 1 to 9.

[2] Evaluation of Flame-Retardant Polycarbonate Resin Composition Using the test pieces of the flame-retardant polycarbonate resin composition obtained in the above [1], evaluation of the performance of each item in Examples 1 to 9 above. Did. The results are shown in Table 2.

[0066]

[Table 1]

[0067]

[Table 2]

[0068]

According to the present invention, it is possible to obtain a molded article which is excellent in fluidity, solvent resistance and flame retardancy and which has excellent antistatic performance without adhering dust. The present invention can provide a reactive polycarbonate resin composition and a molded article thereof.

[Brief description of the drawings]

FIG. 1 is a perspective view of a jig for fixing a test piece used for evaluating the grease resistance of the flame retardant polycarbonate resin composition of the present invention.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 25:18) C08L 25:18) F term (Reference) 4F071 AA22 AA26 AA33X AA43 AA50 AA77 AE07 AF02 AF23 AF36 AF47 AH12 BA01 BB05 BC01 4J002 BB032 BB122 BB152 BB244 BC032 BC062 BC113 BC114 BC123 BD124 BD154 BG012 BG062 BN125 BN142 BN152 BN162 BP012 CC034 CC044 CC054 CF062 CF072 CG011 CG021 CG031 CP00 CP075 CP075 CP075 CP075 FD135 FD136 GN00 GQ00

Claims (10)

[Claims] 1. An aromatic vinyl resin containing 50 to 97.95% by mass of a polycarbonate resin as the component (A), 2 to 47% by mass of a thermoplastic resin other than the polycarbonate resin as the component (B) and an acid-base-containing aromatic vinyl component as the component (C). Resin 0.0
A flame-retardant polycarbonate resin composition comprising 5 to 3% by mass. 2. The polycarbonate resin as the component (A),
The flame-retardant polycarbonate resin composition according to claim 1, which is a polycarbonate copolymer resin having a structural unit derived from an organosiloxane. 3. The flame-retardant polycarbonate resin composition according to claim 1, wherein the thermoplastic resin (B) is a styrene resin or a polyester resin. 4. An aromatic vinyl resin containing an acid base as the component (C) is a metal salt of polystyrene sulfonic acid.
4. The flame-retardant polycarbonate resin composition according to any one of claims 1 to 3. 5. A drip inhibitor of 0.02 to 5 parts by mass as component (D) based on 100 parts by mass of the total of component (A), component (B) and component (C). 1
5. The flame-retardant polycarbonate resin composition according to any one of items 1 to 4. 6. The flame-retardant polycarbonate resin composition according to claim 5, wherein the drip inhibitor of the component (D) is a fluororesin. 7. A functional group-containing silicone compound of 0.1 to 10 parts by mass is added as the component (E) to the total of 100 parts by mass of the components (A), (B) and (C). The flame-retardant polycarbonate resin composition according to claim 1. 8. A core-shell type graft rubber-like elastic material as a component (F) is 0.5 to 10 parts by mass relative to a total of 100 parts by mass of the components (A), (B) and (C). The flame-retardant polycarbonate resin composition according to any one of claims 1 to 7, which comprises: 9. A flame retardant of 0.1 to 30 parts by mass as a component (G) based on a total of 100 parts by mass of the components (A), (B) and (C). 9. The flame-retardant polycarbonate resin composition according to any one of items 1 to 8. 10. An electric / electronic device part obtained by molding the flame-retardant polycarbonate resin composition according to claim 1.