JP2002012746A - Polycarbonate resin composition and molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate resin composition improved in moldability (melt flow characteristics) without detriment to the impact resistance, and improved in flame retardancy without using a halogenated flame retardant, a phosphate flame retardant and the like. SOLUTION: The resin composition contains 100 mass pts. resin mixture comprising (A) 1-99 mass% polycarbonate resin containing a copolyester- carbonate having aliphatic segments and (B) 99-1 mass% styrene resin, (C) 0.01-5 mass pts. polyfluoroolefin resin, and optionally (D) 0.1-30 pts.wt. silicon compound containing functional groups.

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, has improved moldability, that is, melt fluidity, and flame retardancy while maintaining impact resistance which is a characteristic of polycarbonate resin. The present invention relates to a polycarbonate resin composition and a molded article.

[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. A polycarbonate resin composition which has flame retardancy and can improve the level of flame retardancy without using a halogen-based or phosphorus-based flame retardant, and a molded article using the composition. And

[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, Showing flame retardancy, furthermore, when used in combination with a specific silicone compound, it is possible to improve the flame retardancy level without using a halogen-based or phosphorus-based flame retardant,
The present invention has been completed.

That is, the present invention provides: (1) (A) polycarbonate resins 1 to 99 containing a copolyestercarbonate having an aliphatic segment;
A polycarbonate resin composition comprising (C) 0.01 to 5 parts by mass of a polyfluoroolefin resin with respect to 100 parts by mass of a resin composed of 99% to 1% by mass of (B) a styrene-based resin. (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) 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), further comprising (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.
(A) constituting the polycarbonate resin composition of the present invention
The copolyestercarbonate copolymer having an aliphatic segment (hereinafter sometimes abbreviated as PC-PMDC copolymer) is derived, for example, from an aromatic polycarbonate part, a dihydric phenol and polymethylenedicarboxylic acid. A copolymer having a polyester unit, preferably having an aromatic polycarbonate unit having a structural unit represented by the following structural formula (1) and a polyester unit having a structural unit represented by the following structural formula (2) in a molecule: Coalescence can be mentioned.

[0012]

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Wherein R ¹ and R ² have 1 to 1 carbon atoms.
6 represents an alkyl group or a phenyl group, which may be the same or different. Z is a single bond, an alkylene group having 1 to 20 carbon atoms or an alkylidene group having 1 to 20 carbon atoms,
20 cycloalkylene group, or a cycloalkylidene group having 5 to 20 carbon atoms or _{-SO 2, -, - SO -} , - S
-, -O-, and -CO- are shown. Preferably, it is an isopropylidene group.

A and b are an integer of 0 to 4, preferably 0. m represents an integer of 5 to 20, preferably 8 to 12
It is. The viscosity average molecular weight of the PC-PMDC copolymer of the component (A) is preferably from 10,000 to 40,000, and more preferably from 12,000 to 30,000. The measuring method is the same as described below.

The PC-PMDC copolymer is, for example,
Polycarbonate oligomer (hereinafter, abbreviated as PC oligomer) constituting the aromatic polycarbonate portion and polymethylene dicarboxylic acid, which have been prepared in advance, are dissolved in a solvent such as methylene chloride, chlorobenzene, or chloroform. It can be produced by adding an aqueous solution, and performing an interfacial polycondensation reaction in the presence of a terminal stopper using a tertiary amine (such as triethylamine) or a quaternary ammonium salt (such as trimethylbenzylammonium chloride) as a catalyst.

This PC oligomer is produced in the same manner as in the production of ordinary polycarbonate resins. For example, it can be easily produced by reacting a dihydric phenol with a carbonate precursor such as phosgene or a carbonate compound in a solvent such as methylene chloride.

That is, for example, in a solvent such as methylene chloride, a reaction between a dihydric phenol and a carbonate precursor such as phosgene, or a transesterification reaction between a dihydric phenol and a carbonate precursor such as diphenyl carbonate. Manufactured by

Examples of the dihydric phenol include 4,4'-dihydroxydiphenyl; 1,1-bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, and 2,2-bis (4 -Hydroxyphenyl)
Bis (4-hydroxyphenyl) alkane such as propane; bis (4-hydroxyphenyl) cycloalkane;
Bis (4-hydroxyphenyl) oxide; bis (4-
Bis (4-hydroxyphenyl) sulfone; bis (4-hydroxyphenyl) sulfoxide; bis (4-hydroxyphenyl) ether; bis (4-hydroxyphenyl) ketone, and the like. Among them, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) is preferable. These dihydric phenols may be used alone or in combination of two or more.

Examples of the carbonate compound include diaryl carbonates such as diphenyl carbonate and dialkyl carbonates such as dimethyl carbonate and diethyl carbonate.

In the present invention, the PC oligomer used for the production of the PC-PMDC copolymer may be a homopolymer using one of the above-mentioned dihydric phenols or a copolymer using two or more of the above-mentioned dihydric phenols. You may. Further, it may be a thermoplastic random branched polycarbonate obtained by using a polyfunctional aromatic compound in combination with the dihydric phenol. In that case, as a branching agent (polyfunctional aromatic compound), 1,1,1-tris (4-hydroxyphenyl)
Ethane, α, α ′, α ″ -tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene, 1-
[Α-methyl-α- (4′-hydroxyphenyl) ethyl] -4- [α ′, α′-bis (4 ″ -hydroxylphenyl) ethyl] benzene, phloroglucin, trimellitic acid, isatin bis (o-cresol) Etc. can be used.

For controlling the molecular weight, phenol, pt-butylphenol, pt-octylphenol, p-cumylphenol, p-decylphenol, p-dodecylphenol, p-pentadecylphenol and the like are used. Used.

As the above polymethylene dicarboxylic acid, a dicarboxylic acid having a polymethylene group having 5 to 20 carbon atoms is used, and preferably has 8 to 12 carbon atoms.
The copolyestercarbonate having an aliphatic segment in the component (A) can be produced by the above method. Generally, an aromatic polycarbonate resin is produced as a by-product and is produced as a composition, and the overall viscosity average molecular weight is 10,000.
It is preferably from 0 to 40,000, and more preferably from 12,
000 to 30,000. The amount of polymethylene dicarboxylic acid is 1 to 25 mol% based on the dihydric phenol.
It is.

The component (A) may be a mixture of a copolyestercarbonate having a mixed aliphatic segment such as bisphenol-A polycarbonate and another polycarbonate resin. In this case, the viscosity average molecular weight of the newly added polycarbonate resin is preferably 10,000 to 40,000, and more preferably 12,000 to 30,000.

The other polycarbonate resin (PC) is not particularly limited, and includes 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. 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.

Particularly preferred dihydric phenols are bis (hydroxyphenyl) alkanes, particularly those containing bisphenol A as a main raw material. Examples of the carbonate precursor include carbonyl halide, carbonyl ester, and haloformate. Specific examples include phosgene, dihaloformate of dihydric phenol, diphenyl carbonate, dimethyl carbonate, and diethyl carbonate.

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, p-decylphenol, p-dodecylphenol, p-pentadecylphenol and the like are used.

The polycarbonate resin used in the present invention includes a polyester resin obtained by polymerizing a polycarbonate in the presence of a bifunctional aromatic carboxylic acid such as terephthalic acid or an ester precursor such as an ester-forming derivative thereof. It may be a copolymer such as a polycarbonate resin or a mixture of various polycarbonate resins.

Further, as the polycarbonate copolymer, a polycarbonate-polyorganosiloxane copolymer (hereinafter sometimes abbreviated as 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. PC
-PDMS copolymer is disclosed in, for example, JP-A-3-2924.
No. 59, JP-A-4-202465, JP-A-8
-81620, JP-A-8-302178,
It is disclosed in Japanese Patent Application Laid-Open No. 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. Further, the content of polydimethylsiloxane in the PC-PDMS copolymer is usually 0.5 to 30% by mass,
Preferably it is in the range of 1 to 20% by mass. The viscosity average molecular weight of the polycarbonate resin, PC-PDMS copolymer, etc. used in the present invention is usually 10,000 to 100,
000, preferably 11,000 to 30,000, particularly preferably 12,000 to 30,000. Here, the viscosity average molecular weight (Mv) of various polycarbonate-based resins in the component (A) was determined using an Ubbelohde viscometer.
The viscosity of the methylene chloride solution at 20 ° C. is measured, and the intrinsic viscosity [η] is determined from this, and is calculated by the following equation.

[Η] = 1.23 × 10 ⁻⁵ Mv ^0.83 The viscosity average molecular weight of the entire polycarbonate resin of the component (A) is preferably 10,000 to 40,000, more preferably 12,000 to 30,000. And particularly preferably 14,000 to 26,000. If the molecular weight is too low, the mechanical strength of the resin composition of the present invention, especially impact resistance may be poor, if the molecular weight is too high, the fluidity of the resin composition of the present invention, that is, poor moldability. is there.

The content of the polyorganosiloxane when the above-mentioned PC-PDMS copolymer is contained is (A) 0.1 to 10% by mass of the entire polycarbonate resin.
It is preferable in view of the flame retardancy of the resin composition of the present invention. The content is more preferably 0.2 to 5% by mass, and particularly preferably 0.1 to 5% by mass.
3 to 3% by mass.

The amount of the polymethylene dicarboxylic acid is preferably 1 to 15 mol%, more preferably 1 to 12 mol% based on the main monomer (dihydric phenol) of the entire polycarbonate resin (A). Mol%, particularly preferably 2 to 10 mol%. If the amount of polymethylene dicarboxylic acid is too small, the fluidity of the resin composition of the present invention may not be improved, and if it is too large, the heat resistance of the resin composition of the present invention may decrease.

(B) Styrene Resin As the styrene resin, 20 to 100% by mass of a monovinyl aromatic monomer such as styrene and α-methylstyrene, and a vinyl cyanide monomer such as acrylonitrile and methacrylonitrile 0 to 60% by mass, and a monomer or monomer mixture composed of 0 to 50% by mass of another vinyl monomer such as maleimide and methyl (meth) acrylate copolymerizable therewith. Polymer. Examples of these polymers include polystyrene (GPPS) and acrylonitrile-styrene copolymer (AS resin).

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

The 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 rubber polymer containing polybutadiene, acrylate and / or methacrylate, styrene-butadiene-styrene rubber (SB
S), styrene-butadiene rubber (SBR), butadiene-acrylic rubber, isoprene rubber, isoprene-styrene rubber, isoprene-acrylic rubber, ethylene-propylene rubber and the like.

Among them, particularly preferred is polybutadiene. The polybutadiene used here is a low cis polybutadiene (for example, one containing 1 to 30 mol% of 1,2-vinyl bond and 30 to 42 mol% of 1,4-cis bond), and a high cis polybutadiene (for example, 1,2-vinyl bond). (Containing 20 mol% or less of vinyl bonds and 78 mol% or more of 1,4-cis bonds) or a mixture thereof.

The polycarbonate resin composition of the present invention comprises:
By blending a styrene resin with a polycarbonate resin, the melt fluidity of the resin composition is improved. Here, the mixing ratio of both resins is 1 to 99% by mass of the polycarbonate resin of the component (A), preferably 50 to 98%.
%, More preferably 70 to 97% by mass, and (B) the styrene resin is 99 to 1% by mass, preferably 50 to 2% by mass, and more preferably 30 to 3% 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, it is most preferable to comprise 70 to 98% by mass of the polycarbonate resin (A) and 30 to 2% by mass of the rubber-modified polystyrene resin (B).

These compounding ratios are appropriately determined in consideration of the molecular weight of the polycarbonate resin, the type and molecular weight of the styrene resin, the melt flow rate, the content of the rubber, the use of the molded product, the size, the thickness, and the like. .

(C) Polyfluoroolefin Resin The polycarbonate resin composition of the present invention further uses (C) a fluoroolefin resin for the purpose of preventing dripping during melting in a flame retardancy test or the like. Here, the fluoroolefin resin is usually a polymer or copolymer containing a fluoroethylene structure, for example, difluoroethylene polymer, tetrafluoroethylene polymer, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene And a copolymer of fluorine-free ethylene-based monomer. Preferably, it is polytetrafluoroethylene (PTFE), and its average molecular weight is preferably 500,000 or more, and particularly preferably 500,000 to 1
0,000,000. 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 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, 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.

(D) Silicone Compound Next, in the present invention, more preferably used
The functional group-containing silicone compound as the component (D) is a (poly) organosiloxane having a functional group, and its skeleton is represented by the 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, 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 cannot be expected.

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. 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 As the inorganic filler, talc, mica, kaolin, diatomaceous earth, calcium carbonate, calcium sulfate, barium sulfate,
Glass fiber, carbon fiber, potassium titanate fiber and the like can be mentioned. 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 to 50 μm, preferably 0.2 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 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 comprises the above components (A), (B) and (C) for the purpose of improving moldability, impact resistance, appearance, weather resistance and rigidity. In addition to the essential components, optional components such as (D) and (E) used as needed, and additive components commonly used in thermoplastic resins can be contained as necessary. For example, phenol-based, phosphorus-based, sulfur-based antioxidants, antistatic agents, polyamide polyether block copolymers (providing permanent antistatic properties), benzotriazole-based and benzophenone-based ultraviolet absorbers, hindered amine-based light stabilizers (Weathering agent), plasticizer, antibacterial agent, compatibilizer,
Coloring agents (dyes, pigments) and the like can be mentioned. 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. The polycarbonate resin composition of the present invention is obtained by mixing and kneading the above components (A) to (C) at the above ratio, and various optional components used as needed at a predetermined ratio. .
The compounding and kneading at this time are usually used, for example, premixed with a ribbon blender, a drum tumbler or the like, and a Banbury mixer, a single screw extruder, a twin screw extruder, a multi-screw extruder,
It can be performed by a method using a coneder or the like. The heating temperature during kneading is appropriately selected usually in the range of 240 to 300 ° 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 are previously melt-kneaded with the polycarbonate resin or another thermoplastic resin,
That is, it can be added as a master batch.

The polycarbonate resin composition of the present invention comprises:
Molding a molded product directly by the above melt kneading molding machine,
Alternatively, various molded articles can be produced from the obtained pellets by an injection molding method, an injection compression molding method, an extrusion molding method, a blow molding method, a press molding method, a vacuum molding method, a foam molding method, or the like. However, a pellet-shaped molding raw material is produced by the above-mentioned melt-kneading method, and then the pellets can be used particularly suitably for production of an injection molded product by injection molding or injection compression molding. In addition,
As an injection molding method, gas injection molding for preventing sink marks on the appearance or 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, microwave ovens and the like.・ Housings or parts of electronic equipment,
Further, it is used in other fields such as automobile parts.

[0054]

EXAMPLES The present invention will be described more specifically with reference to examples and comparative examples, but the present invention 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.

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.

The reaction solution thus obtained was allowed to stand, whereby 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 PC-PMDC Copolymer [I]] An aqueous solution of decanedicarboxylic acid in sodium hydroxide (317 g of decanedicarboxylic acid, 110 g of sodium hydroxide) was added to 10 liters of the PC oligomer obtained in Production Example 1. , 2 liters of water) and 5.8 ml of triethylamine, and the mixture was stirred at room temperature for 1 hour at 300 rpm to react.
Thereafter, an aqueous sodium hydroxide solution of bisphenol A (534 g of bisphenol, sodium hydroxide 3) was added to the above system.
12 g, 5 liters of water) and p-cumylphenol 13
6 g, mixed with 8 liters of methylene chloride,
The mixture was reacted by stirring at 500 rpm for 1 hour. After the reaction, 7 l of methylene chloride and 5 l of water were added, and the mixture was stirred at 500 rpm for 10 minutes. After the stirring was stopped, the mixture was allowed to stand, and the organic phase and the aqueous phase were separated. The obtained organic phase was sequentially washed with 5 liters of a 0.03 N aqueous sodium hydroxide solution in alkali, washed with 5 liters of 0.2 N hydrochloric acid in acid, and washed twice with 5 liters of water, and finally methylene chloride was removed. A flaky polymer was obtained. The viscosity average molecular weight was 17,000, and the content of decanedicarboxylic acid with respect to all monomers was 5.2 mol%. -PC-PMDC copolymer [II] Lexan SP1010 manufactured by General Electric Co. was used as a commercially available BPA-PMDC copolymer. The comonomer is decane dicarboxylic acid and the terminator is p-
Cumylphenol. The viscosity average molecular weight is 18,80
0, and the content of decanedicarboxylic acid with respect to all the monomers was 8.2 mol%.

Production Example 3 [Production 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 the mixture was mixed at room temperature with 17%. 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 sulphate and evaporated in vacuo to a temperature of 115 ° C.

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 peak of methyl group of isopropyl of bisphenol A observed 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).

Examples 1 to 8 and Comparative Examples 1 to 5 The components were blended at the ratios shown in Tables 1 and 2 (the components (A) and (B) are in mass%). Is
It is shown in parts by mass with respect to 100 parts by mass of the (A) component and (B) component resin. And supplied to a vent-type twin-screw extruder (model name: TEM35, manufactured by Toshiba Machine Co., Ltd.).
The mixture was melt-kneaded at 0 ° 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. After the obtained pellets were dried at 120 ° C. for 12 hours, a molding temperature of 270
A test piece was obtained by injection molding at 80 ° 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 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, terminal blocking agent = p-tert-butylphenol PC-2: Tafflon A1500 (made by Idemitsu Petrochemical Co., Ltd.): bisphenol A polycarbonate resin, M
FR = 50 g / 10 minutes, viscosity average molecular weight: 15,00
0, terminal blocking agent = p-tert-butylphenol PC-PMDC [I]: polyester carbonate resin having an aliphatic unit obtained in the above Preparation Example 3 PC-PMDC [II]: commercially available product PC- PDMS: bisphenol A-polydimethylsiloxane (PDMS) copolymer obtained in Production Example 4

(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 weight, MFR: 8 g / 10 minutes (temperature: 200 ° C., load: 49.03 N) ABS: acrylonitrile butadiene Styrene copolymer (ABS): DP-611 (manufactured by Tekri Polymer Co., Ltd., MFR: 2 g / 10 min) (C) Polyfluoroolefin resin-PTFE: CD076 (manufactured by Asahi ICI Fluoro Chemicals Co., Ltd.)

(D) Silicone compound Silicone-1: vinyl methoxy group-containing methylphenyl silicone, KR219 (manufactured by Shin-Etsu Chemical Co., Ltd.), kinematic viscosity = 18 mm ² / s Silicone-2: methoxy group-containing dimethyl silicone, 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 (specimen thickness: 1.5 mm,
2.5 mm) Note that V-2NG 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)

[0070]

[Table 1]

[0071]

[Table 2]

From the results shown in Table 1, it is clear that the molded articles made of the polycarbonate resin compositions of the present invention of the examples have improved melt flowability while maintaining high impact strength. Also, it has excellent grease resistance. further,
The flame retardancy can be further improved by adding the functional group-containing silicone compound. 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.

[0073]

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.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 51:04 C08L 51:04 27:12 27:12 83:04) 83:04) F-term (Reference) 4F071 AA10 AA22 AA26 AA50 AA67 AA88 AF02 AF20 AF23 AF47 AH12 BB06 BC07 4J002 BC03X BC06X BC09X BD15Y BH01X BN15X BN16X CG04W CP04Z CP05Z CP06Z CP09Z CP10Z CP18Z DA017 EX087 DJ037 DJ087 DJ037 DJ087

Claims (7)

[Claims] 1. A polycarbonate resin 1 containing (A) a copolyestercarbonate having an aliphatic segment.
A polycarbonate resin composition comprising (C) 0.01 to 5 parts by mass of a polyfluoroolefin resin with respect to 100 parts by mass of a resin composed of 99 to 1% by mass of (B) a styrene-based resin. 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, comprising 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.