WO2002059205A1

WO2002059205A1 - Flame-retardant polycarbonate resin compositions and molded article thereof

Info

Publication number: WO2002059205A1
Application number: PCT/JP2002/000137
Authority: WO
Inventors: Akio Nodera; Masahiro Kitayama; Toshio Isozaki
Original assignee: Idemitsu Petrochemical Co., Ltd.
Priority date: 2001-01-26
Filing date: 2002-01-11
Publication date: 2002-08-01

Abstract

(1) A flame-retardant polycarbonate resin composition which comprises 50 to 97.95 wt.% polycarbonate resin, 2 to 47 wt.% thermoplastic resin other than polycarbonate resins, and 0.05 to 3 wt.% acid/base-containing aromatic vinyl resin; (2) a flame-retardant polycarbonate resin composition which comprises 37 to 97.95 wt.% polycarbonate resin, 2 to 60 wt.% inorganic filler, and 0.05 to 3 wt.% acid/base-containing aromatic vinyl resin; and (3) a part for electrical/electronic appliances which is obtained by molding either of these resin compositions.

Description

Specification

Flame retardant polycarbonate resin composition and molded article thereof

Technical field

The present invention relates to a flame-retardant polycarbonate resin composition and a molded article thereof. More specifically, a flame-retardant polycarbonate resin composition with excellent fluidity, solvent resistance, flame retardancy, and excellent durability of antistatic performance, and excellent rigidity and dimensional accuracy, and sustained antistatic performance The present invention relates to a flame-retardant polycarbonate resin composition having excellent heat resistance and molded articles thereof.

Background art

Polycarbonate resins are excellent in impact resistance, heat resistance, electrical properties, dimensional stability, etc., and are used in the electrical and electronic equipment fields such as office automation (OA) equipment, information and communication equipment, and home appliances. It is widely used in various fields such as automobiles and construction. Polycarbonate resins have these excellent properties.However, in order to further improve mechanical strength and dimensional stability, reinforced polycarbonate resin compositions containing an inorganic filler such as glass fiber are used. Used. This polycarbonate resin is a self-extinguishing resin itself, but when used as a material for OA equipment, information, communication equipment, electric and electronic equipment, etc. Is required to be higher.

As a method for improving the flame retardancy of polycarbonate resin, the use of halogen-based flame retardants such as halogenated bisphenol / re A and halogenated polycarbonate ligomers increases the flame retardant efficiency. It has been used with auxiliaries. However, in recent years, there has been a demand for a flame retardant method using a halogen-free flame retardant because of its great impact on the environment during safety and waste incineration. Therefore, When an organic phosphorus-based flame retardant, especially an organic phosphate compound, is blended as a halogenated flame retardant, the organic phosphoric ester compound can be used because it has excellent flame retardancy and also acts as a plasticizer. The flame-retardant polycarbonate resin composition used has been proposed.

By the way, in order to make the polycarbonate resin flame-retardant using this organic phosphate compound, it is necessary to mix the organic phosphate compound in a relatively large amount. In addition, polycarbonate resin has a high molding temperature and a high melt viscosity. Therefore, it is necessary to increase the molding temperature to increase the fluidity in order to cope with thinner and larger molded products. Therefore, this organophosphate compound contributes to flame retardancy, but it is not always sufficient in terms of the molding environment and appearance of the molded product, such as sticking to the mold and generating gas during molding of the polycarbonate resin. May not be available. In addition, molded articles of the flame-retardant polycarbonate resin composition using the organic phosphate compound have a problem that the impact strength is reduced or the color is changed with the history of high temperature and the history of high temperature and high humidity.

In order to solve such problems, Japanese Patent Application Laid-Open No. 50-98546 discloses that a small amount of a metal salt of a polymeric aromatic sulfonic acid, for example, a sodium salt of polystyrene sulfonic acid is used. It is proposed to make the polycarbonate resin flame-retardant by blending. However, if the polycarbonate resin is flame-retarded using sodium polystyrenesulfonate obtained by sulfonating polystyrene by the usual method and neutralizing it with sodium hydroxide, the However, there is a drawback that molded articles have poor appearance due to poor dispersibility of sodium polystyrenesulfonate.

In addition, for such a flame-retardant polycarbonate resin composition, there is a demand for the development of a flame-retardant molding material that maintains the characteristics of the polycarbonate resin. In order to meet such demands, for example, Japanese Patent Application Laid-Open No. Hei 8-176425 discloses a polycarbonate resin containing an organic alkali metal salt or an organic alkaline earth metal salt and an organopolysiloxane. Are proposed. Although this resin composition is excellent in flame retardancy and mechanical strength, a molded article obtained by molding the resin composition has a problem that dust adheres to the surface of the resin composition and the surface thereof is soaked.

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 polystyrene or polyphenylene ether, a resin composition having excellent flame retardancy is indicated, but a polycarbonate resin which maintains the inherent properties of the polycarbonate resin is described. No mention is made of flame-retardant, flame-retardant resin compositions mainly composed of

Therefore, molding that maintains the excellent properties of polycarbonate resin, has excellent fluidity, excellent solvent resistance and flame retardancy, and has excellent antistatic performance without dust adhesion There is a demand for the development of a flame-retardant polycarbonate resin composition from which a product can be obtained.

Furthermore, the reinforced polycarbonate resin composition blended with an inorganic filler such as glass fiber maintains the excellent mechanical strength and dimensional stability of the resin, and maintains the antistatic performance without adhering dust. Development of a flame-retardant polycarbonate resin composition capable of obtaining excellent molded articles has also been demanded.

The present invention relates to a flame-retardant polycarbonate resin composition which is excellent in fluidity, solvent resistance and flame retardancy, and which can obtain a molded article excellent in durability of antistatic performance without adhering dust. The purpose is to provide such molded articles. In addition, the present invention provides excellent mechanical strength and dimensional stability. It is an object of the present invention to provide a flame-retardant polycarbonate resin composition capable of obtaining a molded article excellent in persistence of antistatic performance to which dust does not adhere, and a molded article thereof.

Disclosure of the invention

As a result of various studies to solve the above problems, the present inventors have identified (A) a polycarbonate resin, (B) a thermoplastic resin other than a polycarbonate resin, and (C) an aromatic vinyl resin containing an acid base. Flame-retardant polycarbonate resin composition and (A) polycarbonate resin, and (H) inorganic filler and (C) acid-base-containing aromatic vinyl resin blended at a specific composition ratio According to the flame-retardant polycarbonate resin composition thus obtained, the above-mentioned object can be achieved, and the present invention has been completed based on these findings.

That is, the gist of the present invention is as follows.

[1] 50 to 97.95% by mass of polycarbonate resin as component (A), 2 to 47% by mass of thermoplastic resin other than polycarbonate resin as component (B), and acid base as component (C) Containing aromatic vinyl resin 0.05 to 3 mass. / ₀ , a flame-retardant polycarbonate resin composition.

[2] The polycarbonate resin as the component (A) is a polycarbonate copolymer resin having a structural unit derived from an organosiloxane.

The flame-retardant polycarbonate resin composition according to [1].

[3] The flame-retardant polycarbonate resin composition according to the above [1] or [2], wherein the thermoplastic resin as the component (B) is a styrene-based resin or a polyester-based resin.

[4] The flame-retardant polycarbonate resin composition according to any one of [1] to [3], wherein the acid-base-containing aromatic vinyl resin as the component (C) is a polystyrene sulfonic acid metal salt. [5] 0.02 to 5 parts by mass of the drip inhibitor as the component (D) is added to the 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 [4].

[6] The flame-retardant polycarbonate resin composition according to [5], wherein the dripping inhibitor of the component (D) is a fluororesin.

[7] 0.1 to 10 parts by mass of the functional group-containing silicone compound as the component (E) is added to the 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 [6].

[8] For a total of 100 parts by mass of the component (A), the component (B) and the component (C), the core and shell type graft rubber-like elastic material as the component (F) is 0.5 to 10 The flame-retardant polycarbonate resin composition according to any one of the above [1] to [7], which is compounded by mass.

[9] A flame retardant of 0.1 to 30 parts by mass as a component (G) is added to the 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].

[10] Polycarbonate resin 37 to 97.95% by mass as component (A), 2 to 60% by mass of inorganic filler as component (H) and acid-base-containing fragrance as component (C) A flame-retardant polycarbonate resin composition comprising 0.5 to 3% by mass of an aromatic vinyl resin.

[11] The inorganic filler of the component (H) is at least one filler selected from the group consisting of glass fiber, glass flake, glass beads, talc, myriki, and carbon fiber. [0] The flame-retardant polycarbonate resin composition according to [1]. [12] The flame-retardant polycarbonate resin composition according to the above [10] or [11], wherein the acid-base-containing aromatic vinyl resin as the component (C) is a polystyrenesulfonic acid metal salt.

[13] With respect to a total of 100 parts by mass of the components (A) and (H) and the component (C), 0.02 to 5 parts by mass of the dripping inhibitor as the component (D) is used. The flame-retardant polycarbonate resin composition according to any one of [10] to [12], which is blended.

[14] The flame-retardant polycarbonate resin composition according to [13], wherein the component (D) is a fluororesin.

[15] Based on a total of 100 parts by mass of the components (A), (H) and (C), 0.1 to 10 parts by mass of the functional group-containing silicone compound as the component (E). The flame-retardant polycarbonate resin composition according to any one of the above [10] to [14], which comprises:

[16] For a total of 100 parts by mass of the component (A), the component (H) and the component (C), the component (F) is a core-shell type graphitic rubber-like elastic material 0.5 to 10 The flame-retardant polycarbonate resin composition according to any one of the above [10] to [15], which is compounded by mass.

[17] A total of 100 parts by mass of the components (A), (H) and (C) is blended with 0.1 to 30 parts by mass of a flame retardant as the component (G). The flame-retardant polycarbonate resin composition according to any one of [10] to [16].

[18] A molded article obtained by molding the flame-retardant polycarbonate resin composition according to any one of [1] to [17].

[19] The molded article according to [18], wherein the molded article is an electric or electronic device part.

BRIEF DESCRIPTION OF THE FIGURES 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.

BEST MODE FOR CARRYING OUT THE INVENTION

The flame-retardant polycarbonate resin composition of the present invention comprises 50 to 97.95% by mass of a polycarbonate resin as the component (A) and 2 to 47% by mass of a thermoplastic resin other than the polycarbonate resin as the component (B). And a flame-retardant polycarbonate resin composition comprising 0.05 to 3% by mass of an acid-base-containing aromatic vinyl resin as the component (C). In addition, the flame-retardant polycarbonate resin composition of the present invention can be used as a component (D) for suppressing dripping, if necessary, in addition to the basic components (A), (B) and (C). A silicone rubber compound containing a functional group as the component (E), a core-shell type rubber-like elastic material as the component (F), or a flame retardant as the component (G) is added at a specific ratio. And a flame-retardant polycarbonate resin composition. Further, the flame-retardant polycarbonate resin composition of the present invention contains 37 to 97.95% by mass of the polycarbonate resin (A), 2 to 60% by mass of the inorganic filler (H), (C) A flame-retardant polycarbonate resin composition comprising from 0.05 to 3% by mass of an aromatic base resin containing an acid base as the component. Further, the flame-retardant polycarbonate resin composition of the present invention may further comprise, as necessary, a drip inhibitor as a component (D), in addition to the basic components (A), (H) and (C). A flame-retardant composition obtained by adding a functional group-containing silicone compound as the component (E), a core-shell type rubber-like elastic material as the component (F), or a flame retardant as the component (G) at a specific ratio. It is a reactive polycarbonate resin composition. Next, the polycarbonate resin of the component (A), the thermoplastic resin other than the polycarbonate resin of the component (B), and the inorganic filler of the component (H), which constitute the flame-retardant polycarbonate resin composition of the present invention; Ingredient acid Base-containing aromatic vinyl resin, (D) component dripping inhibitor, (E) component functional group-containing silicone compound, (F) component core 'shell type graphitic rubber-like elastic material and (G) The component flame retardant is described in detail below.

(A) Polycarbonate resin

The polycarbonate resin as the component (A) used as a raw material of the flame-retardant polycarbonate resin composition of the present invention is not particularly limited, and includes polycarbonate resins having various structural units. Usually, an aromatic polycarbonate produced by reacting a divalent phenol with a carbonate precursor can be used. That is, a polycarbonate resin produced by reacting a divalent phenol with a polycarbonate precursor by a solution method or a melting method is suitably used.

Examples of the divalent phenol include 4,4, dihydroxybiphenyl, bis (4-hydroxyphenyl) methane, 1,1,1-bis (4hydroxyphenyl) ethane, 2 , 2- bis (4-arsenate Dorokishifu Eninore) propane, 2, 2 - bis (3 - Mechinore one 4-arsenide Dorokishifue two Honoré) Puronoヽ⁰ emissions, 2, 2 - bis (3, 5 - dimethyl _ 4 - arsenide (Droxyphen) propane, 1,1-bis (4—hydroxyphenyl) cyclohexane, bis (4—hydroxyphenyl) athenole, bis (4—hydroxyphenyl) snorefide, bis (4-) (Hydroxy-phenol) snorehon, bis (4-hydroxyphenyl) snolefoxide, bis (4-hydroxyphenyl) ketone, hydroquinone, Zonoreshin, such as catheter call, and the like. 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. Carbonate precursors include carbonyl halides and carbohydrates. Nyl esters, haloformates and the like. Specific examples include phosgene, diphenol of divalent phenol, diphenyl carbonate, dimethyl carbonate, and getyl carbonate. Further, the polycarbonate resin may have a branched structure in addition to a molecular structure of a polymer chain having a linear structure. Examples of the branching agent for introducing such a branched structure include 1,1,1—tris (4-hydroxyphene / re) ethane and a, ', α ”—tris (4-hydroxy). (Droxypheninole)-1,3,5_triisopropyl 7-lebenzene, fluorodarucine, trimellitic acid, isatin bis (ο-cresol), etc. can be used. Then, it is possible to use phenol, ρ-t-puchinorenoenore, p-t-octylphenenole, ρ-cumylphenol, and the like.

Further, as the polycarbonate resin used in the present invention, in addition to the homopolymer produced using only the above divalent 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 comprising a polymer and a copolymer. Further, it may be a polyester-polycarbonate resin obtained by performing a polymerization reaction of a 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, resin compositions obtained by melt-kneading polycarbonate resins having various structural units can also be used. In addition, as the polycarbonate resin of the component (A) in the present invention, a resin that does not substantially contain a halogen atom in its structural unit is preferably used.

The polycarbonate resin used as the component (A) preferably has a viscosity-average molecular weight of 100,000 to 100,000. New If the viscosity average molecular weight is less than 100,000, the resulting resin composition has insufficient thermal and mechanical properties, and the viscosity average molecular weight is less than 100,000. If the ratio exceeds the above, the moldability of the obtained resin composition will decrease. The viscosity average molecular weight of this polycarbonate resin is more preferably from 11,000 to 40,000, still more preferably from 12,000 to 30,000.

(B) Thermoplastic resin other than polycarbonate resin

Examples of 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 include, for example, general-purpose polystyrene ゃ impact-resistant polystyrene, Gyrotics • Styrenes such as polystyrene, acrylonitrile-butadiene-styrene resin, acrylonitrile-styrene resin, methyl methacrylate butadiene styrene resin, and methyl methacrylate-styrene resin Resins: Polyester resins such as polyethylene terephthalate and polybutylene terephthalate; Polyolefin resins such as polyethylene and polypropylene; Polyamide resins such as Nylon 6, Nylon 66, and Nylon 12 Styrene-butadiene-styrene-based elastomer, styrene-ethylene Thermoplastic elastomers such as butadiene-styrene-based elastomer, ethylene-propylene-based elastomer, polyester-based elastomer, polyamide-based elastomer, etc .; polymethyl methacrylate resin acrylate-olefin copolymer Acrylic resins such as coalescence are mentioned.

Among these thermoplastic resins of the component (B), the styrene-based resin is particularly effective in improving the fluidity of the flame-retardant polycarbonate resin composition obtained when the styrene resin is used as the component (B). Since it is excellent, it is a preferable thermoplastic resin to be used as the component (B). In addition, polyester Resins are flame-retardant poly resins obtained when they are used as the component (B). Molded articles that require solvent resistance because the effect of improving the solvent resistance of the carbonate resin composition are particularly excellent. This is a particularly preferred thermoplastic resin when producing styrene.

(H) Inorganic filler

Examples of the inorganic filler of the (H) component used as a raw material of the flame-retardant polycarbonate resin composition of the present invention include, for example, glass fiber, glass flake, glass beads, glass nonane, tanolek, and clay. , Mai power, nor mai power, silica, alumina, calcium carbonate, calcium sulfate, calcium silicate, titanium oxide, zinc oxide, zinc sulfide, quartz powder, asbestos, graphite, carbon black, carbon fiber, titanate Mineral fibers such as potassium whiskers, aluminum borate whiskers, boron fibers, tetra-potted zinc oxide whiskers, rock wool, metal fibers such as stainless steel fibers, and metal foils such as aluminum foil. Among these inorganic fillers, glass fiber, glass flake, glass beads, talc, myriki, and carbon fiber are particularly preferable. These inorganic fillers are preferably surface-treated in advance because of their good affinity for the resin component, but may be untreated. Examples of the surface treatment agent include a silane coupling agent, a treatment agent such as a higher fatty acid, a fatty acid metal salt, an unsaturated organic acid, an organic titanate, a resin acid, and a polyethylene glycol. Can be used. Next, as glass fibers suitable for use as the component (H), those produced using alkali-containing glass, low-alkali glass, or non-alkali glass as a material are preferable. The form may be any form such as roving, milled fiber, chopped strand, and the like. Also, the diameter of this glass fiber is l ~ 20; um It is preferable to use one having a length of 1 to 6 mm. Regarding the length of this glass fiber, the glass fiber supplied to the kneader breaks during kneading with the resin component, so that the fiber length in the resin composition pellet is 0.01 to 2 mm, preferably It is better to fill to 0.05 to 1 mm.

This glass fiber is treated with a surface treatment agent and then subjected to convergence treatment using a sizing agent in order to improve the adhesiveness to the resin component, and then the above components (A) and (C) are used. It is desirable to mix with the above resin components and melt knead them. Examples of the surface treatment agent for this glass fiber include silane-based coupling agents such as aminosilane, epoxysilane, butylsilane, and acrylsilane, titanate, aluminum, chromium, zirconium, and boron. Coupling agents such as a system. Among them, a silane coupling agent and a titanate coupling agent are particularly preferably used. The surface treatment method may be a general aqueous solution method, an organic solvent method, a spray method, or the like. Examples of the sizing agent used in the sizing treatment after the surface treatment include sizing agents such as urethane-based, acryl-based, acrylonitrile-styrene-based copolymer, and epoxy-based sizing agents. Known methods such as dip coating, roller coating, spray coating, flow coating, and spray coating can be used for the method of convergence treatment of glass fibers with these sizing agents.

As the carbon fiber suitable for use as the component (H), cellulose fiber, acryl fiber, lignin, petroleum pitch or coal pitch fired as a raw material is preferably used. Can be This carbon fiber also has a type such as flame-resistant, carbonaceous, or graphite, depending on the firing conditions, but any type may be used. In addition, the form of carbon fiber is mouth-buffing, milled fiber, and tubing strand. It can be of any kind. The fiber diameter is preferably 5 to 15 μm, and the fiber length is preferably in the range of 0.01 to 10 mm in the kneaded composition pellet with the resin component. . Further, it is preferable that the carbon fiber is previously surface-treated with an epoxy resin or a urethane resin because of its excellent affinity with a resin component.

(C) Acid-base-containing aromatic vinyl resin

The acid-base-containing aromatic vinyl-based resin (C) used as a raw material of the flame-retardant polycarbonate resin composition of the present invention is one of the hydrogen atoms of the aromatic ring in the polymer chain of the aromatic-vinyl-based resin. An aromatic vinyl resin having a structure in which a part is substituted with an acid base is suitably used. The aromatic vinyl resin includes at least styrene in a polymer chain such as polystyrene, rubber-modified polystyrene, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer resin. An aromatic vinyl-based resin having a structural unit derived from styrene can be used. Among these, a polystyrene resin is particularly preferred.

Examples of the acid base to be substituted with a hydrogen atom of the aromatic ring in the aromatic vinyl resin include, for example, an alkali metal salt such as a sulfonic acid group, a borate group and a phosphoric acid group, and an alkaline earth metal. Salt and ammonium salt are available. Further, the substitution ratio of these acid bases is not particularly limited, and can be appropriately selected, for example, within the range of 10 to 100%.

Next, an acid-base-containing polystyrene resin suitable as the acid-base-containing aromatic vinyl resin is represented by the following general formula (1)

[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. In addition, m represents an integer of 1 to 5, n represents a mole fraction of a structural unit derived from styrene substituted with an acid base, and 0 <n ≤ 1. The acid-base-containing polystyrene resin represented by the following formula is preferably used.

In the general formula (1), the acid base represented by X is preferably a sulfonate group, a borate group or a phosphate group, and is preferably an alkali metal such as sodium or potassium of these acids. Suitable examples include salts, alkaline earth metal salts such as magnesium and potassium, aluminum salts, zinc salts, tin salts, and ammonium salts. Further, in the general formula (1), Y is preferably a hydrogen atom, and a hydrocarbon group is particularly preferably a methyl group.

Next, regarding the method for producing the aromatic vinyl-based resin containing the acid base as the component (C), an aromatic vinyl-based monomer having a sulfone group or the like as a monomer or other copolymerizable with these can be used. After polymerization or copolymerization with the above monomer, neutralization with a basic substance can be performed. Alternatively, a method can be employed in which an aromatic vinyl polymer or an aromatic vinyl copolymer, or a mixture thereof is sulfonated and neutralized with a salty substance. In the case where the aromatic vinyl polymer is sulfonated and then neutralized, for example, a polystyrene resin], 2-dichloroethane The solution is reacted with sulfuric anhydride to produce polystyrenesulfonic acid, which is then neutralized with a basic substance such as sodium hydroxide or potassium hydroxide, and purified to obtain an acid-base containing aromatic substance. A group vinyl resin can be obtained.

Here, the acid-base-containing aromatic vinyl-based resin as the component (C) is preferably less than 5% by mass, preferably less than 3% by mass of an inorganic metal salt contained in the acid-base-containing aromatic vinyl-based resin. It is more preferably used that has been reduced. If only the aromatic vinyl resin, for example, polystyrene is sulfonated and then neutralized with sodium hydroxide, the by-produced sodium sulfate will remain in the sodium polystyrene sulfonate. The content of sodium sulfate is 5 mass. If the _ratio exceeds / ₀ , the mechanical properties, thermal properties, and electrical properties of the flame-retardant polycarbonate resin composition obtained using the composition will decrease, and the appearance of the molded product will be poor. This sodium polystyrene sulfonate can be purified by recrystallization using a solvent, by filtering off sodium by-produced by filtration, or by treatment with an ion exchanger, chelating agent, or adsorbent. This can be done by:

As the acid-base-containing aromatic vinyl resin (C), those having a weight average molecular weight of 1,000 to 300,000 are preferably used. If the acid-base-containing aromatic vinyl resin has a weight-average molecular weight of less than 1,000, the physical properties of the resin composition using this as a compounding component are reduced, and If the weight-average molecular weight of the acid-base-containing aromatic vinyl resin exceeds 300,000, the flowability of the resin composition using the resin as a component deteriorates, and the productivity decreases. It is the character that will be invited.

(D) Drip inhibitor Used as a raw material of the flame-retardant polycarbonate resin composition of the present invention (

As the dripping inhibitor of the component (D), a fluororesin, a silicone resin, and a phenol resin are preferably used. As the fluororesin, a fluorinated olefin-based resin is preferable, and a polymer or a copolymer having a polymer chain composed of fluorethylene units is more preferable. Examples of such fluorofluorinated resins include difluoroethylene resin, tetrafluoroethylene resin, tetrafluoroethylene-hexafluoropropylene copolymer resin, and tetrafluoroethylene and fluorine. A copolymer resin with an atom-free ethylene-based monomer may be used. Among these fluororesins, polytetrafluoroethylene resin is particularly preferably used. In addition, these fluororesins may be used alone.

It may be used as the component (D) or a combination of two or more types may be used as the component (D). Further, it is preferable that these fluororesins have an average molecular weight of 500,000 or more, and more preferably 500,000 to: 100,000,000.

Further, among the above polytetrafluoroethylene-based resins, when a resin having a fibril forming ability is used, a higher melting dripping suppression effect can be obtained. Examples of the polytetrafluoroethylene resin having such a fiprill-forming ability include those classified into type 3 in the ASTM standard. Then, this polytetrafluoroethylene-based resin is prepared, for example, by adding tetrafluoroethylene to an aqueous solvent in the presence of sodium, potassium, and ammonium peroxydisulphide in the range of 0.01 to lMP. Those obtained by polymerization at a temperature of 0 to 200 ° C., preferably 20 to 100 ° C. under the pressure of a, are suitably used.

Polytetrafluoroethylene having such bupryl forming ability Teflon 6-J (manufactured by Mitsui 's DuPont Fluorochemicals), Polyflon D-1 and Polyflon F-1 are commercially available resins that are classified as Type 3 of the ASTM standard. 03, polyfluorocarbon F201 (manufactured by Daikin Industries, Ltd.) and CD076 (manufactured by Asahi Glass Fluoropolymers). In addition to those classified into Type 3 of the ASTM standard, there are Argoflon F5 (manufactured by Montefluos), Polyflon MPA, and Polyflon FA-100 (manufactured by Daikin Industries).

Further, as the silicone resin, a polyorganosiloxane resin is preferable, and specifically, a polydimethylsiloxane resin, a polymethylphenylsiloxane resin, a polydiphenylsiloxane resin, a polymethylethylsiloxane resin, These mixtures are mentioned. These silicone resins have a number-average molecular weight of 200 or more, preferably 500 to 5,000, and are in the form of oil, varnish, gum, and powder. Shape and pellet shape.

In addition, phenolic resins include phenols such as phenol, cresol, xylene, and α-IV kirphenol, and aldehydes such as formaldehyde and acetoaldehyde. Those obtained by reacting in the presence of a catalyst are preferably used. The phenolic resin may be a resol type or a novolak type.

(E) Silicone compound containing functional group

As the component (E) used as a raw material of the flame-retardant polycarbonate resin composition of the present invention, a functional group-containing silicone compound is used. This functional group-containing silicon corn _{compound, (R ') a (R} 2) b S i O _ a _ b) / 2 [wherein, R ¹ represents a functional group, R ² is 1 to the number of carbon atoms 1 2 Represents a hydrocarbon group. A and b are integers that satisfy 0 a3, 0≤b <3, and 0 a + b ^ 3, respectively. ] Or a polymer comprising the structural unit represented by It is a polymer. Examples of the functional group represented by R ¹ include an alkoxy group, an aryloxy group, a polyoxyalkylene group, a hydrogen group, a hydroxyl group, a carboxyl group, a silanol group, an amino group, a mercapto group, an epoxy group, and a vinyl group. Among these, an alkoxy group, a hydrogen group, a hydroxyl group, an epoxy group, and a vinyl group are preferable, and a methoxy group and a vinyl group are more preferable. Examples of the hydrocarbon group represented by R ² include a methyl group, an ethyl group, and a phenyl group.

Among these functional group-containing silicone compounds, those particularly highly useful as the component (E) in the present invention are the hydrocarbon groups represented by R ^{2 in the} above formula. It is a functional group-containing silicone compound consisting of a structural unit containing a fluorine group. Further, in the above formula, the functional group represented by R ¹ may be one containing one kind of functional group or one containing a plurality of different kinds of functional groups. It may be a mixture. Those having a functional group (R ¹ ) Z hydrocarbon group (R ² ) value in the above formula of 0.1 to 3, preferably 0.3 to 2 are suitably used. Further, the silicone compound containing the functional group may be in a liquid form or a powder form. For liquids, those with a viscosity at room temperature of about 10 to 500, OOO cst are preferred.

(F) Core. Shell type 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 suitably used. The core-shell type rubber-like elastic body has a two-layer structure consisting of a core and a shell. The core part is in a soft rubber state, the seal part on the surface is in a hard resin state, and the rubber-like elastic body itself is in a powder state (particle state). A certain rubber-like elastic material is preferably used. After being melt-blended with the polycarbonate resin, the particle state of the core rubber elastic body of the core-shell type is mostly maintained in its original form. Therefore, this rubber-like elastic material is uniformly dispersed in the polycarbonate resin, and is less likely to cause surface layer peeling.

The core-shell type graft rubber-like elastic material is, for example, one or a kind obtained from a monomer mainly composed of butadiene, phenolic acrylate, dimethyl methacrylate, and dimethylsiloxane. A polymer obtained by polymerizing one or more vinyl monomers such as styrene in the presence of two or more rubber-like polymers or ethylene-propylene-gen copolymer rubber is preferably used. These alkyl acrylates / alkyl methacrylates have an alkyl group of 2 to 10 carbon atoms, such as ethyl acrylate, butyl acrylate, and 21-ethyl hexyl / reacrylate. Those obtained by using a relay or n-octinolemethacrylate are preferred. Elastomers obtained by using these monomers having alkyl acrylate as a main component include alkyl acrylate of 70% by weight or more, a vinyl monomer copolymerizable therewith, For example, a copolymer obtained by reacting methyl methacrylate, acrylonitrile, vinyl acetate, styrene and the like at a ratio of 30% by weight or less is suitably used. Further, it may be crosslinked with a polyfunctional compound such as divinylbenzene, ethylene dimethacrylate, triaryl cyanurate, triaryl cyanocyanate, or the like.

In addition, aromatic rubber compounds such as styrene and α-methylstyrene, acrylates / esters such as methyl acrylate, ethyl acrylate, methyl methacrylate, and methacrylate It is obtained by polymerizing or copolymerizing methacrylic acid esters such as ethyl acrylate. May be used. In addition, these monomers are copolymerized with other vinyl monomers, for example, vinyl cyanide compounds such as atalylonitrile II and methacrylonitrile, and vinyl ester compounds such as vinyl acetate and vinyl propionate. It may be one obtained by performing the above. As these polymers and copolymers, those obtained by various methods such as bulk polymerization, suspension polymerization, and emulsion polymerization are used, and among them, those obtained by emulsion polymerization are used. Those are particularly preferably used.

Moreover, this core. As a shell type graph Togomu like elastic body, n- Buchiruaku to re-rate 6 0-8 0 weight ^_0/0, styrene and Metaku methyl acrylic acid 2 0-4 in a proportion of 0 wt% A MAS resin elastic material that has been copolymerized is used. The average particle diameter of 0.0 1 polysiloxane rubber component 5-9 5 wt% of poly (meth) and Atta Li Retogomu components 5-9 5 mass ^_0/0 has mutually entangled structure inseparably A composite rubber-based graft copolymer obtained by subjecting at least one type of vinyl monomer to a composite rubber having a thickness of about 1 μm can be used.

Core-Schull type graft rubber-like elastic bodies having these various forms are commercially available as Hyprene B621 (manufactured by Zeon), KM-357P, EXL2602, EXL2 603 (manufactured by Kureha Chemical Industry Co., Ltd.), metaprene W529, methaprene S201, methaprene C223 (manufactured by Mitsubishi Rayon), and the like.

(G) Flame retardant

The component (G) used as a raw material of the flame-retardant polycarbonate resin composition of the present invention includes, for example, an organic phosphorus compound, a silicon compound, a nitrogen-containing compound, a metal hydroxide, a halogen compound, red phosphorus, and an oxidized compound. Known flame retardants such as antimony and expandable graphite alone or in combination Can be used in appropriate combination. Here, examples of the nitrogen-containing compound include melamine and a melamine compound having an alkyl group or an aromatic group as a substituent. Examples of the metal hydroxide include magnesium hydroxide and hydroxide. Aluminum and the like are preferred.

And, as the Haguchigen compound, tetrapromobisphenol

A, halogenated polycarbonate, decap-mouth modiphenyl ether, tetrapromobisphenol epoxy polyol, halogenated polystyrene, halogenated polyolefin, etc. have excellent flame retardant efficiency, but these are resins. It is preferable to use a halogen-free flame retardant because the mold may be corroded at the time of molding the composition and the natural environment may be adversely affected.

Among the halogen-free flame retardants, organic phosphorus compounds are mentioned as having excellent flame retarding efficiency, and among them, phosphoric acid ester flame retardants are preferred. As the phosphate ester flame retardant, a phosphate compound having at least one ester oxygen atom directly bonded to a phosphorus atom is preferably used. Such a phosphate compound is, for example, represented by the following general formula (2)

[In the formula (2), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or an organic group, and X represents a divalent or higher valent organic group. In addition, p represents 0 or 1, q represents an integer of 1 or more, and 1- represents an integer of 0 or more. ] The phosphoric acid ester compound represented by or a mixture thereof is preferably used. Here, examples of the organic group represented by R ^{1 to} R ⁴ in the general formula (2) include an alkyl group which may have a substituent, a cycloalkyl group, and 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 or the like, which is a group obtained by combining these substituents, or an arylsulfonyl aryl group in which these substituents are bonded by an oxygen atom, a nitrogen atom, an io atom, or the like. It may be a group or the like. In the general formula (2), the divalent or higher valent organic group represented by X means a divalent or higher valent group obtained by removing one or more hydrogen atoms bonded to a carbon atom from the above organic group. For example, it may be an alkylene group which may have a substituent, a phenylene group, 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 containing the component (A), the component (B) and the component (C) according to the present invention, the polycarbonate resin of the component (A) has the following composition. The proportion is 50 to 97.95% by mass. The composition ratio of the component (A) is 50 mass. If it is less than / ₀ , it is difficult to maintain the excellent physical properties inherent to the polycarbonate resin in the obtained resin composition, and the composition ratio is 97.95 mass. If the ratio exceeds / ₀ , the resulting resin composition will not have sufficient fluidity ゃ solvent resistance. The composition ratio of the thermoplastic resin other than the polycarbonate resin as the component (B) is 2 to 47% by mass. The composition ratio of this thermoplastic resin is 2 mass. If it is less than / ₀ , the effect of improving the fluidity 配合 solvent resistance of the resin composition obtained by blending the component (B) is not sufficient, and If the composition ratio exceeds 47% by mass, a high flame retardancy of V-2 or more in the UL standard cannot be obtained in the degree of flame retardancy of the obtained resin composition. 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 flame retardancy and antistatic performance of the resin composition obtained by blending the component (C) are considered. If the composition ratio exceeds 3% by mass, physical properties such as impact strength of the obtained resin composition will be reduced. is there. 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 property in a composition having a basic constitution comprising the components (A), (B) and (C). In applications where the ability to maintain performance is required and the flame retardancy is even higher, the dripping of the (D) component is based on a total of 100 parts by mass of these basic components. A flame-retardant polycarbonate resin composition containing 0.02 to 5 parts by mass of an inhibitor is preferably used. If the compounding ratio of the component (D) is less than 0.02 parts by mass, the effect of the compounding is not sufficient, and even if the compounding amount is increased beyond 5 parts by mass, an effect commensurate with it is 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 this flame retardant polycarbonate resin composition, A flame-retardant polycarbonate resin composition obtained by mixing 0.1 to 10 parts by mass of the functional group-containing silicone compound of the component (E) with respect to a total of 100 parts by mass of the basic constituent components If the compounding ratio of the component (E) is less than 0.1 part by mass, the effect of the compounding effect is exerted. This is because the effect is not sufficient, and even if the compounding amount is increased beyond 10 parts by mass, a corresponding effect cannot be obtained, and the mechanical strength of the obtained resin composition is rather lowered. . 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 even higher impact resistance and flame retardancy, the total amount of the above-mentioned basic components is 100 parts by mass. A flame-retardant polycarbonate resin composition obtained by blending 0.5 to 10 parts by mass of a core-shell type elastic rubber-like material of component F) is suitably used. If the compounding ratio of component (E) is less than 0.5 part by mass, the effect of the compounding is not sufficient, and even if the compounding amount is increased beyond 10 parts by mass, an effect commensurate with it is obtained. It is not possible. 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 parts by mass based on a total of 100 parts by mass of the above basic components. Flame-retardant polycarbonate resin compositions containing up to 30 parts by mass are suitably used. If the blending ratio of component (G) is less than 0.1 part by mass, the effect of the blending is not sufficient, and even if the blending amount is increased beyond 30 parts by mass, the effect corresponding thereto cannot be obtained. Because it is.

Next, regarding the composition ratio of each component in the flame-retardant polycarbonate resin composition containing the component (A), the component (I-I) and the component (C), the polycarbonate resin of the component (A) is as follows. The composition ratio is 37 to 97.95% by mass. When the composition ratio of the component (A) is less than 37% by mass, it is difficult to maintain excellent physical properties inherent to the polycarbonate resin in the obtained resin composition, and This composition ratio is 97.95 mass. If the ratio exceeds / o, the obtained resin composition will have insufficient rigidity and dimensional stability. A more preferable composition ratio of the component (A) is 48 to 94.9% by mass. The composition ratio of the inorganic filler (H) is 2 to 60% by mass. If the composition ratio of the thermoplastic resin is less than 2% by mass, the effect of improving the rigidity and dimensional stability of the resin composition obtained by blending the component (H) is not sufficient. Also, if the composition ratio exceeds 60% by mass, the moldability of the obtained resin composition will be reduced. The more preferable composition ratio of the component (H) is 5 to 50% by mass.

Further, the composition ratio of the acid-base-containing aromatic vinyl resin (C) is set to 0.05 to 3% by mass. If 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) has flame retardancy and antistatic properties. If the effect of improving the sustainability of performance is not sufficiently exhibited, and if the composition ratio exceeds 3% by mass, physical properties such as impact strength of the obtained resin composition will be reduced. It is. A more preferable mixing ratio of the component (C) is 0.1 to 2% by mass, and a more preferable mixing ratio is 0.5 to 2% by mass.

The flame-retardant polycarbonate resin composition of the present invention is a composition having a basic constitution comprising the above components (A), (H) and (C), which has practically sufficiently high flame retardancy and antistatic property. Although sustainability of performance can be obtained, in applications where even higher flame retardancy is required, dripping of component (D) can be suppressed for a total of 100 parts by mass of these basic components. A flame-retardant polycarbonate resin composition containing 0.02 to 5 parts by mass of an agent is suitably used. The mixing ratio of the component (D) is 0.02 parts by mass. If the amount is less than 5, the effect of the compounding effect is not sufficiently exhibited, and even if the compounding amount is increased beyond 5 parts by mass, the effect corresponding thereto cannot be obtained. The more preferable mixing ratio of the component (D) is 0.1 to 1 part by mass.

Further, in order to further improve the flame retardancy of the flame retardant polycarbonate resin composition, a total of 10% of the composition comprising each of the above basic components (A), (H) and (C) is used. A flame-retardant polycarbonate resin composition obtained by mixing 0.1 to 10 parts by mass of the functional group-containing silicone compound (E) with respect to 0 parts by mass is preferably used. If the blending ratio of the component (E) is less than 0.1 part by mass, the effect of the blending is not sufficiently exhibited, and even if the blending amount exceeds 10 parts by mass, the effect corresponding thereto cannot be obtained. This is because the mechanical strength of the obtained resin composition is rather lowered. 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 even higher impact resistance and flame retardancy, the above basic components (A), (H) and (G (F) Flame retardant obtained by blending 0.5 to 10 parts by mass of a core / shell type graphitic elastic body of component (F) with respect to a total of 100 parts by mass of the composition comprising the components of A water-soluble polycarbonate resin composition is preferably used. If the blending ratio of the component (E) is less than 0.5 parts by mass, the effect of the blending is not sufficient, and even if the blending amount is increased beyond 10 parts by mass, the effect commensurate with it is obtained. It is not possible. 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 above basic constituents (A), (H) and (C) A flame-retardant polycarbonate resin composition comprising 0.1 to 30 parts by mass of the flame retardant of the component (G) based on a total of 100 parts by mass of the composition comprising Used for 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. Because.

Next, regarding the method for producing the flame-retardant polycarbonate resin composition of the present invention, the components (A), (B) or (H) and (C) are further added at the above-mentioned mixing ratios. Accordingly, the components (D) to (G) may be appropriately blended, mixed and melt-kneaded. The compounding and kneading of each component here are performed by premixing with commonly used equipment, for example, a ribbon blender and a drum tumbler, and then a Banbury mixer, a single screw extruder, and a twin screw extruder. Melt kneading can be carried out using a rewind extruder, a multi-screw screw extruder, or a kneader. The temperature at the time of melt-kneading may be appropriately selected usually in the range of 240 to 300 ° C. The melt-kneaded product is preferably formed by a method of extruding into a strand by an extruder, particularly a vent-type extruder, followed by 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 obtained from the composition containing the component (A), the component (B) and the component (C) of the present invention thus obtained is excellent in flame retardancy and solvent resistance and has dust on the surface. Excellent durability of antistatic performance without adhesion. The component (A), the component (H) and the component (C) of the present invention A molded article obtained from a composition containing styrene has excellent rigidity, dimensional stability, and flame retardancy, and also has excellent durability of antistatic performance without dust adhering to its surface. Therefore, electronic and electrical equipment that is required to have such characteristics, such as copiers, fax machines, televisions, radios, tape recorders, VCRs, personal computers, printers, telephones, and information terminals The composition of the present invention is highly useful in fields such as housings and internal parts of machines, refrigerators and microwave ovens, as well as in automobile parts.

Next, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples.

(Examples 1 to 19)

[1] Production of flame-retardant polycarbonate resin composition

The components (A), (B), (H), (C), (D), (E), (F) and (G) of the raw materials were mixed at the mixing ratios shown in Tables 1 and 2 [ However, each of the components (A), (B), (H) and (C) in the table represents% by mass, and each of the components (D), (E), (F) and (G) The parts by mass of each component are shown with respect to a total of 100 parts by mass of the components (A), ((B) or (H)} and (C). And supplied to a vent-type twin-screw extruder (TEM35, manufactured by Toshiba Machine Co., Ltd.), and melt-kneaded at 280 ° C. Then, the kneaded product was extruded into a strand, cooled, and cut to obtain a pellet of a flame-retardant polycarbonate resin composition.

Next, the obtained pellets were dried at 120 ° C for 12 hours, and then injection-molded at a forming temperature of 270 ° C and a mold temperature of 80 ° C to obtain various test pieces. 'Here, the following were used as the components (A), (B), (H), (C), (D), (E), (F) and (G) of the raw materials. (A) Polycarbonate resin

Polycarbonate resin having a structural unit derived from (A-1) 2,2-bis (4-hydroxyphenyl) propane, having a linear structure and having a viscosity average molecular weight of 19,500 .

(A-2) contains 4% by mass of a block having 30 structural units derived from dimethylsiloxane, and the other comprises structural units derived from 2,2-bis (4-hydroxyphenyl) propane, A polycarbonate resin having a linear structure and a viscosity average molecular weight of 1500.

(B) Thermoplastic resin other than polycarbonate resin

(B-1) Melt flow rate measured at 200 ° C and 5 kg load in accordance with JISK-7210, 8 g / l 0 min, and polybutadiene rubber content 1 0 mass ^_0/0 high impact polystyrene resin is [Idemitsu Petrochemical Co., Ltd.: IT 4 4].

(Β-2) Acrylonitrile-butadiene-styrene copolymer resin (Technopolymer Co., Ltd .: DΡ611).

(Β-3) Acrylonitrile-styrene copolymer resin (Technopolymer: 290).

(Β-4) Polyethylene terephthalate resin [Mitsubishi Rayon Co., Ltd .: Dylanite No. 5 23].

(Η) Inorganic filler

(Η—1) Glass fiber with a fiber diameter of 13 m and a fiber length of 13 mm [M409C manufactured by Asahi Fiber Glass Co., Ltd.].

(H-2) Glass flakes with an average major axis of 140 μm [Nippon Sheet Glass: REFG 101].

(H-3) Talc having an average particle size of 3 μηι [Fuji Talc: Τ-A25]. · (H-4) Carbon fiber with a fiber diameter of 6 / zm and a fiber length of 13 mm [Toho Rayon: HTAC-6 SRS:].

(C) Acid-base-containing aromatic vinyl resin

(C-1) Sodium polystyrenesulfonate having a weight average molecular weight of 20,000 and a sulfonation ratio of 100%.

(C-2) a polystyrene sulfonate having a weight average molecular weight of 20,000 and a sulfonation ratio of 40%.

(D) Drip inhibitor

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

(E) Silicone compound containing functional group

(E-1) Methyl phenyl silicone having a vinyl group and a methoxy group as a functional group [KR 219 manufactured by Shin-Etsu Chemical Co., Ltd.].

(E-2) Methylphenyl silicone containing a methoxy group as a functional group [Toray Dow Corning: DC3037].

(F) Core / shell type graph rubber-like elastic material

(F-1) Methyl methacrylate acrylate-styrene copolymer resin [Kuwa Chemical Industry Co., Ltd. ': KM355P].

(G) Flame retardant

(G-1) resorcinol bis (diphenyl phosphate) [Adeka Stab PFR] manufactured by Asahi Denka Kogyo KK

(G-2) Tetrabromobisphenol A oligomer [manufactured by Teijin Chemicals Ltd .: FG750].

[Comparative Example:! ~ 1 5)

[1] Production of flame-retardant polycarbonate resin composition

The components of the raw materials are shown in Table 3 and Table 4. And supplied to a vented twin-screw extruder (TEM35, manufactured by Toshiba Machine Co., Ltd.) and melt-kneaded at 280 ° C. Next, the kneaded material was extruded into a strand, cooled, and cut to obtain a pellet of a flame-retardant polycarbonate resin composition.

Next, the obtained pellets were dried at 120 ° C for 12 hours, and then injection-molded at a molding temperature of 270 ° C and a mold temperature of 80 ° C, to obtain a test piece and a molded product. did.

Here, as the components of the raw materials and additives, the same components as those in the examples except for the following were used. .

(C) Acid-base-containing aromatic vinyl resin

(C-3) Sodium sodium dodecylbenzenesulfonate [Takemoto Yushi Co., Ltd .: Electacut S412-2].

(C-4) Polyamide elastomer [manufactured by Atofina Japan: PE BAX-MH 1657].

(E) Silicone compound containing functional group

(E-3) dimethyl silicone [manufactured by Toray Dow Corning: SH200].

[2] Evaluation of flame-retardant polycarbonate resin composition

Using the test pieces of the obtained flame-retardant polycarbonate resin composition, the performance of each of the following items was evaluated. The results are shown in Tables 1 to 4.

(1) Melt fluidity

According to JISK 7210, the Meltoff mouth rate was measured under the conditions of a temperature of 280 ° C and a load of 2.16 kg.

(2) Izod impact strength

Conforms to AS TM D 256 and has a specimen thickness of 3.18 mm. The measurement was carried out at 23 ° C.

(3) Grease resistance

It was measured in accordance with the chemical resistance evaluation method (critical strain due to 1/4 ellipse). That is, the test piece (thickness = 3 mm) was fixed to the 1/4 elliptical surface of the jig shown in Fig. 1, and the test piece was coated with Albanian grease (manufactured by Showa Shell Sekiyu KK). Hold for hours. Then, the minimum length (X) at which cracks occurred was read, and the critical strain (%) was obtained by the following equation (1).

b 1

One 3/2 _m

Limit distortion (%) = —— [1— (——) X2 ² "I

]

2 a ² a ^!

(1)

(t: mm)

(4) Flexural modulus

The measurement was performed according to JISK 7203. Here, as a test machine, Orientec Co., Ltd .; ΗΤΜ-250 was used, and the measurement was performed under the conditions of a bending speed of 2.0 mm / min and a span of 60 mm. '

(5) Mold shrinkage

At an injection molding machine at a molding temperature of 300 ° C and a mold temperature of 80 ° C, a plate-like test piece with a side length of 15 Omm and a thickness of 3 mm was formed. After holding for 48 hours in an atmosphere at a temperature of 23 ° C and a humidity of 50% RH, the shrinkage (%) in the resin flow direction (MD) during the molding of this test piece was measured. did.

(6) Half-life of charged voltage A square plate of 25 x 35 mm and thickness of 3 mm was used as a test piece. It was charged for 1 minute at an applied voltage of 9 kv, and the time (seconds) at which the potential after discharge was halved with respect to the charged voltage was measured.

(7) Half-life of charged voltage after washing with water

After washing the test piece used in the above (6) with water at 23 ° C for 1 minute, wipe off the adhering water and apply it for 1 minute at an applied voltage of 9 kV. The time (seconds) at which the potential after the discharge was halved was measured.

(8) Flame retardant

A 1.5 mm thick test piece was used to perform a vertical combustion test according to Underwriters Laboratory, Subject 94.

Table 1

Example Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9

(A— 1) 84.0 89.5 89.5 89.5 88.5 84.0 54.7 89.5 89.5

A

(A— 2) 30.0

(B- 1) 10. 0 10. 0 10. 0 1 0. 0 1 0.0.0 Pair (B--1) 15. 0 1 5.0

B

(B— 3) 10. 0

(B— 4) 15.0

(C-1) 1. 0 0.5 0.5 0.5 0.5 0.5 0.3 0.5 0.5

C

(C-1 2) 1.5 1.0

D (D-1) 0.3 0.3 0.3 0.5 0.5 0.5 0.5 0.5 0.5

(E-1) 2.0 1.0

00 E

(E-2) 2.0

F (F-1) 3.0 3.0 3.0 5.0 5.0 3.0 3.0

(G-1) 5.0

G

(G-2) 5.0 Meltoff π-ray (g / 10min.) 35 33 33 35 30 26 35 40 36 Eye 'Impact strength (kJ / m ² ) 75 40 60 60 65 80 75 55 55 0.8 0.8 0.6 0.6 0.6 0.7 0.8> 1.0.6 0.8 0.6 0.6 Half-life of charged voltage (sec) 20 80 80 85 5 25 1 20 80 80

Half life of charged voltage after washing (seconds) 20 80 80 85 5 25 1 20 80 80 Flame retardant [UL 94] V-2 V- 1 V- 1 V-0 V-0 V-0 V-0 V- 0 V- 0

Table 2

Example Banquet Example 10 Example 11 Example 12 Example 'J 1' 3 υ Lung lJU Example 15 Room Example 16 Example 17 Example 18 Example 19

(A-1) 59.0 SO gg 5 AS ς R4 7 89.5 89.5

A

(H-1) in 0 in Ω in η 20 0 10

H X

(H-3) 1 u u

(H-4) 1

(C-1) (i c U. ς ϋ V. ϋ n u.q 0 u. U ς

C

(C-1 2)

(.3 ϋ 1, v

D (D- 1) U.0 Q U. U, U.0 n ς U.0 c u.0 u.0

CO (E-1)? Η 1 Π

Or E

(E- 2) L. V

F (F- 1) q.y.V ύ o U n u n u

(G-1)

G

(G-2) 0.Izod impact strength (kJ / m ² ) 5 12 1ft 1R 12 J 3 35 15 IS Flexural modulus (MPa) 5800 4000 3800 3900 7100 6500 6100 4800 4100 3800 Evaluation Molding shrinkage (50 MD 2.5 5.0 5.5 5.5 1.8 1.9 1.7 3.0 4.5 5.0 Charge half-life (sec) 20 75 80 85 5 5 15 120 80 85

Half-life of charged voltage after washing (seconds) 20 75 80 85 5 5 15 120 80 '85 Flame retardant (UL 94) V- 0 V-0 V-2 V-0 V-0 V-0 V-0 V-0 V-0 V-0

Table 3

ϊ m face example 1 lt¾ example 2 t 3 thigh example 4 comparative example 5 listening example 6 brain row 7

A (A- 1) 9 9.0 0 9.0 0.0 44.5 8 6.08 8 8.5 8 8.5 8 8.5

(B-1) 1 0. 0 5 5. 0 1 0. 0

B

Pair (B-3) 1 0. 0 1 0. 0 1 0. 0

(C-1) 1.0.0 0.5.4.0

C (C-2) 1.5 1, 5

(C-1) 1.5 D (D-1) 0.3 0.3 0.3 0.5 0.5 0.5 0.5

(E- 2) 6.0 2.0

E

(E-3) 2.0

F (F-l) 3.0 3.0 3.0 3.0 3.0 3.0

CO

Meltoff n-rate (g / IOmin.) 1 8 3 3 75 3 6 4 0 3 0 3 2 Izo 7 Impact strength (kJ / m ² ) 6 0 6 0 5 8 1 0 6 0 5 5 Grease properties 0.4 0.4 0.6 0.8 0.5 0.5 0.6 0.7 0.7 Voltage half-life of charged voltage (seconds) 30 Infinity 1 0 0 2 1 5 1 0 1 5 Valency

Half-life of charged voltage after washing (S »30 Infinity 1 0 0 2 1 5 Infinity 1 5 Flame retardant [UL94] V-2 NG NG V- 1 V— 0 NG NG

Table 4

Industrial applicability

According to the present invention, a flame-retardant polycarbonate resin composition which is excellent in fluidity, solvent resistance and flame retardancy, and which can obtain a molded article excellent in durability of antistatic performance to which dust does not adhere. Flame-retardant polycarbonate resin composition which is excellent in rigidity, dimensional stability and flame retardancy, and which can obtain a molded article excellent in durability of antistatic performance without adhering dust, and molded article thereof Can be provided.

The scope of the claims

1. Polycarbonate resin 50 to 9 7.95 mass% as component (A), thermoplastic resin other than polycarbonate resin as component (B) 2

To 47% by mass and an aromatic vinyl resin containing an acid base as the component (C)

A flame-retardant polycarbonate resin composition comprising 0.05 to 3% by mass.

2. The flame-retardant polycarbonate resin composition according to claim 1, wherein the polycarbonate resin as the component (A) 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. The flame-retardant polycarbonate resin composition according to any one of claims 1 to 3, wherein the acid-base-containing aromatic vinyl resin (C) is a polystyrene sulfonic acid metal salt.

5. A total of 100 parts by mass of component (A), component (B) and component (C) is blended with 0.02 to 5 parts by mass of drip inhibitor as component (D). The flame-retardant polycarbonate resin composition according to claim 1.

6. The flame-retardant polycarbonate resin composition according to claim 5, wherein the component (D) is a fluororesin.

7. A total of 100 parts by mass of the components (A), (B) and (C) is blended with 0.1 to 10 parts by mass of the functional group-containing silicone compound as the component (E). The flame-retardant polycarbonate resin composition according to any one of claims 1 to 6.

8. For a total of 100 parts by mass of component (A), component (B) and component (C), a core-shell type rubber-like rubber is used as component (F).

Claims

The flame-retardant polycarbonate resin composition according to any one of claims 1 to 7, comprising 0.5 to 10 parts by mass of an elastic body.

9. A total of 100 parts by mass of the components (A) and (B) and component (C), and 0.1 to 30 parts by mass of a flame retardant as the component (G). Item 10. The flame-retardant polycarbonate resin composition according to any one of Items 1 to 8.

10. Polycarbonate resin 37 to 9 7.95 mass as component (A). / _0, (H) an inorganic filler 2-6 0 wt% Oyobi (C) an acid salt the aromatic Ingredient vinyl resin 0.0 5 flame retardant polycarbonate resin composition comprising 3 wt% as component .

1 1. The inorganic filler of the component (H) is at least one filler selected from the group consisting of glass fiber, glass flake, glass beads, talc, and carbon fiber. 3. The flame-retardant polycarbonate resin composition according to claim 1.

12. The flame-retardant polycarbonate resin composition according to claim 10 or 11, wherein the acid-base-containing aromatic vinyl resin as the component (C) is a metal salt of polystyrene sulfonic acid.

1 3. For 100 parts by weight of the total of (A) component and (H) component and (C) component, add 0.02 to 5 parts by mass of drip inhibitor as (D) component. The flame-retardant polycarbonate resin composition according to any one of claims 10 to 12, which is blended.

14. The flame-retardant polycarbonate resin composition according to claim 13, wherein the dripping inhibitor of the component (D) is a fluororesin.

1 5. For the total 100 parts by mass of the components (A) and (H) and the component (C), 0.1 to 10 parts by mass of the functional group-containing silicone compound as the component (E) The composition according to any one of claims 10 to 14, wherein Flame retardant polycarbonate resin composition.

1 6. For a total of 100 parts by mass of the components (A) and (H) and the component (C), the core-shell type graft rubber-like elastic body 0.5- The flame-retardant polycarbonate resin composition according to any one of claims 10 to 15, comprising 10 parts by mass.

1 7. A total of 100 parts by mass of component (A), component (H) and component (C) is blended with 0.1 to 30 parts by mass of flame retardant as component (G). The flame-retardant polycarbonate resin composition according to any one of claims 10 to 16.

1 8. A molded article obtained by molding the flame-retardant polycarbonate resin composition according to any one of claims 1 to 17.

19. The molded article according to claim 18, wherein the molded article is an electric or electronic device part.