JP2002212409A - Flame-retardant polycarbonate resin composition, its manufacturing method and molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame-retardant polycarbonate resin composition which can give a molded article exhibiting high flame retardancy and excellence in a recycling property and in antistatic performances and excellent in external appearances while maintaining physical characteristics inherent in the polycarbonate resin by merely adding a small amount of a flame retardancy-imparting component, its manufacturing method and a molded article. SOLUTION: The flame-retardant polycarbonate resin composition comprises (A) 95-99.99 mass% of a polycarbonate resin and (B) 0.01-5 mass% of an acid salt group-containing aromatic vinyl resin containing less than 5 mass% of an inorganic metal salt. The manufacturing method of the flame-retardant polycarbonate resin composition comprises spraying the component (B) in a state of a solution having a concentration of 10-60 mass% on the component (A) and kneading the two components. The molded article is obtained by molding the resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a flame-retardant polycarbonate resin composition, a method for producing the same, and a molded article. More specifically, the present invention relates to a flame-retardant polycarbonate resin composition capable of obtaining a molded article having excellent appearance, a method for producing the same, and a molded article 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, flame-retardant polycarbonate resins using these halogen-based flame retardants have a great impact on the environment when burning incineration of wastes. ing. Therefore, as the non-halogen flame retardant, an organic phosphorus flame retardant, particularly an organic phosphoric ester compound, acts as a plasticizer simultaneously with imparting flame retardancy. Polycarbonate resin compositions have 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 in order to cope with a thinned or large-sized molded product. Therefore, this organic phosphate compound contributes to the improvement of flame retardancy, but it does not always adhere to a mold or generate gas during molding of a polycarbonate resin. Not enough. In addition, molded articles of the flame-retardant polycarbonate resin composition using the organophosphate compound have a problem that the impact strength is reduced or discolored when used in a high-temperature or high-temperature, high-humidity environment. Furthermore, since the molded article of this flame-retardant polycarbonate resin composition has insufficient thermal stability, there remains a problem that it is inferior in recyclability for resource saving.

In order to solve such problems, Japanese Patent Application Laid-Open No. 50-98546 discloses a method in which a small amount of a metallic salt of a polymeric aromatic sulfonic acid, for example, sodium salt of polystyrene sulfonic acid is blended. It is proposed to make the resin flame-retardant. However, when 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, this polystyrene sulfonate sodium salt becomes dispersible. Due to the inferiority, there is a problem that the appearance of the molded article is inferior. Also, JP-A-11-17
Japanese Patent No. 2063 discloses a flame-retardant thermoplastic resin composition comprising an aromatic vinyl resin having an acid base such as an alkali metal salt of sulfonic acid and another thermoplastic resin, or a flame retardant obtained by further blending a flame retardant. Although a thermoplastic resin composition is proposed, even in this case, when a polycarbonate resin is used as the thermoplastic resin, the dispersibility of the aromatic vinyl resin having an acid base in the polycarbonate resin is inferior. There is a problem that the appearance of the molded article is poor and the transparency is lowered.

[0006]

SUMMARY OF THE INVENTION The present invention provides high flame retardancy and excellent recycling properties while maintaining the physical properties inherent to polycarbonate resins by adding only a small amount of a flame retardant component. An object of the present invention is to provide a flame-retardant polycarbonate resin composition having antistatic performance and capable of obtaining a molded article having an excellent appearance, a method for producing the same, and a molded article thereof.

[0007]

Means for Solving the Problems The present inventors have made various studies to solve the above-mentioned problems, and as a result, have found that a polycarbonate resin containing an acid-base-containing aromatic compound having an inorganic metal salt content of less than 5% by mass. The present inventors have found that a flame-retardant polycarbonate resin composition containing a vinyl resin in a specific ratio can achieve the above object, and have completed the present invention based on these findings.

That is, the gist of the present invention is as follows. [1] Polycarbonate resin 95 to 9 as component (A)
A flame-retardant polycarbonate resin composition comprising 9.99% by mass and 0.01 to 5% by mass of an acid-base-containing aromatic vinyl resin having a content of an inorganic metal salt of less than 5% by mass as a component (B). [2] The acid-base-containing aromatic vinyl resin of the component (B) is
The flame-retardant polycarbonate resin composition according to [1], which is an acid-base-containing aromatic vinyl resin having a content of an inorganic metal salt of less than 3% by mass. [3] Further, a polytetrafluoroethylene-based resin as the component (C) is used in an amount of 0.01 to 5 parts by mass based on 100 parts by mass of the total of the components (A) and (B) described in the above [1].
The flame-retardant polycarbonate resin composition according to the above [1] or [2], which is added by mass. [4] Further, a core / shell type elastomer as the component (D) is used in an amount of 0.01 to 1 based on 100 parts by mass of the total of the components (A) and (B) described in the above [1].
The flame-retardant polycarbonate resin composition according to any one of the above [1] to [3], which is added with 0 parts by mass. [5] Further, a phosphate ester flame retardant as the component (E) is used in an amount of 0.01 to 30 parts by mass based on 100 parts by mass of the total of the components (A) and (B) described in the above [1]. The flame-retardant polycarbonate resin composition according to any one of the above [1] to [4], which is added. [6] The above [1] to [1], which are produced by spraying and kneading the acid-base-containing aromatic vinyl resin of the component (B) in a solution having a concentration of 10 to 60% by mass to components other than the component (B). The flame-retardant polycarbonate resin composition according to any one of [5]. [7] In producing the flame-retardant polycarbonate resin composition according to any of [1] to [5], (B)
The acid-base-containing aromatic vinyl resin having a concentration of 10 to 60
A method for producing a flame-retardant polycarbonate resin composition, characterized in that, in a mass% solution state, the mixture is sprayed onto components other than the component (B) and then kneaded. [8] A molded article obtained by molding the flame-retardant polycarbonate resin composition according to any one of [1] to [6].

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention relates to an aromatic vinyl resin containing 95 to 99.99% by mass of a polycarbonate resin as the component (A) and an inorganic base having a content of the inorganic metal salt of less than 5% by mass as the component (B). It is a flame-retardant polycarbonate resin composition comprising 0.01 to 5% by mass of a base resin. In the flame-retardant polycarbonate resin composition, the content of the inorganic metal salt of the component (B) of the acid-base-containing aromatic vinyl resin having a content of less than 5% by mass is 0.01% by mass or more. If the compounding ratio of the component is less than 0.01% by mass, the flame retardancy of the flame-retardant polycarbonate resin composition obtained is insufficient, and the acid-base-containing aromatic component of the component (B) The reason why the content of the vinyl-based resin is set to 5% by mass or less is that flame retardancy can be sufficiently imparted even when the compounding ratio of the component (B) is within 5% by mass. If it exceeds, the physical properties of the obtained flame-retardant polycarbonate resin composition will be reduced.

[0010] The flame-retardant polycarbonate resin composition of the present invention may be used, if necessary, with respect to 100 parts by mass of the resin composition having the basic constitution comprising the components (A) and (B). 0.01 to 5 parts by mass of a polytetrafluoroethylene-based resin as the component (C), and 0.01 to 10 parts by mass of the core / shell type elastomer as the component (D).
In addition, a phosphate ester-based flame retardant can be added as a component (E) in an amount of 0.01 to 30 parts by mass. Component (A), a polycarbonate resin, component (B), an acid-base-containing aromatic vinyl resin having an inorganic metal salt content of less than 5% by mass, component (C), a polytetrafluoroethylene resin, As the core / shell type elastomer of the component and the phosphate ester flame retardant of the component (E), the following are preferably used.

(A) Polycarbonate resin The polycarbonate resin (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, those produced by reacting a dihydric phenol with a carbonate precursor by a solution method or a melting method can be 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.

Further, 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) Acid-base-containing aromatic vinyl resin The acid-base-containing aromatic vinyl resin (B) used as a raw material of the flame-retardant polycarbonate resin composition of the present invention is an aromatic vinyl-based thermoplastic resin. A thermoplastic resin in which part of the hydrogen atoms in the aromatic ring has been substituted with an acid base,
An acid-base-containing aromatic vinyl resin in which the content of the inorganic metal salt remaining in the acid-base-containing aromatic vinyl resin is reduced to less than 5% by mass.

That is, when a part of the hydrogen atoms in the aromatic ring of the aromatic vinyl-based thermoplastic resin is replaced with an acid base, for example, polystyrene is contacted with sulfuric anhydride to be sulfonated and then sodium hydroxide. When the method of neutralization is adopted, sodium sulfate by-produced there remains in sodium polystyrene sulfonate, which is an acid-base-containing aromatic vinyl resin. When a method of neutralization with potassium hydroxide is employed, potassium sulfate is by-produced and remains in potassium polystyrene sulfonate. When the content of sodium sulfate or potassium sulfate exceeds 5% by mass, the physical properties of the flame-retardant polycarbonate resin composition comprising the sodium polystyrene sulfonate or potassium polystyrene sulfonate and the polycarbonate resin, particularly In addition to lowering the inherent mechanical, thermal, recycling, and electrical properties inherent in the resin, the resin also has protrusions on the surface of molded products obtained by molding the composition. The occurrence rate of appearance defects due to the generation of objects increases. Therefore, as the acid-base-containing aromatic vinyl-based resin of the component (B) in the present invention, the content of the inorganic metal salt remaining in the acid-base-containing aromatic vinyl-based resin is reduced to less than 5% by mass. Is used. This (B)
More preferred as the component is an acid-base-containing aromatic vinyl resin in which the content of the inorganic metal salt is reduced to less than 3% by mass.

Next, as the aromatic vinyl resin, polystyrene, rubber-modified polystyrene, styrene-
A thermoplastic resin having at least a structural unit derived from styrene in a polymer chain such as an acrylonitrile copolymer or an acrylonitrile-butadiene-styrene copolymer resin can be used. Among these, a polystyrene resin is particularly preferably used.

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, and alkaline earth metal salts. , 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, an acid-base-containing polystyrene resin suitable as the acid-base-containing aromatic vinyl resin is represented by the following general formula (1):

[0021]

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

Next, regarding the method for producing the acid-base-containing aromatic vinyl resin as the component (B), an aromatic vinyl monomer having a sulfone group or the like as a monomer or a copolymerizable with them. After polymerization or copolymerization with other monomers, neutralization with a basic substance, may be a method of purification, aromatic vinyl-based polymer or aromatic vinyl-based copolymer, or those of The mixture may be sulfonated, neutralized with a basic substance, and then purified.

In the case where the aromatic vinyl polymer is sulfonated, neutralized and purified, for example, a polystyrene resin solution of 1,2-dichloroethane is added with sulfuric anhydride to cause a reaction. And then neutralized with a basic substance such as sodium hydroxide or potassium hydroxide, and then purified. For the purification of sodium polystyrene sulfonate or potassium polystyrene sulfonate, a method of recrystallization using a solvent may be employed, a method of filtering sodium sulfate or potassium sulfate, an ion exchange agent, a chelating agent. Alternatively, a treatment method using an adsorbent may be employed. And the content of inorganic metal salts such as sodium sulfonate remaining in sodium polystyrene sulfonate or potassium polystyrene sulfonate after neutralization is less than 5% by mass,
Preferably, the content reduced to less than 3% by mass is used as the component (B).

Further, the acid-base-containing aromatic vinyl resin (B) has a weight average molecular weight of 1,0.
Those having a value of from 00 to 300,000 are preferably used.
That is, if the weight-average molecular weight of the acid-base-containing aromatic vinyl resin is less than 1,000, the physical properties of the resin composition using this as a compounding component may not be practically sufficient, If the weight-average molecular weight of the acid-base-containing aromatic vinyl-based resin exceeds 300,000, the fluidity of the resin composition using the same as a compounding component becomes poor, leading to a reduction in productivity. .

(C) Polytetrafluoroethylene Resin The flame-retardant polycarbonate resin composition of the present invention basically comprises both of the above components (A) and (B). May be requested. As a flame-retardant polycarbonate resin composition that satisfies such requirements, a polytetrafluoroethylene-based resin as a component (C) is further added, based on a total of 100 parts by mass of both components (A) and (B). 0.
A flame-retardant polycarbonate resin composition obtained by adding 01 to 5 parts by mass is suitably used.

As the polytetrafluoroethylene resin of the component (C), in addition to a homopolymer of tetrafluoroethylene, a copolymer of tetrafluoroethylene with hexafluoropropylene or an ethylene monomer containing no fluorine atom can be used. A polymer or copolymer which is a union and has a structural unit derived from fluoroethylene in the polymer chain is used. These polytetrafluoroethylene resins may be used alone as the component (C), or two or more of them may be used as the component (C). The polytetrafluoroethylene-based resin preferably has an average molecular weight of 500,000 or more, and more preferably 500,000 to 10,000.
More preferably, it is 0.000.

When a resin having a fibril forming ability is used among the polytetrafluoroethylene 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 resin having a fibril forming ability, Teflon 6-J (manufactured by Du Pont-Mitsui Fluorochemicals Co., Ltd.) is a commercially available product classified into ASTM type 3. , 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.

(D) Core / Shell Type Elastomer Further, depending on the use of the flame-retardant polycarbonate resin composition, there may be a case where the flame-retardant polycarbonate resin composition is further required to have excellent impact resistance, especially low-temperature impact characteristics. As a flame-retardant polycarbonate resin composition that satisfies such requirements, a core / shell type elastomer is further used as a component (D), based on a total of 100 parts by mass of both the components (A) and (B). A flame-retardant polycarbonate resin composition obtained by adding 0.01 to 10 parts by mass is suitably used.

As the core / shell type elastomer of the component (D), an elastomer having a two-layer structure composed of a core and a shell is preferably used. The core is in a soft rubber state, the shell part on the surface is in a hard resin state, and the elastomer itself is preferably a powdered (particle) graft elastomer. Even after the core / shell type graft elastomer is melt-blended with the polycarbonate resin, the particle state of the core / shell type graft elastomer mostly maintains its original form. Therefore, this elastomer is uniformly dispersed in the polycarbonate resin, and is less likely to cause surface delamination.

The core / shell type graft elastomer can be prepared, for example, in the presence of one or more rubbery polymers obtained from monomers mainly composed of alkyl acrylate, alkyl methacrylate or dimethyl siloxane. Those obtained by polymerizing one or two or more vinyl monomers such as styrene 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 using these monomers mainly composed of alkyl acrylate include 70% by mass 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 mass 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 the 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 elastomer, n-butyl acrylate 60 to 8
Styrene and methyl methacrylate in 20 to 4 mass%
An MAS resin elastic material graft-copolymerized at a ratio of 0% by mass is used. Also, polysiloxane rubber components 5 to 9
5% by mass and poly (meth) acrylate rubber component 5 to 95
To a composite rubber having an average particle diameter of about 0.01 to 1 μm having a structure entangled with each other so as to be inseparable from the mass%.
A composite rubber-based graft copolymer obtained by graft-copolymerizing at least one vinyl monomer can also be used. Commercially available core / shell type graft elastomers having these various forms include Hybrene B621 (manufactured by Zeon Corporation), KM-357P (manufactured by Kureha Chemical Industry Co., Ltd.), Metablen W529, and Metablen S2.
001, Metablen C223 and Metablen B621 (manufactured by Mitsubishi Rayon Co., Ltd.).

(E) Phosphate Ester Flame Retardant Depending on the use of the flame-retardant polycarbonate resin composition, a resin having even higher flame retardancy may be required. As a flame-retardant polycarbonate resin composition that satisfies such requirements, a phosphate ester-based flame retardant is further added as a component (E) to the total of 100 parts by mass of both components (A) and (B). A flame-retardant polycarbonate resin composition obtained by adding 0.01 to 30 parts by mass is suitably used.

As the phosphate ester flame retardant of the component (E), a phosphate compound having at least one ester oxygen atom directly bonded to a phosphorus atom is used.
Such a phosphate compound is, for example, represented by the following general formula (2)

[0037]

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.

The phosphate compound represented by the general formula (2) includes, for example, trimethyl phosphate,
Triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, tri (2-ethylhexyl) phosphate, diisopropyl phenyl phosphate, trixylenyl phosphate, Tris (isopropylphenyl) phosphate, trinaphthyl phosphate, bisphenol A bisphosphate, hydroquinone bisphosphate, resorcin bisphosphate, resorcinol diphenyl phosphate, trioxybenzene triphosphate, cresyl diphenyl phosphate, or a substituted product thereof is preferable. No.

Commercial products of such phosphate compounds include, for example, TPP [triphenyl phosphate], TXP [trixylenyl phosphate], CR733S [resorcinol (diphenyl phosphate)] CR741 manufactured by Daihachi Chemical Industry Co., Ltd. [Bisphenol A (diphenyl phosphate)], PX200 [1,3-phenylene-tetrakis (2,6-dimethylphenyl) phosphate, PX201 [1,4-phenylene-tetrakis (2,6-dimethylphenyl) phosphate] , P
X202 [4,4'-biphenylene-tetrakis (2,
6-dimethylphenyl) phosphate and the like. Further, the flame-retardant polycarbonate resin composition of the present invention,
In addition to the above components (A) to (E), various additive components may be contained as necessary. Examples of such additives include an antioxidant, an antistatic agent, an ultraviolet absorber, a light stabilizer (weathering agent), an antibacterial agent, a compatibilizer, and a coloring agent (dye, pigment).

Next, regarding the method for producing the flame-retardant polycarbonate resin composition of the present invention, the acid-base-containing aromatic vinyl resin as the component (B) is used in a concentration of 10 to 60% by mass.
In the above solution state, it is preferable to adopt a method of kneading after spraying on components other than the component (B). That is,
When producing a flame-retardant polycarbonate resin composition having a basic composition comprising the components (A) and (B),
(B) The acid-base-containing aromatic vinyl resin of component (B)
In the 0 to 60% by mass solution state, the components (A) and (B) may be kneaded after the components (A) are sprayed.
When producing a flame-retardant polycarbonate resin composition having a composition comprising a combination of (A) to (E),
(B) The acid-base-containing aromatic vinyl resin of component (B)
In a 0 to 60% by mass solution state, after being sprayed on a mixture of the component (A) and the components (C) to (E),
(E) All components may be kneaded.

The reason why the acid-base-containing aromatic vinyl resin of the component (B) is sprayed on other components in the form of a solution having a concentration of 10 to 60% by mass is that the concentration of the component (B) is 10%.
If the amount of the solution is less than mass%, the solvent may not be sufficiently degassed during the kneading of these components, which may cause deterioration in the physical properties of the resin composition. Further, according to the solution in which the concentration of the component (B) exceeds 60% by mass,
This is because the viscosity of the solution becomes too high, which may hinder uniform dispersion in other components. As the solvent for the component (B), water is preferable. In addition, alcohols such as methyl alcohol and ethyl alcohol, and aromatic hydrocarbons such as toluene and xylene can be used.

Then, the solution of the acid-base-containing aromatic vinyl resin of the component (B) is mixed with the components (A) and (C) to
(E) After spraying on the mixture of the components, the mixture was preliminarily mixed with a ribbon blender or a drum tumbler, and then melt-kneaded while removing the solvent with a single-screw or twin-screw extruder equipped with a vent to obtain a mixture. What is necessary is just to cut | disconnect and shape | mold the molded object of a resin composition. The resin temperature during the melt-kneading here can be appropriately selected in the range of 240 to 300 ° C. The flame-retardant polycarbonate resin composition thus obtained is prepared by using the pellets by injection molding, injection compression molding, extrusion molding, blow molding, press molding, vacuum molding, foam molding. It can be formed into various molded products by the above method.

As described above, in producing the flame-retardant polycarbonate resin composition, the acid-base-containing aromatic vinyl resin as the component (B) was sprayed on other components in a solution state having a concentration of 10 to 60% by mass. The flame-retardant polycarbonate resin composition obtained by kneading later has excellent transparency in the resin composition comprising both components (A) and (B) as compared with the generally employed mixing in the solid state, and (A)
In the resin composition comprising a combination of the components (E) to (E), various properties such as flame retardancy and impact resistance can be improved, and all of these molded articles have excellent surface smoothness. A molded article having a good appearance can be obtained.

The molded article obtained by molding the flame-retardant polycarbonate resin composition of the present invention comprises (A) and (B)
A molded article of the resin composition comprising both components is suitably used for parts of lighting equipment requiring high transparency, such as a headlamp lens of an automobile. Also, (A) ~
(E) In a molded article of a resin composition comprising a combination of components, for example, a copying machine, a facsimile, a television,
Radio, tape recorders, VCRs, personal computers, printers, telephones, information terminals, refrigerators, microwave ovens and other housing and parts for electric and electronic equipment, as well as parts for machinery, architecture, automobiles, etc. Widely used.

[0046]

[Example 1]

(1) Production of sodium polystyrene sulfonate As a raw material polystyrene, a weight average molecular weight was 20,000.
Using 0 polystyrene, this was dissolved in 1,2-dichloroethane as a solvent to prepare a solution having a concentration of 1% by mass. Then, 3.7 g of dioxane was added and dissolved per 100 g of the polystyrene solution. The solution thus obtained and sulfuric anhydride were respectively supplied from different supply tubes to a reaction tank containing 1,2-dichloroethane, and reacted at 20 ° C. for 10 minutes with stirring.

Next, the reaction product was aged at 40 ° C. for 30 minutes, and then neutralized to pH 7 by adding an aqueous solution of sodium hydroxide. The crude product obtained here was dissolved in ethanol to remove sodium sulfate as an insoluble component by filtration, and then ethanol was removed by drying to obtain a purified product. This purified sodium polystyrene sulfonate has a sodium sulfate content of 2% by mass and a sulfonation rate of 1%.
00%.

(2) Production of Flame Retardant Polycarbonate Resin Composition As the component (A) of the raw material, a viscosity average molecular weight of 19,000 was used.
And 280 according to JISK 7210.
C., using a polycarbonate resin having a melt flow rate of 19 g / 10 minutes measured under the conditions of a load of 2160 g,
As the component (B), sodium polystyrene sulfonate having a sodium sulfate content of 2% by mass obtained in the above (1) was used. The mixing ratio of these two components is
The amount was determined to be 99.9% by mass of the component (A) and 0.1% by mass of the component (B).

Next, both of these components (A) and (B) and octadecyl-3- (3,5-dibutyl-4-hydroxyphenyl) propionate as an antioxidant (manufactured by Ciba Specialty Chemicals, Inc .; Irganox) 107
6] with respect to 100 parts by mass of both components (A) and (B).
Parts by mass and tris (2,4-di-t-butylphenyl) phosphite [manufactured by Asahi Denka Kogyo Co., Ltd .;
12] with respect to 100 parts by mass of both components (A) and (B).
One part by weight was mixed, supplied to a vent-type twin-screw extruder (manufactured by Toshiba Machine Co., Ltd .: TEM35), melt-kneaded at 280 ° C., and then pelletized. The flame-retardant polycarbonate resin composition pellets thus obtained were
After drying at 12 ° C for 12 hours, injection molding was performed at a molding temperature of 270 ° C and a mold temperature of 80 ° C to obtain a test piece.

(3) Evaluation of Flame Retardant Polycarbonate Resin Composition (a) Izod Impact Strength Measured at 23 ° C. and 0 ° C. in accordance with ASTM D256. A test piece having a thickness of 3.18 mm was used.

(B) Haze Parallel light transmittance was measured in accordance with JIS K 7105. As a test piece, a thickness of 3.2 mm, 25 × 35
mm square plate was used. (C) Weld strength Tensile strength test piece (for weld test)
The measurement was performed by molding with a point gate, molding a test piece having a weld, and performing a tensile test.

(D) Half-life of charged voltage A test piece (25 × 35 × 3 mm) was charged with an applied voltage of 9 kv for 1 minute, and the time (second) at which the potential after the discharge was halved with respect to the charged voltage was measured. did. (E) Appearance of molded article Using an injection molding machine (manufactured by Toshiba Machine Co .; IS-45P), a test piece (80 × 40 × 3 mm) was molded under the conditions of a resin temperature of 320 ° C. and a mold temperature of 80 ° C. The test pieces at the cycle were visually observed and evaluated in four stages: good appearance = ◎, slight bumps = ○, slightly bumps = △, and bumps = ×.

(F) Residual heat stability In the molding in the above (e), 20
The test piece was molded after being retained for one minute, and the color tone change with the test piece before the retention was measured. This measurement is based on JIS 7103
The color difference (ΔE) was determined according to (Yellowness test method). (G) Recyclability Using a molding machine for evaluating the appearance of the molded article, resin temperature 32
Under a condition of 0 ° C. and a mold temperature of 80 ° C., a housing (A4 type) of the notebook personal computer was injection-molded. Then, the molded product was pulverized, and was again injection-molded under the same conditions as a 100% recycled material to form a test molded product.
Then, the Izod impact strength of the recycled molded product was measured according to the above.

(H) High-temperature and high-humidity resistance A molded product was subjected to a temperature of 70.degree.
Treated for 0 hours. The Izod impact strength after the treatment was measured according to the above. (I) Flame retardancy Measured in accordance with the UL94 combustion test. A test piece having a thickness of 3 mm was used. (J) Oxygen index Measured according to JIS K 7201. Table 1 shows the evaluation results of these flame-retardant polycarbonate resin compositions.

Example 2 (1) Production of Flame-Retardant Polycarbonate Resin Composition 99.7% by mass of the same polycarbonate resin as in Example 1 as the component (A) and Example 2 as the component (B) After the preparation was performed in the same manner as in (1) of 1 above, water was added to make
A flame-retardant polycarbonate resin composition was produced using 0.3% by mass of a 5% by mass aqueous solution of sodium polystyrene sulfonate.

In preparing this composition, an aqueous solution of sodium polystyrene sulfonate having a concentration of 35% by mass, which is the component (B), was sprayed uniformly on the polycarbonate resin pellets of the component (A) by spraying. The kneading of both components (A) and (B) was the same as in (2) of Example 1. (2) Evaluation of Flame Retardant Polycarbonate Resin Composition The flame retardant polycarbonate resin composition obtained in the above (1) was evaluated in the same manner as in Example 1, (3). Table 1 shows the evaluation results.

Comparative Example 1 (1) Production of Sodium Polystyrene Sulfonate A sulfonation reaction of polystyrene with sulfuric anhydride was carried out in the same manner as in (1) of Example 1. And the reaction product obtained here is pH adjusted with sodium hydroxide aqueous solution.
After neutralization to 7, the solvent and water were removed under reduced pressure to obtain sodium polystyrene sulfonate. The sodium polystyrene sulfonate thus obtained had a content of sodium sulfate of 6% by mass and a sulfonation ratio of 100%.

(2) Production of Flame-Retardant Polycarbonate Resin Composition Except that the unpurified sodium polystyrene sulfonate obtained in the above (1) was used as the component (B) as a raw material, (2) In the same manner as in (1), a flame-retardant polycarbonate resin composition was produced. (3) Evaluation of flame-retardant polycarbonate resin composition The flame-retardant polycarbonate resin composition obtained in the above (2) was evaluated in the same manner as in Example 1, (3). Table 1 shows the evaluation results.

Example 3 (1) Production of Potassium Polystyrene Sulfonate A sulfonation reaction of polystyrene with sulfuric anhydride was carried out in the same manner as in (1) of Example 1. Then, the obtained reaction product was neutralized to pH 7 with an aqueous potassium hydroxide solution, and then the reaction product was purified in the same manner as (1) of Example 1 to obtain potassium polystyrene sulfonate. No potassium sulfate was detected in the potassium polystyrenesulfonate thus obtained, and the sulfonation ratio was 40%.

(2) Production of Flame Retardant Polycarbonate Resin Composition The same as (2) of Example 1 except that potassium polystyrene sulfonate obtained in (1) was used as the component (B) as a raw material. Thus, a flame-retardant polycarbonate resin composition was produced. (3) Evaluation of flame-retardant polycarbonate resin composition The flame-retardant polycarbonate resin composition obtained in the above (2) was evaluated in the same manner as in Example 1, (3). Table 1 shows the evaluation results.

Example 4 (1) Production of Flame-Retardant Polycarbonate Resin Composition 96.7% by mass of the same polycarbonate resin as in Example 1 as the component (A) and Example 2 as the component (B) After the preparation was performed in the same manner as in (1) of 3 above, water was added to make the concentration 3
A flame-retardant polycarbonate resin composition was produced using 4.3% by mass of an aqueous potassium polystyrene sulfonate solution of 0% by mass. In the production of this composition, an aqueous potassium polystyrene sulfonate solution having a component (B) concentration of 30% by mass was sprayed uniformly onto pellets of the polycarbonate resin as the component (A). The kneading of both components (A) and (B) was the same as in (2) of Example 1. (2) Evaluation of Flame Retardant Polycarbonate Resin Composition The flame retardant polycarbonate resin composition obtained in the above (1) was evaluated in the same manner as in Example 1, (3). Table 1 shows the evaluation results.

Comparative Example 2 (1) Production of Potassium Polystyrenesulfonate A sulfonation reaction of polystyrene with sulfuric anhydride was carried out in the same manner as in (1) of Example 1. Then, the reaction product obtained here is adjusted to pH 7 with an aqueous potassium hydroxide solution.
After neutralization, the solvent and water were removed under reduced pressure to obtain potassium polystyrenesulfonate. The potassium polystyrene sulfonate thus obtained has a potassium sulfate content of 6% by mass and a sulfonation rate of 40%.
%Met.

(2) Production of Flame-Retardant Polycarbonate Resin Composition The same procedure as in (2) of Example 1 was carried out except that the unpurified potassium polystyrenesulfonate obtained in the above (1) was used as the component (B) as a raw material. In the same manner as in (1), a flame-retardant polycarbonate resin composition was produced. (3) Evaluation of flame-retardant polycarbonate resin composition The flame-retardant polycarbonate resin composition obtained in the above (2) was evaluated in the same manner as in Example 1, (3). Table 1 shows the evaluation results.

Example 5 (1) Production of Flame-Retardant Polycarbonate Resin Composition 99.4% by mass of the same polycarbonate resin as in Example 1 as the component (A) and Example 1 as the component (B) After preparing in the same manner as in (1) of item 2, 0.6% by mass of an aqueous solution of sodium polystyrene sulfonate having a concentration of 35% by adding water, and a polytetrafluoroethylene resin having fibril-forming properties as the component (C) [Asahi Glass Fluoropolymers Co., Ltd .; CD076] 0.5 parts by mass with respect to 100 parts by mass of both components (A) and (B), and as component (D), polysiloxane rubber and polyacrylate rubber cannot be separated. Core / shell type elastomer obtained by graft-polymerizing styrene on a composite rubber intertwined to a certain extent [Mitsubrene S-200 manufactured by Mitsubishi Rayon Co., Ltd.]
1) with respect to 100 parts by mass of both components (A) and (B)
A flame-retardant polycarbonate resin composition was produced using parts by mass. In producing this composition, an aqueous solution of sodium polystyrene sulfonate having a concentration of 35% by mass of the component (B) was sprayed uniformly on each of the solid components (A), (C) and (D). The kneading of these components (A) to (D) was the same as in (2) of Example 1.

(2) Evaluation of Flame Retardant Polycarbonate Resin Composition The flame retardant polycarbonate resin composition obtained in the above (1) was evaluated in the same manner as in Example 1, (3). In the UL94 combustion test, a test piece having a thickness of 1.5 mm was also performed. Table 1 shows the evaluation results.

Example 6 (1) Production of Flame-Retardant Polycarbonate Resin Composition 1,3-phenylene-tetrakis (2,6-dimethylphenyl) phosphate [Asahi Denka Kogyo FP500] (A)
(B) A flame-retardant polycarbonate resin composition was produced in the same manner as in Example 5, except that 5 parts by mass was used per 100 parts by mass of both components in total. In producing this composition,
An aqueous solution of sodium polystyrenesulfonate having a concentration of 35% by mass of the component (B) was sprayed onto each of the solid components (A), (C), (D), and (E) so as to be uniformly dispersed. The kneading of these components (A) to (E) was the same as in (2) of Example 1.

(2) Evaluation of Flame Retardant Polycarbonate Resin Composition The flame retardant polycarbonate resin composition obtained in the above (1) was evaluated in the same manner as in Example 1, (3). In the UL94 combustion test, a test piece having a thickness of 1.5 mm and a test piece having a thickness of 0.8 mm were also performed.
Table 1 shows the evaluation results.

Comparative Example 3 (1) Evaluation of Polycarbonate Resin The polycarbonate resin of the component (A) used in (2) of Example 1 was evaluated in the same manner as (3) of Example 1. Table 1 shows the evaluation results.

Comparative Example 4 (1) Production of Flame-Retardant Polycarbonate Resin Composition The polycarbonate resin used in (2) of Example 1 was used as the component (A), and the polycarbonate resin used in Example 2 was used as the component (B). The sodium polystyrene sulfonate obtained in 1 (1) was blended in an amount of 94% by mass of the component (A) and 6% by mass of the component (B), and the mixture was melt-kneaded.
A flame retardant polycarbonate resin composition was produced.

(2) Evaluation of Flame Retardant Polycarbonate Resin Composition The flame retardant polycarbonate resin composition obtained in the above (1) was evaluated in the same manner as in Example 1, (3). Table 1 shows the evaluation results.

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[Table 1]

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According to the present invention, the addition of a small amount of a flame retardant component provides high flame retardancy and excellent recyclability and antistatic performance while maintaining the physical properties inherent to the polycarbonate resin. It is possible to provide a flame-retardant polycarbonate resin composition capable of obtaining a molded article having excellent appearance and a method for producing the same and a molded article.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 25:18 C08L 25:18 27:18 27:18 51:04) 51:04) F-term (Reference) 4F070 AA50 AC55 AC74 AC76 AC79 AE07 FA01 FA15 FA17 FB05 4F071 AA22 AA22X AA27 AA31X AA32X AA33X AA50 AA77 AH07 AH12 AH16 BA01 BB03 BB05 BB06 BC03 4J002 BC10X BD15Y GM12 CG01 BG12 CG01 BN12Z BN01

Claims (8)

[Claims] 1. An acid-base-containing aromatic vinyl-based resin having a content of an inorganic metal salt of less than 5% by mass as a component (A): 95 to 99.99% by mass of a polycarbonate resin as a component (A) and 0.01 to 9% by mass. A flame-retardant polycarbonate resin composition comprising 5% by mass. 2. The flame retardant according to claim 1, wherein the acid-base-containing aromatic vinyl resin (B) is an acid-base-containing aromatic vinyl resin having an inorganic metal salt content of less than 3% by mass. Polycarbonate resin composition. 3. A polytetrafluoroethylene-based resin as component (C) is used in an amount of 0.01 to 100 parts by mass based on a total of 100 parts by mass of components (A) and (B).
3. The flame-retardant polycarbonate resin composition according to claim 1, which is added by 5 parts by mass. 4. 4. Further, a core / shell type elastomer as the component (D) is used in an amount of from 0.01 to 100 parts by mass based on a total of 100 parts by mass of the component (A) and the component (B).
The flame-retardant polycarbonate resin composition according to any one of claims 1 to 3, which is added by 10 parts by mass. 5. A phosphoric ester-based flame retardant as the component (E) is used in an amount of 0.01 to 30 parts by mass based on 100 parts by mass of the components (A) and (B). The flame-retardant polycarbonate resin composition according to any one of claims 1 to 4, wherein the composition is added. 6. An acid-base-containing aromatic vinyl-based resin as the component (B) in a solution state having a concentration of 10 to 60% by mass as the component (B).
The flame-retardant polycarbonate resin composition according to any one of claims 1 to 5, which is produced by spraying and kneading components other than the components. 7. In producing the flame-retardant polycarbonate resin composition according to any one of claims 1 to 5,
The acid-base-containing aromatic vinyl resin (B) having a concentration of 10
A method for producing a flame-retardant polycarbonate resin composition, which comprises applying to a component other than the component (B) in a solution state of 〜60% by mass, followed by kneading. 8. A molded article obtained by molding the flame-retardant polycarbonate resin composition according to claim 1.