JP2002012755A - Polycarbonate resin composition and molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate resin composition which is capable of producing thin-walled molded articles because of improved moldability without deteriorating impact resistance and of improving a flame retardancy without using a halogen- or phosphate-based flame retardant. SOLUTION: The polycarbonate resin composition contains 100 pts. by mass of a resin comprising 1-99% by mass of (A) a polycarbonate-based resin containing a polycarbonate resin of which molecular ends are blocked with a 10-20C alkyl phenol and 99-1% by mass of (B) a styrene-based resin; and 0.01-5 pts. by mass of (C) a polyfluoroolefin resin and, if necessary, can be additionally blended with a functional group-containing silicone compound and/or an inorganic filler.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polycarbonate resin composition, and more particularly to a polycarbonate resin composition which has improved moldability, that is, melt fluidity, without deteriorating the impact resistance, which is a feature of the polycarbonate resin. The present invention relates to a polycarbonate resin composition and a molded article having flame retardancy without using a flame retardant.

[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. In the former (1), the level of flame retardancy is excellent to some extent. 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 phosphoric acid ester compound, a Group 2 metal salt, and the like, in that a flame retardant is essential.

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 is an excellent composition exhibiting excellent flame retardancy in a specific range where the content of polyorganosiloxane is small. However, together with JP-A-10-139964 of the above (1), although the flame retardancy is excellent, there are cases where the impact resistance and the moldability, which are the characteristics of the polycarbonate resin, are insufficient and the moldability is insufficient. There is a need for better methods.

[0008]

SUMMARY OF THE INVENTION According to the present invention, under the above-mentioned circumstances, the moldability, that is, the melt flowability is improved without lowering the impact resistance of a polycarbonate resin, and a thin-walled molded product can be produced. Provided is a polycarbonate resin composition having flame retardancy and capable of improving the level of flame retardancy without using a flame retardant such as a halogen-based or phosphorus-based flame retardant, and a molded article using the composition. It is intended for.

[0009]

Means for Solving the Problems The present inventors have intensively studied improvements in polycarbonate resin such as impact resistance, moldability and flame retardancy. As a result, by selecting and using a specific fluorine-based resin for the resin composed of a combination of a specific polycarbonate resin and a styrene-based resin, the impact resistance is maintained at a high level and the moldability is significantly improved. In addition, it has been found that, when used in combination with a specific silicone compound, the flame retardancy level can be further improved without using a halogen-based or phosphorus-based flame retardant,
The present invention has been completed.

That is, the present invention relates to (1) (A) 1 to 99% by mass of a polycarbonate resin containing a polycarbonate resin whose molecular terminal is sealed with an alkylphenol having 10 to 20 carbon atoms, and (B) a styrene resin 99 A polycarbonate resin composition containing (C) 0.01 to 5 parts by mass of a polyfluoroolefin resin with respect to 100 parts by mass of a resin consisting of 1% by mass to 1% by mass. (2) The polycarbonate resin composition according to (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. . (3) The resin is (A) a polycarbonate resin 70 to
The polycarbonate resin composition according to (1) or (2), comprising 98% by mass and 30 to 2% by mass of a rubber-modified styrene resin as the component (B). (4) Further, a resin 10 comprising (A) and (B)
The polycarbonate resin composition according to any one of (1) to (3), which comprises 0.1 to 10 parts by mass of the functional group-containing silicone compound (D) with respect to 0 parts by mass. (5) Further, a resin 10 comprising (A) and (B)
The polycarbonate resin composition according to any one of (1) to (4), containing (E) 1 to 100 parts by mass of an inorganic filler with respect to 0 parts by mass. (6) A molded article comprising the polycarbonate resin composition according to any one of (1) to (5). (7) 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 (5).

[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) 1 to 99% by mass of a polycarbonate-based resin containing a polycarbonate resin whose molecular terminal is capped with an alkylphenoxy group having 10 to 20 carbon atoms, and (B) a styrene-based resin 99 to (C) 0.01 to 5 parts by mass of a polyfluoroolefin resin per 100 parts by mass of a resin consisting of 1% by mass.

The polycarbonate resin composition of the present invention comprises:
As the polycarbonate resin as the component (A), a polycarbonate resin having a molecular terminal capped with a phenoxy group having an alkyl group having 10 to 20 carbon atoms (hereinafter sometimes abbreviated as a terminal-modified PC) is included. 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) Styrene resin The styrene resin as the component (B) of the polycarbonate resin composition of the present invention includes styrene, α
Monovinyl aromatic monomers such as methylstyrene 20
0 to 100% by mass, 0 to 60% by mass of a vinyl cyanide monomer such as acrylonitrile and methacrylonitrile, and 0 other vinyl monomer such as maleimide and methyl (meth) acrylate copolymerizable therewith. There is a polymer obtained by polymerizing a monomer or a monomer mixture consisting of up to 50% by mass. These polymers include polystyrene (G
PPS), acrylonitrile-styrene copolymer (AS
Resin).

As the styrene resin, a rubber-modified styrene resin is 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 content of the rubber in the rubber-modified styrenic resin is, for example, 2 to 50% by mass, preferably 5 to 30% by mass, particularly 5 to 15% by mass. 2% by mass of rubber
If it is less than 50%, the impact resistance becomes insufficient, and if it exceeds 50% by mass, 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 rubbery polymer containing polybutadiene, acrylate and / or methacrylate, styrene-butadiene-styrene rubber (SBS), 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 (eg, 1,2
1 to 30 mol% of vinyl bonds and 3 to 1,4-cis bonds
0-42 mol%), high cis polybutadiene (for example, 20 mol% or less of 1,2-vinyl bond, 1,4
-Containing at least 78 mol% of a cis bond), or a mixture thereof.

The polycarbonate resin composition of the present invention comprises:
By blending a styrene-based resin with a polycarbonate resin, the melt fluidity of the resin composition is improved. Here, the compounding ratio of the two resins is such that the polycarbonate resin of the component (A) is 1 to 99% by mass, preferably 50 to 9% by mass.
It is 8% by mass, more preferably 70 to 95% by mass, and (B) the styrene resin is 99 to 1% by mass, preferably 50 to 2% by mass, and more preferably 30 to 5% by mass. here,
If the polycarbonate resin as the component (A) is less than 1% by mass, heat resistance and strength are not sufficient, and if the styrene resin as the component (B) is less than 1% by mass, the effect of improving moldability is insufficient. In this case, as the styrene resin (B), the above-mentioned rubber-modified styrene resin is preferably used. In the case of this rubber-modified polystyrene resin,
(A) 70 to 98% by mass of a polycarbonate resin as a component
And (B) 30 to 2% by mass of a rubber-modified polystyrene resin.

These compounding ratios are determined in consideration of the molecular weight of the terminal-modified polycarbonate resin and other polycarbonate resins, the type of the styrene resin, the melt flow rate, the content of the rubber, the use of the molded product, the size, the thickness, and the like. Is determined as appropriate.

(C) Polyfluoroolefin Resin The polycarbonate resin composition of the present invention is used for the purpose of preventing dripping during melting in a flame retardancy test or a flame retardancy test.
(C) A polyfluoroolefin resin is used. Here, the polyfluoroolefin resin is usually a polymer containing a fluoroethylene structure, a copolymer,
For example, it is a difluoroethylene polymer, a tetrafluoroethylene polymer, a tetrafluoroethylene-hexafluoropropylene copolymer, or a copolymer of tetrafluoroethylene and an ethylene monomer containing no fluorine. Preferably, polytetrafluoroethylene (PTF
E), whose average molecular weight is preferably at least 500,000, particularly preferably 500,000.
-10,000,000. As the polytetrafluoroethylene that can be used in the present invention, all types currently known can be used.

When a polytetrafluoroethylene having a 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), 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 fluoroolefin resin is determined based on the resin 10 comprising the components (A) and (B).
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, the UL-94 V
It can be appropriately determined in consideration of the amount of other components used, etc., based on −0, V-1, V-2 and the like.

(D) Silicone Compound Next, in the present invention, the functional group-containing silicone compound (D), which is preferably used for further improving flame retardancy, is a (poly) organo compound having a functional group. Siloxanes. 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 group-containing silicone compounds, silicone compounds having a plurality of functional groups and silicone compounds 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 0.1 to 3,
Preferably it is about 0.3 to 2.

These silicone compounds are liquids, powders, etc., and 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. Here, if a silicone compound having no functional group is used, the effect of improving the flame retardancy of the present invention is hardly obtained.

This functional group-containing silicone compound is
0.1 to 10 parts by mass, preferably 0.2 to 5 parts by mass, per 100 parts by mass of the resin comprising the components (A) and (B).
It can be contained in 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 cannot be expected. When the polycarbonate resin containing a PC-PDMS copolymer is used as the polycarbonate-based resin, the content of the functional group-containing silicone compound is appropriately determined in consideration of the silicone content in the entire composition. Can be determined. 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.

(E) Inorganic Filler The polycarbonate resin composition of the present invention may contain an inorganic filler for improving rigidity and the like. Examples of the inorganic filler include talc, mica, kaolin, diatomaceous earth, calcium carbonate, calcium sulfate, barium sulfate, glass fiber, carbon fiber, potassium titanate fiber and the like. Among them, plate-like talc and mica, and fibrous fillers such as glass fiber and carbon fiber are preferable. As the talc, a hydrated silicate of magnesium, which is generally commercially available, can be used. The average particle size of the inorganic filler such as talc is 0.1%.
５０50 μm, preferably 0.2-20 μm. By containing these inorganic fillers, especially talc,
In some cases, in addition to the effect of improving rigidity, the amount of the silicone compound can be reduced.

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 resin comprising the components (A) and (B). 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 further comprises the above components (A) to (C) for the purpose of improving moldability, impact resistance, appearance, weather resistance and rigidity. If necessary, the components (D) and (E) used in the above method may contain a thermoplastic resin such as a polyester resin or a polyamide resin, or an additive component commonly used in thermoplastic resins. For example, phenolic,
Phosphorus-based, sulfur-based antioxidants, antistatic agents, polyamide polyether block copolymers (providing permanent antistatic performance), benzotriazole- and benzophenone-based ultraviolet absorbers, hindered amine-based light stabilizers (weathering agents),
Examples thereof include a plasticizer, an antibacterial agent, a compatibilizer, and a colorant (dye, pigment). The amount of the optional component is not particularly limited as long as 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. In the polycarbonate resin composition of the present invention, the above components (A) to (C) are used in the above proportions, and if necessary, (D) and (E).
It is obtained by blending the components and various optional components at a predetermined 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, and the like, and a Banbury mixer,
It can be performed by a method using a single-screw extruder, a twin-screw extruder, a multi-screw extruder, a co-kneader or the like. The heating temperature during kneading is usually 240 to 300 ° C.
Is appropriately selected within the range. 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:
A molded product is directly manufactured using the above-mentioned melt-kneading molding machine, or an injection molding method, an injection compression molding method, an extrusion molding method, a blow molding method, a press molding method, and a vacuum molding are performed using the obtained pellet as a raw material. Various molded products can be produced by a 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 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 copiers, faxes, televisions, radios, tape recorders, video decks, personal computers, printers, telephones, information terminals, refrigerators and microwave ovens.・ Housings or parts of electronic equipment,
Further, it is used in other fields such as automobile parts.

[0048]

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

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.

Next, 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 50 liter stirring vessel with 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 and reacted at 300 rpm for 1 hour. Thereafter, a sodium hydroxide solution of bisphenol A (bisphenol A: 720 g,
412 g of sodium hydroxide and 5.5 liters of water), and 8 liters of methylene chloride was added thereto.
The mixture was stirred and reacted. After the reaction, 7 liters of methylene chloride and 5 liters of water are added, and 500 rpm for 10 minutes.
After stirring was stopped, the mixture was allowed to stand, and the organic phase and the aqueous phase were separated. The organic phase obtained was treated with 5 liters of alkali (0.03
(Normal-NaOH), 5 liters of acid (0.2N-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.

Preparation 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 for 17 hours. 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 g
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 (branched dodecyl group) used in Production Example 2 was replaced with 96 g of p-tert-butylphenol in Production Example 4. (Contained) A terminal-modified PC-PDMS copolymer was obtained in the same manner as in Production Example 4 except that 168 g was used. The viscosity average molecular weight of the obtained PC-PDMS copolymer was 17,10.
0 and the PDMS content was 4.0% by mass.

Examples 1 to 8 and Comparative Examples 1 to 6 Each component was blended in the proportions shown in Tables 1 and 2 (the components (A) and (B) are in mass%). The ingredients are
It is shown in parts by mass with respect to 100 parts by mass of the resin composed of the components (A) and (B). 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 0.1 parts by mass of ADK STAB C (manufactured by Asahi Denka Kogyo) were used as antioxidants. Was blended. The obtained pellet was dried at 120 ° C. for 12 hours, and then injection molded at a molding temperature of 270 ° C. and a mold temperature of 80 ° C. to obtain a test piece. 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 method are shown below. (A) Polycarbonate resin ・ PC-1: Teflon A1900 (manufactured by Idemitsu Petrochemical Co., Ltd.): bisphenol A polycarbonate resin, M
FR = 19 g / 10 minutes (temperature: 300 ° C., load: 11.
77N), viscosity average molecular weight: 19,000, p-ter
t-butylphenoxy group terminal blocking PC-2: Tafflon A1500 (manufactured 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) copolymer obtained in Preparation Example 4 Coalescence, PDMS content = 4.0% by mass, viscosity average molecular weight:
17,000, p-tert-butylphenoxy group end-capping Terminal-modified PC-PDMS: bisphenol A-polydimethylsiloxane (PDMS) obtained in Production Example 5 above
Copolymer, PDMS content = 4.0% by mass, viscosity average molecular weight: 17,100, p-dodecylphenoxy group end-capping

(B) Styrene resin • HIPS: high impact polystyrene (HIPS): ID
EMITSU PS IT44 (manufactured by Idemitsu Petrochemical Co., Ltd.) Polybutadiene grafted with styrene, rubber content 10% by mass, MFR: 8 g / 10 min (J
IS K 7210: temperature: 200 ° C., load: 49.0
3N) ABS: Acrylonitrile butadiene styrene copolymer (ABS): DP-611 (manufactured by TECRIPOLYMER CO., LTD.), MFR: 2 g / 10 minutes (C) Polyfluoroolefin resin Made by company)

(D) 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 (E) Inorganic filler ・ Talc: FFR (manufactured by Asada Flour Milling Co., Ltd.), average particle size = 0.7
μm ・ GF: glass fiber, 03MA419 (manufactured by Asahi Fiber Glass Co., Ltd.), fiber diameter = 13 μm, fiber length = 3 mm

[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) According to ASTM D256, 23 ° C (wall thickness: 3.2m)
m) (3) Flexural modulus Conforms to JIS K 7202 [Span: 60 mm, test speed: 2.0 mm / min (4) Flame retardancy Conforms to UL94 combustion test V-2NG is V-0, V- 1 and V-2.

(5) Grease Resistance The grease resistance was based on the chemical resistance evaluation method (critical distortion due to 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).

[0068]

(Equation 1)

[0069]

[Table 1]

[0070]

[Table 2]

From the results shown in Table 1, it is clear that the molded articles made of the polycarbonate resin composition of the present invention of the examples have improved melt fluidity while maintaining high impact strength. Also, it has excellent grease resistance. further,
By adding the functional group-containing silicone compound, the flame retardancy can be further improved. Further, even when the rigidity (flexural modulus) is increased by adding an inorganic filler, the impact strength and the formability can be made high. Therefore, it is possible to reduce the thickness of a molded product as well as the moldability and flame retardancy.

[0072]

The polycarbonate resin composition of the present invention has a high level of impact resistance and melt fluidity. In addition, by blending a specific silicone compound and an inorganic filler, a molded article having excellent flame retardancy and rigidity can be obtained without using a halogen-based or phosphorus-based compound while ensuring moldability. Therefore, it is possible to contribute to environmental problems and resource saving, in combination with thinning of a molded product due to good moldability. Therefore, it is expected that the application fields of OA equipment, information equipment, electric / electronic equipment such as home appliances, and 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 51/04 51/04 83/04 83/04 C08K 5/54 F-term (reference) 4F071 AA22 AA26 AA50 AA77 AB00 AC16 AH12 BB06 BC07 4J002 BC03X BC06X BC07X BC09X BD12Y BD15Y BD16Y BN15X BN16X CG01W CG02W CP04Z CP05Z CP06Z CP09Z CP10Z DA017 DE187 DE237 DG057 DJ017 EX070 DJ077 DJ077 DJ070

Claims (7)

[Claims] 1. A mass ratio of (A) 1 to 99% by mass of a polycarbonate-based resin containing a polycarbonate resin capped with a phenoxy group having an alkyl group having 10 to 20 carbon atoms and (B) a styrene-based resin 99 to 1 A polycarbonate resin composition containing (C) 0.01 to 5 parts by mass of a polyfluoroolefin resin based on 100 parts by mass of a resin consisting of 100% by mass. 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, wherein the resin comprises (A) 70 to 98% by mass of a polycarbonate resin and (B) 30 to 2% by mass of a rubber-modified styrene resin. . 4. The composition according to claim 1, further comprising 0.1 to 10 parts by mass of the functional group-containing silicone compound (D) based on 100 parts by mass of the resin comprising (A) and (B).
The polycarbonate resin composition according to any one of the above. 5. An inorganic filler (E) in an amount of 1 to 10 parts by mass per 100 parts by mass of the resin (A) and (B).
The polycarbonate resin composition according to any one of claims 1 to 4, which contains 0 parts by mass. 6. A molded article comprising the polycarbonate resin composition according to claim 1. 7. A housing or component for an electric / electronic device comprising the polycarbonate resin composition according to claim 1.