JP2002012754A - Polycarbonate resin composition and molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a poiycarbonate resin composition which is improved in moldability, namely a melt fluidity while maintaining impact resistance, and is excellent in flame retardancy, thermal resistance and recyclability. SOLUTION: The polycarbonate resin composition contains 100 pts. by mass of (A) a polycarbonate-based resin containing a polycarbonate resin of which molecular ends are blocked with a 10-20C alkyl phenol; 0.1-10 pts. by mass of (B) a functional group-containing silicone compound; and 0.2-10 pts. by mass of (C) a core/shell-type graft rubbery elastomer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polycarbonate resin composition, and more particularly to a polycarbonate resin composition which has excellent moldability (melt fluidity) without deteriorating impact resistance, and further uses a halogen-based or phosphorus-based flame retardant. The present invention relates to a polycarbonate resin composition and a molded article having no flame retardancy.

[0002]

2. Description of the Related Art Polycarbonate resins are known for their excellent impact resistance, heat resistance, electrical characteristics, etc., and are used for electrical and electronic equipment such as OA (office automation) equipment, information and communication equipment, home electric equipment, automobile fields, and construction. It is widely used in various fields such as fields. Polycarbonate resins are generally self-extinguishing resins,
There are fields that require a high degree of flame retardancy, mainly in the field of electrical and electronic devices such as A-devices, information and communication devices, and home appliances, and improvements are being made by adding various flame retardants.

As a method for improving the flame retardancy of a polycarbonate resin, halogen-based flame retardants such as halogenated bisphenol A and halogenated polycarbonate oligomer have been used together with a flame retardant auxiliary such as antimony oxide from the viewpoint of flame retardant efficiency. . However, from the viewpoints of recent safety and impact on the environment at the time of disposal and incineration, a flame retardant method using a halogen-free flame retardant is required from the market. As a non-halogen flame retardant, an organic phosphorus flame retardant, in particular, a polycarbonate resin composition containing an organic phosphate compound exhibits excellent flame retardancy and also acts as a plasticizer, and many methods have been proposed. I have.

[0004] In order to make a polycarbonate resin flame-retardant with a phosphate ester compound, it is necessary to add a relatively large amount of the phosphate ester compound. Further, polycarbonate resins have high molding temperatures and high melt viscosities, so that molding temperatures tend to be higher and higher in order to cope with thinner and larger moldings. For this reason, the phosphoric ester compound generally contributes to the flame retardancy, but may not always be sufficient in terms of the molding environment and the appearance of the molded product, such as mold corrosion and gas generation during molding. In addition, it has been pointed out that problems such as a decrease in impact strength and the occurrence of discoloration when the molded article is placed under heating or under high temperature and high humidity.
Furthermore, there remains a problem that it is difficult to attain recyclability in recent resource saving due to insufficient heat stability.

[0005] On the other hand, it is also known that a flame retardancy can be imparted to a polycarbonate resin by adding a silicone compound thereto without generating harmful gas during combustion. For example, (1) JP-A-10-139964
Japanese Patent Application Laid-Open Publication No. Hei 11 (1995) discloses a flame retardant comprising a silicone resin having a specific structure and a specific molecular weight.

Also, (2) JP-A-51-45160, JP-A-1-318180, and JP-A-6-306
265, JP-A-8-12868, JP-A-8-12868
JP-295796, JP-B-3-48947 and the like also disclose flame-retardant polycarbonate resins using silicones. However, in the former (1), although the flame retardancy level is excellent to some extent, the impact resistance may not be sufficient. In the latter (2), silicones are not used alone as a flame retardant, but are used as exemplified compounds for the purpose of improving dropping resistance, or as other flame retardant additives. , A phosphate ester compound, a metal salt of Group 2 of the periodic table, and the like. Further, there is another problem that the moldability and physical properties are deteriorated due to the inclusion of the flame retardant.

Further, a flame-retardant resin composition comprising a polycarbonate-polyorganosiloxane copolymer-containing resin and a polycarbonate resin composition comprising polytetrafluoroethylene having a fibril-forming ability is also known. (JP-A-8-81
620). This composition has excellent flame retardancy in a specific range where the content of polyorganosiloxane is small. However, although the flame retardancy is excellent, the impact resistance, which is a feature of the polycarbonate resin, may be reduced.

[0008]

SUMMARY OF THE INVENTION Under the above circumstances, the present invention has improved moldability, that is, melt fluidity, while maintaining impact resistance, which is a feature of polycarbonate resins, and has flame retardancy and heat resistance. It is an object of the present invention to provide a polycarbonate resin composition which is excellent in recyclability and can cope with thinning of a molded article from the viewpoint of weight reduction and resource saving, and a molded article using this composition.

[0009]

DISCLOSURE OF THE INVENTION The present inventors have intensively studied improvements in moldability, in addition to impact resistance, heat resistance, and recyclability, in making a polycarbonate resin flame-retardant with a silicone compound. As a result, in the polycarbonate resin composition, a specific small amount of a silicone compound and a specific rubber-like elastic material are selectively used, and by selecting a specific polycarbonate resin, the moldability and the difficulty are reduced without lowering the impact resistance. It has been found that the flammability is remarkably improved, and the present invention has been completed.

That is, the present invention provides: (1) (A) 100 parts by mass of a polycarbonate-based resin containing a polycarbonate resin whose molecular terminal is sealed with a phenoxy group having an alkyl group having 10 to 20 carbon atoms: (B) A polycarbonate resin composition comprising 0.1 to 10 parts by mass of a functional group-containing silicone compound and (C) 0.2 to 10 parts by mass of a core / shell type graft rubber-like elastic material. (2) The polycarbonate resin composition according to (1), wherein (A) the polycarbonate-based resin contains at least a polycarbonate-polyorganosiloxane copolymer and the polyorganosiloxane content in the polycarbonate-based resin is 0.1 to 10% by mass. object. (3) Further, (A) polycarbonate-based resin 100
The polycarbonate resin composition according to (1) or (2), wherein the polyfluoroolefin resin (D) is contained in an amount of 0.02 to 5 parts by mass with respect to parts by mass. (4) A molded article comprising the polycarbonate resin composition according to any one of (1) to (3). (5) An object of the present invention is to provide a housing or component of an electric / electronic device comprising the polycarbonate resin composition according to any one of (1) to (3).

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The polycarbonate resin composition of the present invention comprises (A) a functional group (B) based on 100 parts by mass of a polycarbonate-based resin containing a polycarbonate resin whose molecular terminal is sealed with a phenoxy group having an alkyl group having 10 to 20 carbon atoms. It comprises 0.1 to 10 parts by mass of a group-containing silicone compound and 0.2 to 10 parts by mass of (C) a core / shell type graft rubber-like elastic material.

The polycarbonate resin composition of the present invention comprises:
Examples of the polycarbonate resin as the component (A) include a polycarbonate resin having a molecular terminal capped with a phenoxy group having an alkyl group having 10 to 20 carbon atoms (hereinafter, may be abbreviated as a terminal-modified PC). It is characterized by using a polycarbonate resin.

The polycarbonate resin whose molecular terminal is capped with a phenoxy group having an alkyl group having 10 to 20 carbon atoms has an alkyl group having 10 to 20 carbon atoms as a terminal stopper in the production of the polycarbonate resin. It can be obtained by using an alkylphenol. These alkylphenols are not particularly limited, and decylphenol, undecylphenol, dodecylphenol, tridecylphenol, tetradecylphenol, pentadecylphenol, hexadecylphenol, heptadecylphenol, octadecylphenol, nonadecylphenol, eicosyl Phenol can be exemplified.

The alkyl group of these alkylphenols may be at any of o-, m- and p-positions to the hydroxyl group, but is preferably at the p-position. The alkyl group may be linear, branched, or a mixture thereof. This substituent may be at least one of the above alkyl groups having 10 to 20 carbon atoms.
The number is not particularly limited, and may be an alkyl group having 1 to 9 carbon atoms, an aryl group having 6 to 20 carbon atoms, a halogen atom or unsubstituted.

The specific terminal-modified PC may be any of the polycarbonate resins described below. For example, in the reaction of a dihydric phenol with phosgene or a carbonate compound, these alkyl phenols are used to adjust the molecular weight. It is obtained by using it as a sealant.

For example, in a methylene chloride solvent,
It is obtained by reacting a dihydric phenol with phosgene or a polycarbonate oligomer in the presence of a triethylamine catalyst and the phenol having an alkyl group having 10 to 20 carbon atoms. Here, the phenol having an alkyl group having 10 to 20 carbon atoms seals one end or both ends of the polycarbonate resin to modify the end. In this case, the terminal modification is at least 20%, preferably 5%, based on all terminals.
0% or more. That is, the other terminal is a hydroxyl terminal or a terminal sealed with another terminal blocking agent described below.

Here, as other terminal blocking agents, phenol, p-tert-butylphenol, p-tert-butylphenol commonly used in the production of polycarbonate resin are used.
Phenols such as octyl phenol and p-cumyl phenol, and the use of only these phenols cannot provide a composition satisfying both excellent moldability and impact resistance of the present invention.

The component (A) of the polycarbonate resin composition of the present invention contains a polycarbonate resin having a molecular terminal capped with a phenoxy group having an alkyl group having 10 to 20 carbon atoms. Although the modified PC can be used alone, it can also be used as a mixture with another polycarbonate resin. The content of the specific terminal-modified PC in this case is not particularly limited, but in order to improve moldability (melt fluidity), taking into consideration all terminals of the polycarbonate resin as the component (A),
It is usually at least 20% by mass, preferably at least 50% by mass, more preferably at least 70% by mass. The content is determined based on the ratio of the phenoxy group having an alkyl group having 10 to 20 carbon atoms in the terminal-modified PC, the type of the other terminal, the type of the terminal of another polycarbonate resin, the melt fluidity of the target composition, and the like. It can be determined appropriately in consideration of the above.

The polycarbonate resin constituting the component (A) of the polycarbonate resin composition of the present invention is not particularly limited, and may be various ones. Usually, an aromatic polycarbonate produced by reacting a dihydric phenol with a carbonate precursor can be used.
That is, a solution 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, or a transesterification method of a dihydric phenol with diphenyl carbonate 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 dihydric phenols are bis (hydroxyphenyl) alkanes, especially those containing bisphenol A as a main raw material. Examples of the carbonate precursor include carbonyl halide, carbonyl ester, and haloformate. Specific examples include 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-bidroxyphenyl) -1,3,5
-Triisopropylbenzene, phloroglucin, trimellitic acid, isatin bis (o-cresol) and the like. In order to control the molecular weight, phenol and p-
t-butylphenol, pt-octylphenol,
p-cumylphenol or the above-mentioned carbon number of 10 to 2
Alkylphenols having 0 alkyl group are used.

The polycarbonate resin composition of the present invention comprises
As this molecular weight regulator, at least the above-mentioned carbon number 10
It is characterized in that it includes a terminal-modified PC in which the molecular terminal is blocked with an alkylphenol having an alkyl group of from 20 to 20.

The polycarbonate resin and the terminal-modified PC used in the present invention include polycarbonates in the presence of an ester precursor such as a bifunctional carboxylic acid such as terephthalic acid or polymethylenedicarboxylic acid or an ester-forming derivative thereof. It may be a polyester-polycarbonate copolymer obtained by performing polymerization, or a mixture of various polycarbonate resins.

Further, as the polycarbonate copolymer, a polycarbonate-polyorganosiloxane copolymer (hereinafter sometimes abbreviated as a PC-PDMS copolymer) can be particularly exemplified. The PC-PDMS copolymer is composed of a polycarbonate portion and a polyorganosiloxane portion. For example, a polyorganosiloxane (polydimethylsiloxane, polydiethylsiloxane having a reactive group at a terminal constituting the polycarbonate oligomer and the polyorganosiloxane portion) is used. Siloxane, polymethylphenylsiloxane, etc.) in a solvent such as methylene chloride, add an aqueous solution of sodium hydroxide of bisphenol A, and carry out an interfacial polycondensation reaction using a catalyst such as triethylamine. These PC-PDMS copolymers are described, for example, in JP-A-3-29.
No. 2,359, JP-A-4-202465, JP-A-8-81620, JP-A-8-302178, and JP-A-10-7897.

The degree of polymerization of the polycarbonate part of the PC-PDMS copolymer is preferably 3 to 100, and the degree of polymerization of the polydimethylsiloxane part is preferably about 2 to 500. The content of polydimethylsiloxane in the PC-PDMS copolymer (including bisphenol A polycarbonate as a by-product) is usually 0.2 to 30% by mass,
Preferably it is in the range of 0.3 to 20% by mass. The viscosity average molecular weight of a copolymer such as a polycarbonate resin and a PC-PDMS copolymer used in the present invention is usually 10.0 or less.
00 to 100,000, preferably 11,000 to 4
000, particularly preferably 12,000 to 30,000
0. Here, these viscosity average molecular weights (Mv)
Measured the viscosity of the methylene chloride solution at 20 ° C. using an Ubbelohde viscometer and calculated the intrinsic viscosity [η].
Is calculated by the following equation.

[Η] = 1.23 × 10 ⁻⁵ Mv ^0.83 The polycarbonate resin composition of the present invention comprises (A)
As the component, a mixed resin with the specific terminal-modified polycarbonate resin, PC-PDMS copolymer, bisphenol A polycarbonate, or the like can also be used. In this case, the content of polydimethylsiloxane in the entire polycarbonate resin in the component (A) is 0.1%.
It is blended so as to be 1 to 10% by mass, preferably 0.3 to 5% by mass.

(B) Functional Group-Containing Silicone Compound The functional group-containing silicone compound as the component (B) of the polycarbonate resin composition of the present invention is a (poly) organosiloxane having a functional group. The skeleton has the following formula: R ¹ aR ² bSiO _{(4-ab) / 2 wherein} R ¹ is a functional group-containing group, R ² is a hydrocarbon group having 1 to 12 carbon atoms, and a and b are 0 < a ≦ 3, 0 ≦ b <3,
0 <a + b ≦ 3], a polymer having a basic structure represented by the following formula:
It is a copolymer. The functional group contains an alkoxy group, an aryloxy, a polyoxyalkylene group, a hydrogen group, a hydroxyl group, a carboxyl group, a cyanol group, an amino group, a mercapto group, an epoxy group, and the like.

As these functional groups, a silicone compound having a plurality of functional groups and a silicone compound having different functional groups can be used in combination. The silicone compound having this functional group has a functional group (R ¹ ) / hydrocarbon group (R ² ) of usually about 0.1 to 3, preferably about 0.3 to ² .

These silicone compounds are liquids, powders and the like, but those having good dispersibility in melt kneading are preferred. For example, the kinematic viscosity at room temperature is 10 to 50.
A liquid of about 000 mm ² / s can be exemplified.
The polycarbonate resin composition of the present invention has a great feature that even when the silicone compound is in a liquid state, it is uniformly dispersed in the composition and less bleeds during molding or on the surface of a molded article.

This functional group-containing silicone compound is
(A) For 100 parts by mass of a polycarbonate resin,
0.1 to 10 parts by mass, preferably 0.2 to 5 parts by mass. Here, if the amount is less than 0.1 part by mass, the effect of improving the flame retardancy is small, and if it exceeds 10 parts by mass, the effect corresponding thereto is reduced. The content of the functional group-containing silicone compound, when using a polycarbonate resin containing a PC-PDMS copolymer as the polycarbonate resin, taking into account the silicone content in the entire composition, It can be determined appropriately.
In this case, since a certain amount of silicone is already contained, the content of the functional group-containing silicone compound can be reduced, and even if the silicone content in the entire composition is reduced, the flame retardancy level is reduced. There is an effect that can be maintained high.

The silicone compound having a functional group of the component (B), and a dimethyl silicone compound which is a non-functional group and is a general alkyl group, improves the flame retardancy as shown in the comparative examples described later. No effect can be expected.

(C) Core / shell type graft rubber-like elastic material The core / shell type graft rubber-like elastic material as the component (C) of the polycarbonate resin composition of the present invention comprises a core (core) and a shell (shell). The graft rubber has a structured two-layer structure, the core part is in a soft rubber state, the shell part on the surface is in a hard resin state, and the elastic body itself is in a powder state (particle state). Elastic body. Most of the core / shell type graft rubber-like elastic material retains its original shape even after being melt-blended with a polycarbonate resin. Since most of the compounded graft rubber-like elastic body maintains the original form, an effect of uniformly dispersing and preventing the surface layer from peeling can be obtained.

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

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 0 alkyl groups are preferred. Specifically, for example, ethyl acrylate, butyl acrylate,
Examples thereof include 2-ethylhexyl acrylate and n-octyl methacrylate. The rubber-like elastic material obtained from these alkyl acrylate-based monomers includes alkyl acrylates of 70% by mass or more and other vinyl monomers copolymerizable therewith, such as methyl methacrylate and acrylonitrile. , Vinyl acetate, styrene, and the like, and 30% by mass 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, acrylates 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 core / shell type graft rubber-like elastic material thus obtained preferably contains the rubber-like polymer in an amount of 20% by mass or more. Specific examples of such a core / shell type graft rubber-like elastic body include a MAS resin elastic body such as a graft copolymer of 60 to 80% by mass of n-butyl acrylate, styrene and methyl methacrylate. Can be Further, the polysiloxane rubber component has a structure in which 5-95% by mass of a polyacryl (meth) acrylate rubber component and 95-5% by mass of a polyacryl (meth) acrylate rubber component are entangled with each other so as to be inseparable, and have an average particle size of 0.01-1 μm. Particularly preferred is a composite rubber-based graft copolymer obtained by graft-polymerizing at least one vinyl monomer to a composite rubber of a certain degree. The copolymer has a higher impact resistance improving effect than the graft copolymer of each rubber alone. This composite rubber-based graft copolymer is commercially available as Metablen S-200 manufactured by Mitsubishi Rayon Co., Ltd.
1 and so on.

The content of the core / shell type graft rubber-like elastic material as the component (C) is 0.2 to 1 based on 100 parts by mass of the polycarbonate resin as the component (A).
0 parts by mass, preferably 0.5 to 5 parts by mass. Here, if the content of the graft rubber-like elastic material is less than 0.2 parts by mass, the effect of improving impact resistance is low, and if it exceeds 10% by mass, flame retardancy, heat resistance, and rigidity may decrease. Yes, usually up to 10 parts by weight is sufficient. The polycarbonate resin composition of the present invention provides excellent effects for the first time by using a relatively small amount of the functional group-containing silicone compound (B) and the core / shell type graft rubber-like elastic body (C). To demonstrate. In addition,
When another graft copolymer is used instead of the core / shell type graft rubber-like elastic material, the impact resistance may be improved in some cases, but the flame-retardant level must be maintained. Can be difficult.

In the polycarbonate resin composition of the present invention, the above three components can sufficiently achieve the object of the present invention from the viewpoints of moldability (melt fluidity), impact resistance and flame retardancy. . However, for the purpose of preventing melt dripping during combustion in a flame retardancy test or the like, a known melt dripping inhibitor can be further contained.

(D) Polyfluoroolefin resin As the anti-dripping agent, (D) polyfluoroolefin resin can be suitably used. Here, the polyfluoroolefin resin is usually a polymer or copolymer having a fluoroethylene structure, for example, a difluoroethylene polymer, a tetrafluoroethylene polymer, a tetrafluoroethylene-hexafluoropropylene copolymer, It is a copolymer of ethylene 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 10,000,000. As the polytetrafluoroethylene that can be used in the present invention, all types currently known can be used.

When polytetrafluoroethylene having a fibril-forming ability is used, higher anti-dripping properties 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 in the range of 0.01 to 1 MPa.
Under the pressure of a, the temperature is 0 to 200 ° C., preferably 20 to 10 ° C.
It is obtained by polymerizing at 0 ° C.

Here, the content of the polyfluoroolefin resin is determined based on the polycarbonate resin 10 as the component (A).
0.02 to 5 parts by mass, preferably 0 parts by mass,
It is 0.05 to 2 parts by mass. Here, if the amount is less than 0.02 parts by mass, the effect of preventing the molten dripping in the intended flame retardancy may not be sufficient. If the amount exceeds 5 parts by mass, 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, V-1, V-2 of UL-94, etc. is appropriately determined in consideration of the usage amount of other components. be able to.

Further, the 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. Among them, plate-like talc and mica, and fibrous fillers such as glass fiber and carbon fiber are preferable. The talc is a hydrous silicate of magnesium, and a commercially available talc can be used. The average particle size of the inorganic filler such as talc is 0.1 to 50 μm, preferably 0.1 to 50 μm.
2 to 20 μm. By incorporating these inorganic fillers, especially talc, the amount of the silicone compound can be reduced in some cases, in addition to the effect of improving rigidity.

Here, the content of the inorganic filler is 1 to 100 parts by mass, preferably 2 to 50 parts by mass with respect to 100 parts by mass of the polycarbonate resin as the component (A). If the amount is less than 1 part by mass, the intended rigidity and flame retardancy improvement effect may not be sufficient, and if it exceeds 100 parts by mass, the impact resistance and the melt fluidity may decrease, and 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.

The polycarbonate resin composition of the present invention comprises:
For the purpose of improving moldability, impact resistance, appearance improvement, weather resistance, rigidity, etc., the essential components consisting of (A), (B) and (C), and optional components such as (D) and inorganic filler Along with, thermoplastic resin such as polyester resin, polyamide resin,
Additive components commonly used in thermoplastic resins can be included as needed. For example, phenol-based, phosphorus-based, sulfur-based antioxidants, antistatic agents, polyamide polyether block copolymers (providing permanent antistatic performance),
Examples include benzotriazole-based and benzophenone-based ultraviolet absorbers, hindered amine-based light stabilizers (weathering agents), plasticizers, antibacterial agents, compatibilizers, and colorants (dye and pigment). It is desirable that the compounding amount of the optional component is in a range where the characteristics of the polycarbonate resin composition of the present invention are maintained.

Next, a method for producing the polycarbonate resin composition of the present invention will be described. The polycarbonate resin composition of the present invention comprises the above components (A), (B),
It is obtained by blending (C) at a predetermined ratio and various optional components used as necessary, such as (D), in predetermined amounts and kneading them. The compounding and kneading at this time
Preliminary mixing using a commonly used equipment, for example, a ribbon blender, a drum tumbler, etc., can be performed by a method using a Banbury mixer, a single screw extruder, a twin screw extruder, a multi-screw extruder, a co-kneader or the like. it can. The heating temperature during kneading is usually 240 to 30.
It is appropriately selected within the range of 0 ° C. As the melt-kneading molding, it is preferable to use an extruder, particularly a vent-type extruder. The components other than the polycarbonate resin can be previously melt-kneaded with the polycarbonate resin or another thermoplastic resin, that is, added as a master batch.

The polycarbonate resin composition of the present invention comprises:
Molding a molded product directly with the above melt-kneading molding machine, or, using the obtained pellets as a raw material, injection molding method, injection compression molding method, extrusion molding method, blow molding method, press molding method, vacuum molding method, Various molded articles can be manufactured by 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 for preventing sink marks on the appearance or for reducing the weight can be employed.

Molded articles obtained from the polycarbonate resin composition of the present invention include electric machines such as copying machines, fax machines, televisions, radios, tape recorders, video decks, personal computers, printers, telephones, information terminals, refrigerators, microwave ovens and the like.・ Housings or parts of electronic equipment,
Further, it is used in other fields such as automobile parts.

[0050]

EXAMPLES The present invention will be described more specifically with reference to Production Examples, Examples and Comparative Examples, but the present invention is not limited by these Examples.

Production Example 1 [Production of PC oligomer] 60 kg of bisphenol A was added to 400 liters of a 5% by mass aqueous sodium hydroxide solution.
Was dissolved to prepare a sodium hydroxide aqueous solution of bisphenol A.

Then, this aqueous solution of sodium hydroxide of bisphenol A, which was kept at room temperature, was supplied at a flow rate of 138 liters / hour and methylene chloride was supplied at a flow rate of 69 liters / hour to a tubular reactor having an inner diameter of 10 mm and a length of 10 m. The phosgene is introduced through an orifice plate,
Blowing was performed at a flow rate of 0.7 kg / hour, and the reaction was continuously performed for 3 hours. The tubular reactor used here was a double tube, and the outlet temperature of the reaction solution was kept at 25 ° C. by passing cooling water through the jacket. The pH of the discharged liquid is 10 to 11
It was adjusted to be.

By leaving the reaction solution thus obtained to stand, the aqueous phase was separated and removed, and the methylene chloride phase (2
20 liters) were collected and the PC oligomer (concentration 31
7 g / l). The degree of polymerization of the PC oligomer obtained here was 2 to 4, and the concentration of the chloroformate group was 0.7 normal.

Production Example 2 [Production of terminal-modified polycarbonate] 10 liters of the PC oligomer obtained in Production Example 1 was placed in a stirred container having an internal volume of 50 liters, and p-dodecylphenol (containing a branched dodecyl group) [oil Chemical Schenectady] 162
g was dissolved. Next, an aqueous sodium hydroxide solution (53 g of sodium hydroxide, 1 liter of water) and 5.8 cc of triethylamine were added, and the mixture was stirred at 300 rpm for 1 hour.
Reacted. Thereafter, a sodium hydroxide solution of bisphenol A (bisphenol A: 720 g, sodium hydroxide 412 g, 5.5 liters of water) was mixed with the above system,
Add 8 liters of methylene chloride, 500 rpm for 1 hour
And reacted. After the reaction, 7 liters of methylene chloride and 5 liters of water were added, and the mixture was stirred for 10 minutes at 500 rpm.
The obtained organic phase was washed with 5 liters of alkali (0.03 N-NaOH), 5 liters of acid (0.2 N-hydrochloric acid) and 5 liters of water (twice). Thereafter, the methylene chloride was evaporated to obtain a flaky polymer.
The viscosity average molecular weight was 17,500.

Production Example 3 [Preparation of Reactive PDMS] 1,483 g of octamethylcyclotetrasiloxane, 96 g of 1,1,3,3-tetramethyldisiloxane and 35 g of 86% sulfuric acid were mixed and mixed at room temperature. Stirred for hours. Thereafter, the oil phase was separated, 25 g of sodium hydrogen carbonate was added, and the mixture was stirred for 1 hour. After filtration, 150 ° C., 3 torr (4 × 10 ² P
Vacuum distillation was carried out in a) to remove low-boiling substances to obtain an oil.

60 g of 2-allylphenol and 0.00
To a mixture of 14 g of platinum as a platinum chloride-alcoholate complex with 294 g of the oil obtained above at 90 ° C.
At a temperature of. The mixture was stirred for 3 hours while maintaining the temperature at 90-115 ° C. The product was extracted with methylene chloride and washed three times with 80% aqueous methanol to remove excess 2-allylphenol. The product was dried over anhydrous sodium sulfate and heated to 115 ° C. in vacuo to distill off the solvent. The obtained terminal phenol PDMS was NM
As a result of the measurement of R, the number of repeating dimethylsilanooxy units was 30.

Production Example 4 [Production of PC-PDMS Copolymer] 182 g of the reactive PDMS obtained in Production Example 3 was dissolved in 2 L of methylene chloride, and 10 L of the PC oligomer obtained in Production Example 1 was mixed. There, 26 g of sodium hydroxide was added to water 1
Liter and triethylamine 5.7
After adding cc, the mixture was stirred and reacted at 500 rpm at room temperature for 1 hour.

After completion of the reaction, 5.2% by weight was added to the above reaction system.
A solution of 600 g of bisphenol A in 5 liters of aqueous sodium hydroxide solution, 8 liters of methylene chloride and 96 g of p-tert-butylphenol were added.
The mixture was stirred and reacted at 00 rpm at room temperature for 2 hours.

After the reaction, 5 l of methylene chloride was added,
Further, water washing with 5 liters of water, alkali washing with 5 liters of 0.03 N aqueous sodium hydroxide solution, acid washing with 5 liters of 0.2 N hydrochloric acid, and water washing twice with 5 liters of water are successively performed. It was removed to obtain a flake PC-PDMS copolymer. PC-PDM obtained
The S copolymer was vacuum dried at 120 ° C. for 24 hours. The viscosity average molecular weight is 17,000 and the PDMS content is 4.
It was 0% by mass.

The viscosity average molecular weight and PDPS content were determined as follows. (1) Viscosity-average molecular weight (Mv) The viscosity of a methylene chloride solution at 20 ° C. was measured with an Ubbelohde viscometer, and the intrinsic viscosity [η] was determined from this.

[Η] = 1.23 × 10 ⁻⁵ Mv ^0.83 (2) PDMS content The peak of bisphenol A isopropyl methyl group at 1.7 ppm in ¹ H-NMR and 0.2 ppm
Was determined on the basis of the intensity ratio with the peak of the methyl group of dimethylsiloxane, which was observed in (1).

Production Example 5 [Production of terminal-modified PC-PDMS copolymer] p-Dodecylphenol (containing a branched dodecyl group) used in Production Example 2 in Preparation Example 4 in place of 96 g of p-tert-butylphenol A terminally modified PC-PDMS copolymer was obtained according to Production Example 4 except that 168 g was used. The obtained terminal-modified PC-PDMS copolymer was vacuum-dried at 120 ° C. for 24 hours. The viscosity average molecular weight is 17,000,
The PDMS content was 4.0% by mass.

Examples 1 to 6 and Comparative Examples 1 to 7 Each component was blended in the proportions shown in Tables 1 and 2 (the component (A) was% by mass). Ingredient 100
Shown in parts by mass relative to parts by mass. And supplied to a vent-type twin-screw extruder (model: TEM35, manufactured by Toshiba Machine Co., Ltd.), melt-kneaded at 280 ° C., and pelletized. In all Examples and Comparative Examples, 0.2 parts by mass of Irganox 1076 (manufactured by Ciba Specialty Chemicals) and ADK STAB C were used as antioxidants.
0.1 part by mass (manufactured by Asahi Denka Kogyo KK) was blended.
After drying the obtained pellets at 120 ° C. for 12 hours,
A test piece was obtained by injection molding at a molding temperature of 270 ° C and a mold temperature of 80 ° C. The performance was evaluated by various tests using the obtained test pieces, and the results are shown in Tables 1 and 2.

The molding materials used and the performance evaluation methods are shown below. (A) Polycarbonate resin PC-1: Tafflon A1700 (manufactured by Idemitsu Petrochemical Co., Ltd.): bisphenol A polycarbonate resin, melt flow rate (MFR) = 27 g / 10 min [JIS
K7210: temperature: 300 ° C, load: 11.77
N], viscosity average molecular weight: 17,000, p-tert-
Butylphenoxy end capping.・ PC-2: Toughlon A1500 (made by Idemitsu Petrochemical Co., Ltd.): bisphenol A polycarbonate resin, M
FR = 50 g / 10 minutes, viscosity average molecular weight: 15,00
0, p-tert-butylphenoxy group end capping.

Terminal-modified PC: p-dodecylphenoxy group-terminated polycarbonate resin obtained in Preparation Example 2 PC-PDMS: Bisphenol A-polydimethylsiloxane (PDMS) obtained in Preparation Example 4 Copolymer, PDMS content = 4.0% by mass, viscosity average molecular weight:
17,000, p-tert-butylphenoxy endcapping. Modified PC-PDMS: bisphenol A-polydimethylsiloxane (PDMS) copolymer obtained in Production Example 5, PDMS content = 4.0% by mass, viscosity average molecular weight: 17,100, p-dodecylphenoxy group End sealing

(B) Silicone compound Silicone-1: methyl phenyl silicone containing vinyl group methoxy group, KR219 (manufactured by Shin-Etsu Chemical Co., Ltd.), kinematic viscosity = 18 mm ² / s Silicone-2: dimethyl silicone containing methoxy group KC-89 (manufactured by Shin-Etsu Chemical Co., Ltd.), kinematic viscosity =
20 mm ² / s ・ Silicone-3: dimethyl silicone, SH200
(Manufactured by Toray Dow Corning Co., Ltd.), kinematic viscosity = 350 m
m ² / s

(C) Core-shell type graft rubber-like elastic body Rubber-like elastic body-1: Composite rubber-based graft copolymer: Metablen S2001 (manufactured by Mitsubishi Rayon Co., Ltd.): Polydimethylsiloxane content: 50% by mass or more Rubber-like elastic body-2: MBS-based graft copolymer: Metablen C223 (manufactured by Mitsubishi Rayon Co., Ltd.) Polybutadiene content: 60% by mass or more Rubber-like elastic body-3: SBS-based graft copolymer (comparative): VECTOR8550 -5 (DexcoPoly
(D) polyfluoroolefin resin-PTFE: CD076 (Asahi IC fluoropolymers)

[Performance Evaluation Method] (1) Melt fluidity MFR (melt flow rate): JIS K7210
Compliant with. Temperature: 300 ° C, Load: 11.77N (2) IZOD (Izod impact strength), (Thickness: 3.
2 mm) Measured at 23 ° C. in accordance with ASTM D256 (3) Flame retardancy In compliance with UL94 combustion test V-2NG indicates that it does not correspond to any of V-0, V-1, and V-2. (5) Grease resistance It was based on the chemical resistance evaluation method (critical distortion by 1/4 ellipse). A sample piece (thickness = 3 mm) was fixed to the 1/4 elliptical surface shown in FIG. 1 (perspective view), Albanian grease (manufactured by Showa Shell Sekiyu KK) was applied to the sample piece, and held for 48 hours. The minimum length (X) at which cracks occurred was read, and the critical strain (%) was determined from the following equation (1).

[0069]

(Equation 1)

(5) Recyclability A notebook personal computer housing (A4 type) was molded from each composition pellet by injection molding at a molding temperature of 300 ° C. and a mold temperature of 80 ° C. This molded product was pulverized, and a test piece was again molded under the same conditions as a 100% recycled material. -IZOD impact strength of the recycle molded test piece was measured. -The color tone change of the recycled molded test piece was measured. JIS
The hue (L, a, b) of the test piece before and after recycling was measured with a color difference meter according to H7103 (yellowing degree test method), and the hue change was calculated as (ΔE).

[0071]

[Table 1]

[0072]

[Table 2]

From the results shown in Table 1, it is clear that the molded articles from the polycarbonate resin compositions of the present invention of the examples have improved moldability (melt fluidity) while maintaining high impact strength. . It also has excellent grease resistance and recyclability. Furthermore, it is clear that the flame retardancy is excellent at the level of V-0 by the addition of PTFE.

[0074]

The polycarbonate resin composition of the present invention can be used in all of impact resistance, melt fluidity, and flame retardancy without using a halogen-based or phosphorus-based flame retardant and containing a small amount of additives. At a high level. In addition, it is excellent in recyclability, can be reused, and can cope with thinned and large-sized molded products due to good moldability, thereby contributing to environmental problems and resource saving. Therefore, OA equipment,
It is expected that electric and electronic devices such as information devices and home electric appliances, and application fields such as automobile parts will be expanded.

[Brief description of the drawings]

FIG. 1 is a perspective view of a test piece mounting jig for evaluating the grease resistance of the composition of the present invention.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) C08L 27:12) C08L 27:12) F-term (Reference) 4F071 AA22X AA26 AA28X AA33X AA34X AA50 AA50X AA67 AA67X AA76 AA77 AF23 AF47 AF53 AH07 AH12 BA01 BB03 BB05 BB06 BC03 BC04 BC06 4J002 BD12Z BN12Y CK021 CP05X CP09X CP10X CP171 GN00 GQ00

Claims (5)

[Claims] 1. A functional group-containing silicone compound (B) with respect to 100 parts by mass of a polycarbonate resin containing a polycarbonate resin whose molecular terminal is capped with a phenoxy group having an alkyl group having 10 to 20 carbon atoms. 0.1 ~
A polycarbonate resin composition containing 10 parts by mass and (C) 0.2 to 10 parts by mass of a core / shell type graft rubber-like elastic material. 2. The polycarbonate according to claim 1, wherein (A) the polycarbonate resin contains at least a polycarbonate-polyorganosiloxane copolymer, and the polyorganosiloxane content in the polycarbonate resin is 0.1 to 10% by mass. Resin composition. 3. The polycarbonate resin composition according to claim 1, further comprising (D) 0.02 to 5 parts by mass of a polyfluoroolefin resin based on 100 parts by mass of the polycarbonate resin (A). object. 4. A molded article comprising the polycarbonate resin composition according to claim 1. 5. A housing or part of an electric / electronic device comprising the polycarbonate resin composition according to claim 1.