JP2000119504A - Flame-retardant polycarbonate resin composition and its injection-molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame-retardant polycarbonate resin composition made to become flame-retardant with red phosphorus, easy to be toned into a composition having thin and bright color and capable of molding a molded article excellent in impact strength and external appearance, and also to provide a molded article using the same composition. SOLUTION: This flame-retardant polycarbonate resin composition comprises 100 pts.wt. resin consisting of (A) 20-100 wt.% polycarbonate resin and (B) 80-0 wt.% styrenic resin, (C) 0.1-10 pts.wt. red phosphorus treated with titanium oxide so as to be stabilized. The above red phosphorus is pref. compositely treated with an other surface treating agent such as a thermosetting resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a flame-retardant polycarbonate resin composition and a molded article, and more particularly, to a flame-retardant polycarbonate resin composition and a molded article.
The present invention relates to a flame-retardant polycarbonate resin composition which is flame-retarded by red phosphorus, has good coloring properties, and has excellent impact strength, and a molded article.

[0002]

2. Description of the Related Art Polycarbonate resin has excellent impact resistance, heat resistance, electrical characteristics, and dimensional stability.
It is widely used in various fields such as OA (office automation) devices, information and communication devices, electric and electronic devices, home electric appliances, automobile fields, and construction fields. Polycarbonate resin is generally a self-extinguishing resin, but there are fields where high flame retardancy is required, especially in OA equipment, information and communication equipment, electric and electronic equipment, and home appliances. The improvement has been achieved by adding a flame retardant.

On the other hand, recently, when molded articles are OA equipment such as copying machines and fax machines, information and communication equipment such as telephones and communication equipment, parts and housings of electric and electronic equipment, and the like, the shape becomes complicated. The melt fluidity of the polycarbonate resin, that is, injection moldability, is due to the fact that irregularities such as ribs and bosses are formed on the molded product, the molded product is thinner from the viewpoint of weight reduction and resource saving. Are required. In order to improve the moldability, many compositions having a rubber-modified styrene resin have been proposed in consideration of physical properties such as impact resistance.

In order to improve the melt fluidity of polycarbonate resin, acrylonitrile-butadiene-styrene resin (ABS resin), rubber-modified polystyrene resin (HIP
S), a composition in which a styrene-based resin such as an acrylonitrile-styrene resin (AS resin) is blended with a polycarbonate resin is used as a polymer alloy in many molded article fields by utilizing its heat resistance and impact resistance properties. Is coming. On the other hand, among these applications, OA equipment, information and
2. Description of the Related Art In the case of communication devices, electric / electronic devices, and the like, a certain level of flame retardancy is required to enhance the safety of the products.

As a method for improving the flame retardancy of polycarbonate resins, halogen-based flame retardants such as halogenated bisphenol A and halogenated polycarbonate oligomers have been used together with flame retardant aids such as antimony oxide in view of flame retardant efficiency. . However, from the viewpoints of recent safety and impact on the environment, there is a need in the market for a flame retardant method using a halogen-free flame retardant. As a non-halogen flame retardant, an organic phosphorus flame retardant, particularly a polycarbonate resin composition containing an organic phosphate compound exhibits excellent flame retardancy, and many methods have been proposed.

Specifically, for example, Japanese Patent Application Laid-Open No. 61-551
No. 45 discloses, in (A) an aromatic polycarbonate resin,
A thermoplastic resin composition comprising (B) an ABS resin, (C) an AS resin, (D) a halogen compound, (E) a phosphate, and (F) a polytetrafluoroethylene component is described. JP-A-2-32154 discloses (A) an aromatic polycarbonate resin, (B) an ABS resin, and (C) A
A flame-retardant high-impact polycarbonate molding composition comprising an S resin, (D) a phosphate ester, and (E) a polytetrafluoroethylene component is described. JP-A-8-239
No. 565 discloses (A) an aromatic polycarbonate,
A polycarbonate resin composition containing (B) an impact-resistant polystyrene resin containing a rubber-like elastic body, (C) a halogen-free phosphate ester, (D) a core shell type graft rubber-like elastic body, and (D) talc is described. ing.

These are all aimed at improving moldability, impact resistance, and flame retardancy by improving the melt flowability of polycarbonate, and have been used as various molded articles by taking advantage of their excellent effects. I have. However, when a good melt flowable composition comprising a polycarbonate resin or a polycarbonate resin and a rubber-modified styrenic resin is made flame-retardant with an organic phosphorus-based flame retardant, a relatively large amount of a phosphate ester compound or the like is required. There is. Phosphoric acid ester compounds contribute to flame retardancy, but mold corrosion during molding and reduced impact strength and discoloration when molded products are heated or exposed to high humidity There are problems such as occurrence of

[0008] On the other hand, it is well known that red phosphorus is used as a non-halogen flame retardant method for polycarbonate resins. For example, Japanese Patent Publication No. 5-18356 discloses a flame-retardant thermoplastic resin composition containing red phosphorus converted to spherical red phosphorus without a crushed surface, which is directly obtained by a yellow phosphorus conversion treatment method. Coating is also disclosed. Japanese Patent Application Laid-Open No. 7-53779 discloses the use of sphere-like or finely powdered red phosphorus which has been converted in the presence of a dispersant and surface-treated with red phosphorus. As is clear from these descriptions, red phosphorus as a flame retardant is stored, stored, transported, and handled by a stabilization treatment of coating the surface with a thermosetting resin or an inorganic compound. At the time of kneading, safety is ensured and generation of phosphine gas is suppressed.

[0009] However, red phosphorus exhibits excellent flame retardancy when added in a relatively small amount. However, when added to a polycarbonate resin, red phosphorus is colored, has a light color or a light color (for example, an L value of 70 or more). When red is colored, red coloring due to red phosphorus occurs, and it is necessary to add a large amount of titanium oxide to compensate for the red coloring. If 3% by weight or more of titanium oxide is added to the polycarbonate resin, the resin is liable to be decomposed at the time of melting by heating, resulting in problems such as a significant decrease in strength such as impact strength, and generation of silver on the surface of the molded product. Despite its excellent flame retardant effect, the use of red phosphorus is severely restricted.

[0010]

SUMMARY OF THE INVENTION Under the above-mentioned circumstances, the present invention has no adverse effect on polycarbonate resin in flame retardation of polycarbonate resin by red phosphorus, and has an impact strength,
An object of the present invention is to provide a flame-retardant polycarbonate resin composition capable of molding a molded article having an excellent appearance, and a molded article using the composition.

[0011]

Means for Solving the Problems In order to achieve the object of the present invention, the present inventors have intensively studied improvements in moldability, appearance, physical properties, and the like in making a flame-retardant polycarbonate resin flame-retardant with red phosphorus. did. As a result, a polycarbonate resin containing red phosphorus as a flame retardant, or a resin composition containing a rubber-modified styrenic resin, the flame retardancy is reduced by selectively using a specific stabilized red phosphorus. The present invention was found to be able to prevent a decrease in formability, appearance, and impact strength without causing the present invention, and completed the present invention.

That is, the present invention provides: (1) (A) 20 to 100% by weight of a polycarbonate resin
And (B) a flame-retardant polycarbonate resin composition containing (C) 0.1 to 10 parts by weight of titanium oxide-stabilized red phosphorus per 100 parts by weight of a resin composed of 80 to 0% by weight of a styrene resin. (2) The flame-retardant polycarbonate resin composition according to the above (1), wherein the titanium oxide stabilization treatment red phosphorus is a composite treatment red phosphorus with another stabilization treatment. (3) The styrene-based resin is a rubber-modified styrene-based resin, and (A) or (2) wherein (A) 50 to 95% by weight of a polycarbonate resin and (B) 50 to 5% by weight of a rubber-modified styrene-based resin. )
The flame-retardant polycarbonate resin composition according to the above. (4) Further, (D) a fluoroolefin resin,
The flame-retardant polycarbonate resin composition according to any one of the above (1) to (3), containing 0.05 to 5 parts by weight based on 100 parts by weight of the resin composed of (A) and (B). (5) The above (1) to (1) to (E), which further contain 1 to 30 parts by weight of the core-shell type graft rubber-like elastic body based on 100 parts by weight of the resin composed of (A) and (B).
The flame-retardant polycarbonate resin composition according to any one of (4). (6) Further, (F) a functional group-containing silicone compound is
The flame-retardant polycarbonate resin composition according to any one of the above (1) to (5), containing 0.05 to 5 parts by weight based on 100 parts by weight of the resin composed of (A) and (B). (7) A molded article having an L value of 70 or more obtained by molding the flame-retardant polycarbonate resin composition according to any one of (1) to (6). (8) OA equipment, information / communication equipment, electric / electronic equipment or home electric appliance housings or those obtained by injection-molding the flame-retardant polycarbonate resin composition according to any of (1) to (6) above. Parts.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
First, the components (A) to (C) of the flame-retardant polycarbonate resin composition of the present invention will be described. (A) Polycarbonate resin (PC) The polycarbonate resin (PC) as the component (A) constituting the flame-retardant polycarbonate resin composition of the present invention is not particularly limited, and various ones can be mentioned. Usually, an aromatic polycarbonate produced by reacting a dihydric phenol with a carbonate precursor can be used.
That is, a product prepared by reacting a dihydric phenol with a carbonate precursor by a solution method or a melting method, that is, a reaction of a dihydric phenol with phosgene by a transesterification method of a dihydric phenol with diphenyl carbonate or the like is used. be able to.

As the dihydric phenol, various ones can be mentioned. In particular, 2,2-bis (4-hydroxyphenyl) propane [bisphenol A], bis (4-hydroxyphenyl) methane, 1,1-bis ( 4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxy-
3,5-dimethylphenyl) propane, 4,4'-dihydroxydiphenyl, bis (4-hydroxyphenyl)
Cycloalkane, bis (4-hydroxyphenyl) oxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) ether, bis ( 4-hydroxyphenyl) ketone and the like.

Particularly preferred divalent phenols are bis (hydroxyphenyl) alkanes, particularly those containing bisphenol A as a main raw material. Examples of the carbonate precursor include carbonyl halide, carbonyl ester, and haloformate, and specifically, phosgene, dihaloformate of dihydric phenol, diphenyl carbonate, dimethyl carbonate, and diethyl carbonate. In addition, examples of the dihydric phenol include hydroquinone, resorcin, and catechol. These dihydric phenols may be used alone or in combination of two or more.

The polycarbonate resin may have a branched structure. Examples of the branching agent include 1,1,1-tris (4-hydroxyphenyl) ethane, α, α ′,
α "-tris (4-hydroxyphenyl) -1,3,5
-Triisopropylbenzene, phloroglysin, trimellitic acid, isatin bis (o-cresol) and the like. In order to control the molecular weight, phenol and p-
t-butylphenol, pt-octylphenol,
For example, p-cumylphenol is used.

The polycarbonate resin used in the present invention may be a copolymer having a polycarbonate portion and a polyorganosiloxane portion, or a polycarbonate resin containing this copolymer. Further, it may be a polyester-polycarbonate resin obtained by polymerizing polycarbonate in the presence of a bifunctional carboxylic acid such as terephthalic acid or an ester precursor such as an ester-forming derivative thereof. Also, a mixture of various polycarbonate resins can be used. The polycarbonate resin of the component (A) used in the present invention preferably has substantially no halogen in the structure. Further, from the viewpoint of mechanical strength and moldability, its viscosity average molecular weight is from 10,000 to 100,0.
00, preferably 14,000 to 40,000.
A value of 0 is preferred.

(B) Styrene resin The styrene resin of the component (B) constituting the flame-retardant polycarbonate resin composition of the present invention is styrene, α-
Monovinyl aromatic monomers such as methylstyrene 20 to 20
100% by weight, 0 to 60% by weight of vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, and 0 to 60% by weight of other vinyl monomers such as maleimide and methyl (meth) acrylate copolymerizable therewith. There is a polymer obtained by polymerizing a monomer or a monomer mixture consisting of 50% by weight. These polymers include polystyrene (GP
PS) and acrylonitrile-styrene copolymer (AS resin).

As the styrene resin, a rubber-modified styrene resin can be preferably used. The rubber-modified styrene resin is preferably an impact-resistant styrene resin obtained by graft-polymerizing at least a styrene monomer onto rubber. Examples of the rubber-modified styrene resin include impact-resistant polystyrene (HIPS) in which styrene is polymerized in rubber such as polybutadiene, ABS resin in which acrylonitrile and styrene are polymerized in polybutadiene, and MBS in which methyl methacrylate and styrene are polymerized in polybutadiene. Resin, rubber-modified styrenic resin,
Two or more of them can be used in combination, and can also be used as a mixture with the above-mentioned rubber-unmodified styrene resin.

The rubber content in the rubber-modified styrenic resin is, for example, 2 to 50% by weight, preferably 5 to 30% by weight, particularly 5 to 15% by weight. 2% by weight of rubber
When the amount is less than 50%, the impact resistance becomes insufficient. When the amount exceeds 50% by weight, problems such as a decrease in thermal stability, a decrease in melt fluidity, generation of a gel, and coloring may occur.
Specific examples of the rubber include a rubber polymer containing polybutadiene, acrylate and / or methacrylate, styrene-butadiene-styrene rubber (SB
S), styrene-butadiene rubber (SBR), butadiene-acrylic rubber, isoprene rubber, isoprene-styrene rubber, isoprene-acrylic rubber, ethylene-propylene rubber and the like. Among them, particularly preferred is polybutadiene. The polybutadiene used here is a low cis polybutadiene (for example, 1 to 30 mol% of 1,2-vinyl bond and 30 to 42% of 1,4-cis bond).
Mol%) or high cis polybutadiene (for example, those containing 1,2-vinyl bonds of 20 mol% or less and 1,4-cis bonds of 78 mol% or more). May be used.

Next, in the present invention, the styrene resin as the component (B) has no direct relation to the flame retardancy of the present invention, and is blended when it is necessary to improve the melt fluidity of the polycarbonate resin. Things. Here, the compounding ratio of (A) the polycarbonate resin and (B) the styrene resin is usually 20 to 100% by weight, preferably 50 to 95% by weight of the (A) polycarbonate resin, and 80 to 0% by weight of the (B) styrene resin. % By weight, preferably 50 to 5% by weight. Here, the polycarbonate resin of the component (A) is 20
If the amount is less than 5% by weight, the heat resistance and strength are not sufficient, and if the amount of the styrene resin (B) is less than 5% by weight, the effect of improving the moldability may be insufficient. In this case, (B)
As the styrene resin, the above-mentioned rubber-modified styrene resin is preferably used. These compounding ratios are appropriately determined in consideration of the molecular weight of the polycarbonate resin, the type and molecular weight of the styrene resin, the melt index, the rubber content, the use of the molded product, the size, the thickness, and the like.

(C) Titanium oxide stabilizing red phosphorus Titanium oxide stabilizing red phosphorus used in the present invention is a titanium oxide stabilizing treatment (surface coating) from among various treatments for stabilizing red phosphorus. ). The red phosphorus used for the titanium oxide may be one obtained by sieving crushed red phosphorus that has been known for a long time to adjust the particle size, or may be a spherical one obtained directly by thermally converting yellow phosphorus. . The processing amount for stabilization by titanium oxide is usually about 1 to 50% by weight based on red phosphorus. The treatment of red phosphorus with titanium oxide is indispensable, but other known surface treatment (surface coating) for stabilizing red phosphorus may be used in combination. Is preferably used.

As these other stabilizing surface treatments, there are treatments with thermosetting resins, inorganic compounds, metals and the like.
Phenolic resins, phenol-
Examples include formalin resin, urea resin, urea-formalin resin, melamine resin, melamine-formalin resin, alkyd resin, epoxy resin, unsaturated polyester resin and the like. As inorganic compounds, silica, bentonite,
Zeolite, kaolin, zinc oxide, magnesium oxide,
Magnesium carbonate, barium sulfate, calcium phosphate,
Examples thereof include aluminum hydroxide, magnesium hydroxide, zinc hydroxide, and titanium hydroxide. In addition, the metal is usually a metal that can be electrolessly plated,
Examples include iron, nickel, cobalt, copper, zinc, manganese, and aluminum.

Further, two or more of these stabilizing surface treatments can be used in combination. The surface treatment and the surface treatment of titanium oxide can be performed simultaneously, or the titanium oxide treatment can be separately performed in two steps before and after the other stabilizing surface treatment. It is preferable that the content of red phosphorus is 20% by weight or more in terms of the flame retardant efficiency and the cost. The stabilized red phosphorus used in the present invention has an average particle size of 0.1 to 100 μm, preferably 0.5 to 50 μm.

The content of the component (C) titanium oxide-stabilized red phosphorus is 0.1 to 10 parts by weight based on 100 parts by weight of the resin (A) containing the polycarbonate resin and (B) the styrene resin. Parts, preferably 0.2 to 6 parts by weight, more preferably 0.3 to 4 parts by weight. here,
If the content is less than 0.1, the flame retardancy of the molded product is not sufficient, and if it exceeds 10 parts by weight, it is not desirable in terms of odor generation and physical properties during molding. In the present invention, together with red phosphorus, a phosphite-based compound such as triphenyl phosphite or tris (2,4-di-t-butylphenyl phosphite, distearyl pentaerythritol diphosphite) known as a stabilizer is used (A ) And (B), the stability can be further improved by using the same in an amount of 0.05 to 5 parts by weight with respect to 100 parts by weight of the resin composed of (B). The content of the phosphite-based compound is determined in consideration of the required flame retardant properties of the molded article, and includes the content of red phosphorus in the stabilized red phosphorus, the content of other rubber-like elastic materials and inorganic fillers, and the like. Is determined by comprehensive judgment.

The flame-retardant polycarbonate resin composition of the present invention further comprises (D)
It can contain a fluoroolefin resin. Here, the (D) fluoroolefin resin is usually a polymer or copolymer containing a fluoroethylene structure, for example, a difluoroethylene polymer, a tetrafluoroethylene polymer, a tetrafluoroethylene-hexafluoropropylene copolymer, It is a copolymer of tetrafluoroethylene and an ethylene monomer containing no fluorine. Preferably, it is polytetrafluoroethylene (PTFE), and its average molecular weight is preferably 500,000 or more, and particularly preferably 500,000 to 10,000.
1,000,000. As the polytetrafluoroethylene that can be used in the present invention, all types currently known can be used.

When polytetrafluoroethylene having fibril-forming ability is used, higher anti-dripping property can be imparted. Polytetrafluoroethylene (PTF) having fibril-forming ability
E) is not particularly limited, and includes, for example, those classified into type 3 in the ASTM standard. Specific examples thereof include, for example, Teflon 6-J (manufactured by DuPont Fluorochemicals, Mitsui), Polyflon D-1, Polyflon F-103, Polyflon F201 (manufactured by Daikin Industries, Ltd.), and CD076 (Asahi IC fluoropolymers Co., Ltd.) Manufactured by a company).

Other than those classified into the above-mentioned type 3, for example, Algoflon F5 (manufactured by Montefluos Co., Ltd.), polyflon MPA, polyflon FA-100
(Manufactured by Daikin Industries, Ltd.). These polytetrafluoroethylene (PTFE) may be used alone or in combination of two or more. Polytetrafluoroethylene (PTFE) having a fibril-forming ability as described above can be obtained, for example, by mixing tetrafluoroethylene in an aqueous solvent in the presence of sodium, potassium, and ammonium peroxydisulfide at 1 to 100 psi.
Under a pressure of 0 to 200 ° C., preferably 20 to 100 ° C.
It is obtained by polymerizing at ° C.

Here, the content of the fluoroolefin resin is from 0.05 to 5 parts by weight, preferably from 0.1 to 5 parts by weight, based on 100 parts by weight of the resin comprising the components (A) and (B).
2 parts by weight. Here, if the amount is less than 0.05 part by weight, the melt dripping resistance in the intended flame retardancy may not be sufficient. Even if the amount exceeds 5 parts by weight, the effect corresponding thereto is not improved, and The impact and the appearance of the molded product may be adversely affected. Therefore, the degree of flame retardancy required for each molded article, for example, V-0 and V- of UL-94.
It can be appropriately determined in consideration of the amount of other components to be used and the like according to 1, V-2, and the like.

The flame-retardant polycarbonate resin composition of the present invention further contains a core-shell type rubber-like elastic material as a component (E) for further improving the impact resistance of the flame-retardant polycarbonate resin composition. be able to. Its content is 100% of the resin (A) and (B).
1 to 30 parts by weight, preferably 2 to 20 parts by weight with respect to parts by weight
Parts by weight. The content of the rubber-like elastic body is determined by comprehensively considering impact resistance, heat resistance, rigidity, and the like required for a target molded product. The core-shell type rubber-like elastic body of the component (E) has a two-layer structure composed of a core (core) and a shell (shell), and the core portion is in a soft rubber state. The shell portion is in a hard resin state, and the elastic body itself is preferably a core-shell type graft rubber-like elastic body in a powder state (particle state). Even after the rubber-like elastic body is melt-blended with the polycarbonate resin, the particle state of the rubber-like elastic body mostly maintains its original form. Since most of the compounded rubber-like elastic body maintains the original shape, an effect of preventing surface layer peeling can be obtained.

Various examples of the core-shell type graft rubber-like elastic body can be given. Examples of commercially available products include Hybrene B621 (manufactured by Zeon Corporation), KM-330 (manufactured by Rohm & Haas Co., Ltd.), Metablen W529, Metablen S2001, Metablen C223, and Metablen B621 (manufactured by Mitsubishi Rayon Co., Ltd.). Can be

Among them, for example, one or more vinyl monomers are added in the presence of a rubbery polymer obtained from a monomer mainly composed of alkyl acrylate, alkyl methacrylate or dimethyl siloxane. Examples include those obtained by polymerization. Here, alkyl acrylates and acrylic methacrylates have 2 to 1 carbon atoms.
Those having a zero alkyl group are preferred. In particular,
For example, ethyl acrylate, butyl acrylate, 2-
Examples include ethylhexyl acrylate and n-octyl methacrylate. The rubber-like elastic material obtained from these monomers mainly composed of alkyl acrylates includes 70% by weight or more of alkyl acrylates and another vinyl monomer copolymerizable therewith, such as methyl methacrylate and acrylonitrile. , Vinyl acetate, styrene, and the like, and 30% by weight or less. In this case, a polyfunctional monomer such as divinylbenzene, ethylene dimethacrylate, triallyl cyanurate, triallyl isocyanurate or the like may be appropriately added as a crosslinking agent and reacted.

Examples of the vinyl monomer to be reacted in the presence of the rubbery polymer include aromatic vinyl compounds such as styrene and α-methylstyrene, acrylic esters such as methyl acrylate and ethyl acrylate, and methacrylic acid. And methacrylates such as methyl acrylate and ethyl methacrylate. These monomers may be used alone or in combination of two or more. Further, other vinyl polymers such as vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, vinyl acetate, and propionic acid It may be copolymerized with a vinyl ester compound such as vinyl. This polymerization reaction can be performed by various methods such as bulk polymerization, suspension polymerization, and emulsion polymerization. In particular,
Emulsion polymerization is preferred.

The thus obtained core-shell type graft rubber-like elastic body preferably contains the rubber-like polymer in an amount of 20% by weight or more. Specific examples of such a core-shell type graft rubber-like elastic material include M-polymers such as a graft copolymer of 60 to 80% by weight of n-butyl acrylate, styrene and methyl methacrylate.
AS resin elastic body is mentioned. Above all, the polysiloxane rubber component has a structure in which 5-95% by weight of the polyacryl (meth) acrylate rubber component and 95-5% by weight of the polyacryl (meth) acrylate rubber component are entangled with each other so as to be inseparable.
Particularly preferred is a composite rubber-based graft copolymer obtained by graft-polymerizing at least one vinyl monomer on a composite rubber having a diameter of about 1 to 1 μm. The copolymer has a higher impact resistance improving effect than the graft copolymer of each rubber alone. This composite rubber-based graft copolymer can be obtained as a commercially available product such as Metablen S-2001 manufactured by Mitsubishi Rayon Co., Ltd.

The flame-retardant polycarbonate resin composition of the present invention further comprises (F) a functional group-containing silicone compound per 100 parts by weight of a resin comprising (A) a polycarbonate resin and (B) a styrene resin. , 0.05
To 5 parts by weight, preferably 0.1 to 2 parts by weight. Although the cause of this functional group-containing silicone compound is not clear, it is possible to obtain a composition having more excellent moldability and strength due to its action of suppressing the generation of phosphine gas from red phosphorus.

Here, the silicone compound having a functional group is a (poly) organosiloxane having a functional group, and the skeleton thereof has the formula R ¹ aR ² bSiO
_{(4-ab) / 2} [R ¹ is a functional group-containing group, R ² is a group having 1 to 1 carbon atoms.
2 hydrocarbon groups, 0 <a <2, 0 ≦ b <2, 0 <a + b
≦ 2]. Further, as the functional group, an alkoxy group, a hydrogen group,
It contains a carboxyl group, a cyanol group, an amino group, an epoxy group and the like. These silicone compounds are liquids, powders and the like.

The flame-retardant polycarbonate resin composition of the present invention may contain an inorganic filler, if necessary, to further improve the rigidity and the flame retardancy of the molded product. Here, examples of the inorganic filler include talc, mica, kaolin, diatomaceous earth, calcium carbonate, calcium sulfate, barium sulfate, glass fiber, carbon fiber, and potassium titanate fiber. Of these, plate-like talc, mica, and the like, and fibrous fillers are preferable. As the talc, a hydrated silicate of magnesium, which is generally commercially available, can be used. Talc, in addition to the main components of silicic acid and magnesium oxide, may contain a small amount of aluminum oxide, calcium oxide, iron oxide, but in order to produce the resin composition of the present invention, these are included. It doesn't matter. The average particle size of the inorganic filler such as talc is 0.1 to 50.
μm, preferably 0.2 to 20 μm. By including these inorganic fillers, especially talc, the compounding amount of the halogen-free phosphate ester as a flame retardant can be reduced in addition to the effect of improving rigidity.

Here, the content of the inorganic filler is 1 to 100 parts by weight, preferably 2 to 50 parts by weight, based on 100 parts by weight of the resin comprising (A) and (B). If the amount is less than 1 part by weight, the intended effect of improving the rigidity and the flame retardancy may not be sufficient. If the amount exceeds 100 parts by weight, the impact resistance and the melt fluidity may decrease. It can be appropriately determined in consideration of the required properties and moldability of the molded article, such as the thickness of the article and the resin flow length.

In the polycarbonate resin composition of the present invention, as is conventionally known, as a flame retardant, an organic phosphorus flame retardant other than red phosphorus, particularly an organic phosphorus flame retardant containing no halogen, is used. 1 to 20 parts by weight, preferably 100 parts by weight of the resin comprising (A) and (B),
2 to 15 parts by weight may be used in combination. The halogen-free organic phosphorus-based flame retardant can be used without any particular limitation. Preferably, a phosphate compound having at least one ester oxygen atom directly bonded to a phosphorus atom is used.

As the phosphoric ester compound, for example, the following formula (1)

[0041]

Embedded image

(Wherein R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or an organic group, and X represents 2
Represents an organic group having a valence of at least 1, p is 0 or 1, and q is 1
And r represents an integer of 0 or more. ) Is a phosphate compound. In the formula (1), the organic group includes an alkyl group, a cycloalkyl group, and an aryl group which may or may not be substituted.
Examples of the substituent when it is substituted include an alkyl group, an alkoxy group, an aryl group, an aryloxy group, and an arylthio group. Further, those having a substituent such as an arylalkoxyalkyl group which is a group obtained by combining these substituents, or an arylsulfonylaryl group obtained by combining these substituents by bonding with an oxygen atom, a nitrogen atom, a sulfur atom, or the like. and so on.

In the formula (1), the divalent or higher valent organic group X is a divalent or higher valent group formed by removing one or more hydrogen atoms bonded to a carbon atom from the above-mentioned organic groups. means. For example, those derived from an alkylene group, a (substituted) phenylene group, and bisphenols which are polynuclear phenols. Preferred are bisphenol A, hydroquinone, resorcinol, diphenylmethane, dihydroxydiphenyl, dihydroxynaphthalene and the like.

The halogen-free phosphate compound may be a monomer, an oligomer, a polymer or a mixture thereof. Specifically, 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 these Examples of substitutions That.

The commercially available halogen-free phosphate ester compounds include, for example, TPP [triphenyl phosphate], TXP manufactured by Daihachi Chemical Industry Co., Ltd.
[Trixylenyl phosphate], PFR [resorcinol (diphenyl phosphate)], PX200 [1,
3-phenylene-teslakis (2,6-dimethylphenyl) phosphate, PX201L [1,4-phenylene-tetrakis (2,6-dimethylphenyl) phosphate, PX202 [4,4'-biphenylene-teslakis) 2 , 6-dimethylphenyl) phosphate and the like.

The flame-retardant polycarbonate resin composition of the present invention comprises the following essential components (A) and (C) for the purpose of improving moldability, impact resistance, appearance, weather resistance, rigidity, etc. (B), (E) to (F), as well as one or more optional components selected from inorganic fillers and phosphoric ester compounds, and, if necessary, various additive components commonly used in thermoplastic resins. be able to. For example, phenol-based, phosphorus-based, sulfur-based antioxidants, antistatic agents, polyamide polyether block copolymers (providing permanent antistatic properties), benzotriazole-based and benzophenone-based ultraviolet absorbers, hindered amine-based light stabilizers (Weathering agent), antibacterial agent, compatibilizer, coloring agent (dye, pigment) and the like. The amount of the optional component is not particularly limited as long as the properties of the flame-retardant polycarbonate resin composition of the present invention are maintained.

Next, a method for producing the flame-retardant polycarbonate resin composition of the present invention will be described. The flame-retardant polycarbonate resin composition of the present invention comprises the components (A) described above,
(C) is used at the above-mentioned ratio, if necessary,
It is obtained by blending (B), various optional components (E) to (F), and further other components at an appropriate ratio and kneading them. The compounding and kneading at this time are preliminarily mixed with a commonly used device, for example, a ribbon blender, a drum tumbler or the like, and a Henschel mixer, a Banbury mixer, a single screw extruder, a twin screw extruder,
It can be carried out by a method using a multi-screw extruder, a kneader or the like. The heating temperature during kneading is usually 240 to 3
It is appropriately selected within the range of 00 ° C. The components other than the polycarbonate resin and the styrene-based resin may be previously melt-kneaded with the polycarbonate resin, the styrene-based resin, or another thermoplastic resin, that is, added as a master batch.

The flame-retardant polycarbonate resin composition of the present invention can be obtained by injection molding, injection compression molding, extrusion molding, blow molding, press molding using the above-mentioned melt-kneading molding machine or the obtained pellets as a raw material. Various molded products can be manufactured by a molding method, a vacuum molding method, a foam molding method, or the like. However, a pellet-shaped molding raw material is produced by the above-mentioned melt-kneading method, and then the pellets can be used particularly suitably for production of an injection molded product by injection molding or injection compression molding. In addition, as the injection molding method,
Gas injection molding may be employed to prevent sink marks on the appearance or to reduce the weight.

Molded articles obtained from the flame-retardant polycarbonate resin composition of the present invention (especially injection molded articles including injection compression molding) include copying machines, fax machines, televisions, radios, tape recorders, video decks, personal computers, and printers. , Telephones, information terminals, refrigerators, OA equipment such as microwave ovens, information and communication equipment, electrical and electronic equipment or home electric appliances housing or various parts thereof,
Further, it is used in other fields such as automobile parts. In particular, the present invention is suitable for producing a molded article having an L value of 70 or more, that is, a molded article having a light-colored or light-colored appearance. In addition, L value is JIS K710
5 According to “Test method for optical properties of plastic”, L,
This is obtained by measuring a and b.

[0050]

EXAMPLES The present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited thereto. Examples 1 to 4 and Comparative Examples 1 and 2 The components were blended at the ratios shown in Table 1 [Components (A) and (B) are% by weight, and the other components are resins 100 composed of (A) and (B). Shown in parts by weight relative to parts by weight. And supplied to an extruder (model name: VS40, manufactured by Tanabe Plastic Machinery Co., Ltd.), melt-kneaded at 260 ° C., and pelletized. In all Examples and Comparative Examples, 0.2 parts by weight of Irganox 1076 (manufactured by Ciba Specialty Chemicals Co., Ltd.) and 0.1 parts by weight of Adekastab C (manufactured by Asahi Denka Kogyo KK) were used as antioxidants. Parts were blended.

In the examples and comparative examples of the present invention, the Munsell number is 2.0Y7.5 / 0.5 (light gray).
It is an experiment about the case where the color is adjusted by using a coloring agent. That is, the color was adjusted by adjusting the amount of titanium oxide added later so that the color became light gray as the Munsell number. The obtained pellet was dried at 80 ° C. for 12 hours, and then injection molded at a molding temperature of 260 ° C. to obtain a test piece. The performance was evaluated by various tests using the obtained test pieces,
The results are shown in Table 1.

The molding materials used and the performance evaluation method are shown below. (A) Polycarbonate resin PC: Toughlon (A1900: manufactured by Idemitsu Petrochemical Co., Ltd.): bisphenol A polycarbonate resin, MI =
20 g / 10 min (300 ° C., 1.2 Kg load), viscosity average molecular weight: 19000 (B) Styrene resin HIPS: Impact resistant polystyrene resin (IDEMITSU)
PS IT44: Idemitsu Petrochemical Co., Ltd.): Polybutadiene grafted with styrene, rubber content = 10% by weight, MI: 8 g / 10 min (200
ABS: acrylonitrile butadiene styrene copolymer (DP-611: manufactured by Techno Polymer Co., Ltd.), MI:
2 g / 10 min (200 ° C., 5 kg load) (C) Red phosphorus P-1: Stabilization treatment of phenolic resin and titanium oxide composite red phosphorus (Nova Red 280C: manufactured by Rin Kagaku Kogyo Co., Ltd.), amount of titanium oxide: about 50% by weight, average particle size: 8μ
mP-2: phenolic resin stabilized red phosphorus (Nova Red Excel 140: manufactured by Rin Kagaku Kogyo Co., Ltd.), average particle diameter: 28 μm (D) fluoroolefin resin PTFE (F201L: manufactured by Daikin Chemical Co., Ltd.), Molecular weight 4,000,000 to 5,000,000 (E) Rubber-like elastic body (core-shell type graft rubber-like elastic body) Composite rubber-based graft copolymer (METABLEN S2001:
(Mitsubishi Rayon Co., Ltd.), polydimethylsiloxane content: 50% by weight or more (F) Methoxy silicone (KC-89: Shin-Etsu Chemical Co., Ltd.) Titanium oxide (CR63: Ishihara Sangyo Co., Ltd.) [Performance evaluation method] (1) Melt fluidity Flow value (Q value): JIS K7210: × 10 ^-2 ml /
s (280 ° C, 160kg load) (2) Appearance evaluation of molded article Visual observation of molded test piece (3) IZOD (Izod impact strength) According to ASTM D256, 23 ° C (1/8 inch wall thickness), unit: kJ / m ² (4) Flame retardancy Compliant with UL94 combustion test (test piece thickness: 1.5 mm)

[0053]

[Table 1]

As is evident from the results in Table 1, the molded article made of the flame-retardant polycarbonate resin composition of the present invention showed a large amount of post-added titanium oxide for toning from Example 1 and Comparative Example 1. It is clear that less is needed. As a result, in the same color tone, the titanium oxide in the whole composition can be reduced, the decomposition of the polycarbonate resin is prevented (the Q value increases in Comparative Example 1), the impact strength is not reduced, and the flame retardancy level is also reduced. high. Further, it is clear that even a light-colored or light-colored molded product having an L value of 70 or more can be molded with less influence of red coloring due to red phosphorus, excellent molded product appearance, flame retardancy, and strength. is there. This is the same for a composite composition with a styrene resin.

[0055]

The flame-retardant polycarbonate resin composition of the present invention is halogen-free and has excellent flame retardancy and moldability.
In addition to having impact strength, it excels in decomposition of resin during molding due to improved heat resistance and appearance of molded products. In addition, the use amount of titanium oxide can be significantly reduced in light and light color toning. Moreover, the use of titanium oxide for the treatment of red phosphorus can provide completely different effects even with the same titanium oxide, which is an unexpected effect far beyond expectation. Therefore, the flame-retardant polycarbonate resin composition of the present invention can sufficiently cope with the enlargement and thinning of OA equipment, information and communication equipment, electric and electronic equipment, home electric appliances, automobile parts, and the like. Application fields are expected to expand.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) // B29C 45/00 B29C 45/00 47/00 47/00 (C08L 69/00 25:02 51:04 27:12 83:04) B29K 69:00 F term (reference) 4F206 AA03 AA13 AA28 AA33 AA45 AB05 AB16 AH33 AH51 AR15 JA07 JF02 4F207 AA03 AA13 AA28 AA33 AA45 AB05 AB16 AH33 AH51 AR15 KA01 KA17 KF02

Claims (8)

[Claims] (A) polycarbonate resin 20 to 10
Flame-retardant polycarbonate resin containing (C) 0.1 to 10 parts by weight of titanium oxide-stabilized red phosphorus per 100 parts by weight of 0% by weight and (B) 80 to 0% by weight of a styrene resin. Composition. 2. The flame-retardant polycarbonate resin composition according to claim 1, wherein the titanium oxide-stabilized red phosphorus is a composite-treated red phosphorus with another stabilizing treatment. 3. The styrene resin is a rubber-modified styrene resin, wherein (A) 50 to 95% by weight of a polycarbonate resin and (B) 50 to 5% by weight of a rubber-modified styrene resin.
The flame-retardant polycarbonate resin composition according to claim 1, comprising: 4. The composition according to claim 1, further comprising 0.05 to 5 parts by weight of the fluoroolefin resin (D) based on 100 parts by weight of the resin comprising (A) and (B). The flame-retardant polycarbonate resin composition according to the above. 5. The resin (E) comprising the core-shell type graft rubber-like elastic body (A) and (B).
1 to 30 parts by weight based on 00 parts by weight.
5. The flame-retardant polycarbonate resin composition according to any one of items 1 to 4. 6. The method according to claim 1, further comprising (F) a functional group-containing silicone compound in an amount of 0.05 to 5 parts by weight based on 100 parts by weight of the resin comprising (A) and (B). A flame-retardant polycarbonate resin composition according to any one of the above. 7. A molded article having an L value of 70 or more obtained by molding the flame-retardant polycarbonate resin composition according to any one of claims 1 to 6. 8. A housing of an OA device, an information / communication device, an electric / electronic device, a home electric appliance, or a housing thereof obtained by injection-molding the flame-retardant polycarbonate resin composition according to any one of claims 1 to 6. parts.