JP2002069282A - Polycarbonate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame-retardant polycarbonate resin composition which excels in sliding properties and an excellent appearance of molded articles without adversely effecting on the inherent mechanical strength and heat resistance which polycarbonate resins possess. SOLUTION: The flame-retardant polycarbonate resin composition comprises (A) 100 pts.wt. polycarbonate resin, (B) 0.05-5 pts.wt. silicone oil (BH) having a kinematic viscosity at 25 deg.C of >=10,000 mm2/s, (c) 0.5-25 pts.wt. composite rubber having a structure in which a polyorganosiloxane rubber component and a polyalkyl (meth)acrylate rubber component are entangled with each other, and (D) 1-30 pts.wt. phosphoric ester compound.

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 having excellent slidability.

[0002]

2. Description of the Related Art In recent years, in order to reduce the size and weight of OA equipment and electronic equipment and to reduce the number of parts, cases in which synthetic resin is used for sliding members have been increasing. Polycarbonate resins are used for parts of sliding members such as gears because of their excellent dimensional accuracy and mechanical strength. In such applications, a sliding agent is added to the polycarbonate resin in order to improve the slidability.

[0003] For example, JP-A-63-21355 discloses a resin composition comprising a polycarbonate resin and a tetrafluoroethylene resin. However, in the case of such a resin composition, it is necessary to use a large amount of a fluororesin having no affinity, so that there is a disadvantage that delamination or mold deposit occurs during molding. In addition, Japanese Unexamined Patent Publication No.
No. 136065 discloses a resin composition comprising polybutylene terephthalate and polycarbonate. However, in the case of such a resin composition, not only the excellent properties (mechanical strength, heat resistance, and flame retardancy) inherent to the polycarbonate resin are impaired, but also phase separation occurs.

[0004] Further, a resin composition in which silicone oil is blended with a polycarbonate resin has been proposed. However, in the case of such a resin composition, since the silicone oil on the surface of the molded product oozes out in a short time, there is a problem that the surface is sticky and the slidability is easily lowered. Therefore, for example, use of a high molecular weight silicone oil has been attempted. However, in this case, it is necessary to add a large amount of silicone oil in order to obtain sufficient sliding properties. As a result, unevenness in gloss due to phase separation of the silicone oil easily occurs on the surface of the molded product, which is impractical. It is enough.

Further, for example, Japanese Patent Application Laid-Open No. 9-255864 discloses that in order to improve the compatibility between a polycarbonate resin and a silicone oil, a high viscosity dimethyl silicone oil and a polyolefin, polystyrene, acrylonitrile-styrene resin or acrylonitrile are added to the polycarbonate resin. -A polycarbonate resin composition to which butadiene-styrene resin is added is disclosed. However, such polycarbonate resin compositions are not necessarily sufficient in balance of mechanical properties, molded appearance, and slidability. In some cases, further flame retardancy is required in addition to such slidability, and even in this case, the conventional technology cannot cope with the situation at present.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has as its object to improve the sliding property and appearance of a molded product without impairing the original mechanical strength and heat resistance of a polycarbonate resin. It is to provide a flame-retardant polycarbonate resin composition having excellent heat resistance.

[0007]

That is, the gist of the present invention resides in that 100 parts by weight of a polycarbonate resin (A) is
It has a structure in which 0.05 to 5 parts by weight of a silicone oil (BH) having a kinematic viscosity at 25 ° C. of 10,000 mm ² / s or more, a polyorganosiloxane rubber component and a polyalkyl (meth) acrylate rubber component are intertwined with each other. A polycarbonate resin composition comprising 0.5 to 25 parts by weight of a composite rubber (C) and 1 to 30 parts by weight of a phosphate compound (D).

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The polycarbonate resin (A) (hereinafter referred to as “P
It may be referred to as "C resin". ) Is aromatic PC
Examples thereof include a resin, an aliphatic PC resin, and an aromatic-aliphatic PC resin. Among them, an aromatic PC resin is preferable. As the aromatic PC resin, obtained by reacting an aromatic hydroxy compound or a small amount thereof with a phosgene or a carbonic acid diester,
Examples thereof include a thermoplastic aromatic polycarbonate polymer or copolymer which may be branched. The method for producing the PC resin is not particularly limited, and a phosgene method (interfacial polymerization method), a melting method (ester exchange method), or the like is employed. In the present invention, an aromatic PC resin produced by a melting method and having an adjusted amount of terminal OH groups can also be used.

The aromatic dihydroxy compound includes:
2,2-bis (4-hydroxyphenyl) propane (=
Bisphenol A), tetramethylbisphenol A,
Bis (4-hydroxyphenyl) -P-diisopropylbenzene, hydroquinone, resorcinol, 4,4-
Examples thereof include dihydroxydiphenyl, and among them, bisphenol A is preferable. In order to further enhance the flame retardancy, a compound in which at least one tetraalkylphosphonium sulfonate is bonded to the aromatic dihydroxy compound and / or a polymer or oligomer having a phenolic OH group at both ends and having a siloxane structure is used. You can do it.

In order to obtain a branched aromatic PC resin, phloroglucin, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-2,4 , 6-dimethyl-2,
4,6-tri (4-hydroxyphenyl) heptane,
2,6-dimethyl-2,4,6-tri (4-hydroxyphenylheptene-3,1,3,5-tri (4-hydroxyphenyl) benzene, 1,1,1-tri (4-hydroxyphenyl ) In addition to polyhydroxy compounds such as ethane, 3,3-bis (4-hydroxyaryl) oxindole (= isatin bisphenol), 5-chlorisatin, 5,7-dichlorisatin, 5-bromoisatin and the like may be used. These amounts are usually 0.0
It is 1 to 10 mol%, preferably 0.1 to 2 mol%.

In order to adjust the molecular weight, a monovalent aromatic hydroxy compound may be used.
And p-methylphenol, m- and p-propylphenol, p-tert-butylphenol and p-long-chain alkyl-substituted phenol.

As the aromatic PC resin, preferably,
Examples include a PC resin derived from 2,2-bis (4-hydroxyphenyl) propane and a PC copolymer derived from 2,2-bis (4-hydroxyphenyl) propane and another aromatic dihydroxy compound. For the purpose of further increasing the flame retardancy, a polymer or oligomer having a siloxane structure can be copolymerized. As the aromatic PC resin, a mixture of two or more resins may be used.

The viscosity average molecular weight of the PC resin is usually from 16,000 to 3 as a value converted from the solution viscosity measured at a temperature of 25 ° C. using methylene chloride as a solvent.
000. When the viscosity average molecular weight is less than 16,000, the mechanical strength is insufficient, and when the viscosity average molecular weight is more than 30,000, the appearance of the molded article tends to be poor. The viscosity average molecular weight of the PC resin is preferably from 17,000 to 25,000.
0, more preferably 18,000 to 23,000.

The silicone oil (B) used in the present invention
H) requires that the kinematic viscosity at 25 ° C. be 10,000 mm ² / s or more. Silicone oil (BH)
If the kinematic viscosity at 25 ° C. is less than 10,000 mm ² / s, it is difficult to maintain the slidability for a long period of time. The kinematic viscosity of the silicone oil (BH) at 25 ° C. is preferably 100,000 mm ² / s or more, more preferably 50,000 mm ² / s.
More than 000 mm ² / s, particularly preferably
It is not less than 000 mm ² / s.

In the present invention, the silicone oil (B
The content of H) is 0.05 to 5 parts by weight based on 100 parts by weight of the PC resin (A). If the content of silicone oil is less than 0.05 parts by weight, the slidability is insufficient,
If the amount exceeds 5 parts by weight, the appearance of the molded product is reduced. The content of the silicone oil is preferably 0.1 to 4 parts by weight, more preferably 0.2 to 3 parts by weight, based on 100 parts by weight of the PC resin (A).

In the present invention, the silicone oil (B
When the kinematic viscosity at 25 ° C of H) is 100,000 mm ² / s or more, the kinematic viscosity at 25 ° C is 100,000 mm / s.
If the silicone oil (BL) of less than 0 mm ² / s is used in combination and the ratio of the silicone oil (BH) to the silicone oil (BL) is 2/1 to 200/1 by weight, the specific wear amount Is preferred because it can reduce.

In the above case, the kinematic viscosity of the silicone oil (BH) at 25 ° C. is preferably 500,000 mm ²
/ S or more, more preferably 1,000,000 mm ² /
s or more. Also, 25 of silicone oil (BL)
Kinematic viscosity at ℃ is preferably 50,000 mm ² / s, more preferably not more than 10,000 mm ² / s. The ratio between the silicone oil (BH) and the silicone oil (BL) is preferably 5/1 to 1 by weight.
It is 50/1, more preferably 10/1 to 100/1. When the amount of the silicone oil (BH) is too large, the specific abrasion tends to decrease, and further, the appearance of the molded article tends to be adversely affected. On the other hand, silicone oil (B
If L) is too large, the specific wear properties tend to be low, and the molded product may be sticky.

The silicone oil in the present invention is not particularly limited as long as it satisfies the above kinematic viscosity conditions, and can be arbitrarily selected from known silicone oils. For example, a silicone oil composed of polydimethylsiloxane, a silicone oil in which some or all of the methyl groups of polydimethylsiloxane are substituted with a phenyl group, hydrogen, an alkyl group having 2 or more carbon atoms, a halogenated phenyl group or a fluoroester group And epoxy-modified silicone oil having an epoxy group, amino-modified silicone oil having an amino group, alcohol-modified silicone oil having an alcoholic hydroxyl group, and polyether-modified silicone oil having a polyether structure. These can be used alone or in combination of two or more. As described above, when a silicone oil (BH) having a high kinematic viscosity and a silicone oil (BL) having a low kinematic viscosity are used in combination, a preferable silicone oil (BL) is a silicone oil having a phenyl group.

In the present invention, a composite rubber (C) having a structure in which a polyorganosiloxane rubber component and a polyalkyl (meth) acrylate rubber component are entangled with each other is used. Examples of the main skeleton of the polyorganosiloxane rubber component in the composite rubber (C) include a polymer having a repeating unit selected from dimethylsiloxane, diphenylsiloxane, and methylphenylsiloxane. On the other hand, the main skeleton of the polyalkyl (meth) acrylate rubber component includes methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, and 2-ethylhexyl (meth). A polymer having a repeating unit selected from acrylates is exemplified.

The method for producing the composite rubber (C) in the present invention is preferably an emulsion polymerization method. That is, first, a latex of polyorganosiloxane rubber is prepared,
It is preferable to impregnate the particles of the polyorganosiloxane rubber latex with a monomer for synthesizing an alkyl (meth) acrylate rubber and then polymerize the monomer.

The weight ratio of the polyorganosiloxane rubber component to the polyalkyl (meth) acrylate rubber component is usually 90/10 to 20/80, preferably 85/1.
5/30/70, more preferably 80 / 20-40 / 6
0. If the amount of the polyalkyl (meth) acrylate rubber component is too small, the affinity with the PC resin is low, and the appearance of the molded product is lowered. If the amount is too large, the effect of improving the slidability is not sufficient.

The composite rubber (C) can be graft-polymerized with a vinyl monomer. As a vinyl monomer,
Various vinyl monomers such as aromatic alkenyl compounds such as styrene, (meth) acrylates such as methyl methacrylate, and vinyl cyanide compounds such as acrylonitrile, which may be used alone or in combination of two or more. Can be done. The composite rubber (C) is sold, for example, by Mitsubishi Rayon Co., Ltd. under the trade name of “METABLEN” and can be easily obtained.

The content of the composite rubber (C) is 0.5 to 25 parts by weight based on 100 parts by weight of the PC resin (A). If the amount of the composite rubber (C) is too small, the effect of improving the slidability is insufficient, and if the amount is too large, the mechanical strength decreases. The content of the composite rubber (C) is 100% of the PC resin (A).
The amount is preferably 0.8 to 20 parts by weight, more preferably 1 to 15 parts by weight based on parts by weight.

The ratio between the silicone oil (BH) and the composite rubber (C) is usually 5/1 to 1/50, preferably 2/1 to 1/30 by weight. When the ratio between the silicone oil (BH) and the composite rubber (C) is out of the above range, the mechanical strength and the appearance of the molded product are liable to decrease. The phosphoric acid ester compound (D) used in the present invention is preferably a halogen-free phosphoric acid ester compound.

[0025]

Embedded image

(Where R ¹ , R ² , R ³ , and R ⁴ each independently represent a hydrogen atom or an organic group, X represents a divalent or higher valent organic group, and p represents 0 or 1. And q represents an integer of 1 or more, and r represents an integer of 0 or more.). In equation (1),
The organic group in the definition of R ¹ , R ² , R ³ , and R ⁴ is an alkyl group, a cycloalkyl group, an aryl group, which may or may not be substituted. Examples of the substituent when it is substituted include an alkyl group, an alkoxy group, an aryl group, an aryloxy group, and an arylthio group.
Further, those having a substituent such as an arylalkoxyalkyl group which is a group obtained by combining these substituents, or an arylsulfonylaryl group obtained by combining these substituents by bonding with an oxygen atom, a nitrogen atom, a sulfur atom or the like. and so on.

In the formula (1), the divalent or higher valent organic group X means a divalent or higher valent group formed by removing two or more hydrogen atoms bonded to carbon atoms of the organic compound. . For example, it is a group derived from an alkylene group, an arylene group (for example, a phenylene group), a cycloalkylene group, or a polynuclear phenol, for example, a bisphenol.
Preferred examples of the organic group X include groups derived from bisphenol A, hydroquinone, resorcinol, diphenylmethane, dihydroxydiphenyl, dihydroxynaphthalene, and the like. These groups may be substituted with the same substituents as the organic groups in the definitions of R ¹ , R ² , R ³ and R ⁴ described above.

The halogen-free phosphate compound is
It may be a monomer, an oligomer, a polymer, or a mixture thereof. Specific examples of such a phosphate compound (D) include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl Phosphate, tri (2-ethylhexyl) phosphate, diisopropylphenyl phosphate, trixylenyl phosphate, tris (isopropylphenyl) phosphate, trinaphthyl phosphate, bisphenol A bisphosphate, hydroquinone bisphosphate, resorcinol bisphosphate, resorcinol-diphenyl phosphate, trioxy Benzene triphosphate, cresyl diphenyl phosphate Over DOO, or substituted versions thereof, and condensates may be exemplified.

In the present invention, examples of the halogen-free phosphoric acid ester compound which can be suitably used as the component (D) include, for example, "T
PP "(triphenyl phosphate)," CR733
S ”(resorcinol bis (diphenyl phosphate)),“ CR741 ”(bisphenol A bis (diphenyl phosphate)),“ FP ”from Asahi Denka Kogyo KK
500 "(resorcinol bis (dixylenyl phosphate)) and is readily available.

In the polycarbonate resin composition of the present invention, the content of the phosphate compound (D) is 1 to 30 parts by weight based on 100 parts by weight of the PC resin (A).
When the amount of the phosphate ester compound (D) is too small, the effect of improving the flame retardancy is insufficient, and when the amount is too large, the decrease in heat resistance is extremely undesirable. Phosphate ester compound (D)
Is preferably 3 to 20 parts by weight, more preferably 5 to 15 parts by weight, based on 100 parts by weight of the PC resin (A).

In the present invention, for the purpose of preventing dripping during combustion, it is preferable to include a fluororesin (E). Here, the fluororesin is a polymer or copolymer having 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 10,000,000.
It is. 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 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. As a specific example, for example, Teflon 6-J (trade name, Mitsui
DuPont Fluorochemical Co., Ltd.), Polyflon D-
1, commercial products such as Polyflon F-103, Polyflon F201 (trade name, manufactured by Daikin Industries, Ltd.), and CD076 (trade name, manufactured by Asahi ICI Fluoropolymers Co., Ltd.).

Other than those classified into the above-mentioned type 3, for example, Algoflon F5 (trade name, manufactured by Montefluos Co., Ltd.), polyflon MPA, polyflon FA-1
00 (trade name, manufactured by Daikin Industries, Ltd.) and the like. These polytetrafluoroethylene (PTF
E) 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 adding tetrafluoroethylene in an aqueous solvent in the presence of sodium, potassium, and ammonium peroxydisulfide.
It is obtained by polymerizing at a temperature of 0 to 200 ° C., preferably 20 to 100 ° C. under a pressure of 1 to 100 psi. The content of these fluororesins is PC resin (A) 1
The amount is 0.05 to 5 parts by weight, preferably 0.1 to 2 parts by weight based on 00 parts by weight. Here, if the amount is less than 0.05 part by weight, the anti-dripping property is insufficient, and if it exceeds 5 parts by weight, the impact resistance and the appearance of the molded product are adversely affected.

The PC resin composition of the present invention may contain, if necessary, stabilizers such as an ultraviolet absorber and an antioxidant, additives such as pigments, dyes, lubricants and mold release agents, glass fibers, glass flakes, carbon Reinforcing materials such as fibers and whiskers such as potassium titanate and aluminum borate can be added.

Further, the PC resin composition of the present invention contains a P resin for the purpose of improving performance such as moldability and chemical resistance.
A thermoplastic resin other than the C resin can be blended. The type and the amount of the thermoplastic resin can be appropriately selected. Examples of the thermoplastic resin other than the PC resin include polyester resin, polyamide resin, polyolefin resin, polyphenylene ether resin, styrene resin, polysulfone, polyether sulfone, polyphenylene sulfide, polyarylate, polyamide imide, polyether imide, and the like. .

Examples of the polyester resin include polybutylene terephthalate, polyethylene terephthalate, polybutylene naphthalate, and polyethylene naphthalate. Examples of the polyolefin resin include polyethylene and polypropylene. As polyphenylene ether-based resin, polyphenylene ether resin,
Polyphenylene ether and polystyrene and / or HI
A resin mixed with PS and the like are included. As the styrene resin, polystyrene, HIPS (impact polystyrene) resin, AS (acrylonitrile-styrene) resin, A
BS (acrylonitrile-butadiene-styrene) resin and the like.

The amount of the thermoplastic resin other than the PC resin is as follows:
Normally, 5 to the total amount of PC resin and resin other than PC resin
It is less than 0% by weight, preferably 40% by weight or less, more preferably 30% by weight or less, and the lower limit is usually 1% by weight.

The method for producing the PC resin composition of the present invention includes mixing and kneading the above components with various kneaders, for example, a uniaxial or multiaxial kneader, a Banbury mixer, a roll, a Brabender plastogram or the like. After that, the mixture is cooled and solidified by a melt-kneading method, a suitable solvent, for example, hexane, heptane, benzene, toluene, xylene and other hydrocarbons and their derivatives are added to the above components, and the components to be dissolved or insoluble with the components to be dissolved A solution mixing method in which the components are mixed in a suspension state may be mentioned. The melt kneading method is preferred from the viewpoint of cost.

The method of molding the PC resin composition of the present invention is not particularly limited, and molding methods generally used for thermoplastic resin compositions, for example, injection molding, hollow molding, extrusion molding, sheet molding, heat molding, and the like. Various molding methods such as molding, rotational molding, and lamination molding can be adopted.

[0040]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist. In the examples and comparative examples, the raw materials described below were used, and the evaluation method described later was employed.

<Raw Materials> (1) PC resin: poly-4,4-isopropylidene diphenyl carbonate (viscosity average molecular weight: 21,000,
(Trade name: Iupilon (registered trademark) S-3000) manufactured by Mitsubishi Engineering-Plastics Corporation) (2) Silicone oil (B1): polydimethylsiloxane (kinematic viscosity at 25 ° C .: 6,000,000 mm ² /
(3) Silicone oil (B2): polydimethylsiloxane (kinematic viscosity at 25 ° C .: 500 mm ² / s, manufactured by Shin-Etsu Silicone Co., Ltd. “Product name: VRS-01”) KF-96 ") (4) Silicone oil (B3): Master batch containing 40% by weight of polydimethylsiloxane in PC resin (Kinematic viscosity of polydimethylsiloxane at 25 ° C .:
100,000 mm ² / s or more, manufactured by Dow Corning Toray Silicone Co., Ltd. “Product name: BX27-015”

(5) Silicone oil (B4): phenyl-modified polydimethylsiloxane (kinematic viscosity at 25 ° C .: 4)
00 mm ² / s, manufactured by Shin-Etsu Silicone Co., Ltd. “Product name: KF-
54 ") (6) Silicone oil (B5): 50 in ABS resin
Master batch containing polydimethylsiloxane by weight (polydimethylsiloxane kinematic viscosity at 25 ° C .: 100,000 mm ² / s or more, manufactured by Dow Corning Toray Silicone, “product name: BY27-007”) (7) ) Polyorganosiloxane-poly-alkyl (meth) acrylate composite rubber: polydimethylsiloxane-
Poly-n-butyl acrylate composite rubber (polydimethylsiloxane rubber component content: 70% by weight, "trade name: Metablen SX005" manufactured by Mitsubishi Rayon Co., Ltd.) (8) Phosphate compound: resorcinol bis (dixylenyl phosphate) (Product name: FP500, manufactured by Asahi Denka Kogyo Co., Ltd.) (9) Fluororesin polytetrafluoroethylene (Daikin Chemical Industries, Ltd.)
"Product name: F201L", molecular weight 4,000,000 to 500
Ten thousand)

<Evaluation Method> (1) Izod Impact Test: A notched Izod impact test was performed in accordance with ASTM D256. (2) Flexural modulus: A three-point bending test was performed according to a bending test method according to ASTM D790. (3) Heat deformation temperature: 1.8 according to ASTM D648
A load deflection test was performed under the conditions of 2 MPa. (4) Flexural fatigue failure: Ty according to ASTM D671
Using a peA test piece, a test was performed at 23 ° C. and an actual stress of 19 MPa, and the number of times of destruction was evaluated. (5) Slidability: According to JIS K7218 A method, a ring made of S45C was used as a mating material, under the conditions of a load of 5 kg (surface pressure of 2.5 kg / cm ² ), a peripheral speed of 10 cm / sec, and a running time of 10 hours. A sliding test was performed, and a specific wear amount was calculated from the wear amount by the following equation.

[0044]

## EQU1 ## Specific wear (mm ³ / kg · km) = wear (g) /
Density (g / mm ³ ), load (kg), mileage (km)

(6) Appearance of molded article: The appearance of the test piece used for the repeated bending fatigue test was visually observed, and the results were evaluated as follows: ○: good, Δ: slight defect observed, ×: defective And (7) Flammability In accordance with the UL94 vertical combustion test, evaluation was performed with a test piece thickness of 1.6 mm. In this case, NG means that it did not become V-2.

Examples 1 to 4 Using a PC resin and a silicone oil shown in Table 1 below, and uniformly mixing them with a mixer so that the weight ratio becomes 90/10, a twin screw extruder (Nippon Steel Corporation) was used. 280 ° C, screw rotation speed 250
Pelletization was performed at rpm to obtain a master pellet. The obtained master pellet, the PC resin, the composite rubber, the phosphate compound, and the fluororesin are uniformly mixed with a mixer so as to have a ratio shown in Table 1 below, and then a twin-screw extruder (manufactured by Nippon Steel Works) And pelletized at a cylinder temperature of 280 ° C. and a screw rotation speed of 250 rpm. The obtained resin pellets were injection-molded to form molded articles, and various evaluations were made. The injection molding machine used was an injection molding machine manufactured by Japan Steel Works, and had a mold clamping force of 50 T and a cylinder temperature of 2.
The conditions of 80 ° C. and mold temperature: 80 ° C. were adopted. Table 1 shows the evaluation results.

Examples 5 and 6 Pellets were prepared in the same manner as in Example 1 except that the silicone oil (B1) was replaced by silicone oil (B3) which is a master batch product of PC resin. Then, molding and various evaluations were performed in the same manner as in Example 1. Table 2 shows the evaluation results. In addition, the compounding amount of the silicone oil (B3) shown in Table 2 is an amount calculated by dividing the silicone oil (B3) into the silicone oil and the PC resin since the silicone oil (B3) is a master batch product.

Examples 7 and 8 In Example 1, the silicone oil (B4) having a low viscosity was used together with the silicone oil (B1) in the proportions shown in Table 2.
A master pellet was obtained and pelletized in the same manner as in Example 1 except that the above was used in combination. Using the obtained pellets, molding and various evaluations were performed in the same manner as in Example 1. Table 2 shows the evaluation results.

COMPARATIVE EXAMPLES 1-2 PC resin and composite rubber were uniformly mixed by a mixer so as to have the ratio shown in Table 3, and then the cylinder temperature was 280 using a twin screw extruder (manufactured by Nippon Steel Works). C., and pelletized at a screw rotation speed of 250 rpm. Using the obtained pellets, molding and various evaluations were performed in the same manner as in Example 1. Table 3 shows the evaluation results.

Comparative Example 3 A master pellet was obtained and pelletized in the same manner as in Example 3 except that no composite rubber was used. Using the obtained pellets, molding and various evaluations were performed in the same manner as in Example 1. Table 3 shows the evaluation results.

Comparative Example 4 A master pellet was obtained in the same manner as in Comparative Example 3, except that the amount of silicone oil was increased.
It was pelletized in the same manner. Using the obtained pellets, molding and various evaluations were performed in the same manner as in Example 1. Table 3 shows the evaluation results.

Comparative Example 5 A master pellet was obtained and pelletized in the same manner as in Example 1 except that the silicone oil (B2) was used instead of the silicone oil (B1). Using the obtained pellets, molding and various evaluations were performed in the same manner as in Example 1. Table 4 shows the evaluation results.

Comparative Example 6 Pelletization was carried out in the same manner as in Example 1 except that the silicone oil (B1) was replaced by an ABS resin master batch product (B5). Using the obtained pellets, molding and various evaluations were performed in the same manner as in Example 1. Table 4 shows the evaluation results. The blending amount of the silicone oil (B5) shown in Table 6 is an amount calculated by dividing the silicone oil (B5) into the silicone oil and the PC resin since the silicone oil (B5) is a master batch product. Comparative Examples 7 and 8 The phosphate ester compounds in Examples 1 and 2, respectively,
A master pellet was obtained and pelletized in the same manner as in Example 1 except that the fluororesin was not added.
Using the obtained pellets, molding and various evaluations were performed in the same manner as in Example 1. Table 4 shows the evaluation results.

[0054]

[Table 1]

[0055]

[Table 2]

[0056]

[Table 3]

[0057]

[Table 4]

[0058]

The PC resin composition of the present invention is a flame-retardant material having excellent Izod impact strength, flexural modulus, flexural fatigue fracture, heat resistance, slidability and appearance of a molded product. It is useful for various sliding applications, and its industrial value is large, and it can be widely used in the fields of electric and electronic devices, OA equipment components, and the like.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 27:12) C08L 27:12) (72) Inventor Naoto Obayashi 5-6-1 Higashi-Hachiman, Hiratsuka-shi, Kanagawa Prefecture No. Mitsubishi Engineering Plastics Co., Ltd. Technology Center (72) Inventor Takashi Miyajima 5-6-2 Higashi-Hachiman, Hiratsuka-shi, Kanagawa Prefecture Mitsubishi Engineering Plastics Co., Ltd. Technology Center F-term (reference) 4J002 BD124 BD154 BG043 BG053 CG001 CP032 EW046 GM05

Claims (14)

[Claims] 1. A kinematic viscosity at 25 ° C. of 10,000 mm ² / s with respect to 100 parts by weight of a polycarbonate resin (A).
0.5 to 25 parts by weight of a composite rubber (C) having a structure in which the above silicone oil (BH) is 0.05 to 5 parts by weight, a polyorganosiloxane rubber component and a polyalkyl (meth) acrylate rubber component are intertwined with each other; And 1 to 30 parts by weight of a phosphoric ester compound (D). 2. A fluoroolefin resin (E) 0.05.
The polycarbonate resin composition according to claim 1, wherein the composition comprises from 5 to 5 parts by weight. 3. The polycarbonate resin composition according to claim 1, wherein the kinematic viscosity of the silicone oil (BH) at 25 ° C. is 100,000 mm ² / s or more. 4. The polycarbonate resin composition according to claim 1, wherein the kinematic viscosity at 25 ° C. of the silicone oil (BH) is 500,000 mm ² / s or more. 5. The polycarbonate resin composition according to claim 1, wherein the kinematic viscosity at 25 ° C. of the silicone oil (BH) is 1,000,000 mm ² / s or more. 6. The polycarbonate resin composition according to claim 1, wherein the viscosity average molecular weight of the polycarbonate resin (A) is 16,000 to 30,000. 7. The composite rubber (C) according to claim 1, wherein the weight ratio of the polyorganosiloxane rubber component to the polyalkyl (meth) acrylate rubber component is 90/10 to 20/80. The polycarbonate resin composition according to the above. 8. The polycarbonate resin composition according to claim 1, wherein the weight ratio of the silicone oil (BH) and the composite rubber (C) is 5/1 to 1/50. 9. 25 ° C. with silicone oil (BH)
The silicone oil (BL) having a kinematic viscosity of less than 100,000 mm ² / s is used in combination, and the ratio of the silicone oil (BH) to the silicone oil (BL) is 2/1 to 200/1 by weight. 2. The method according to claim 1, wherein
9. The polycarbonate resin composition according to any one of items 1 to 8. 10. The polycarbonate resin composition according to claim 9, wherein the kinematic viscosity at 25 ° C. of the silicone oil (BL) is 50,000 mm ² / s or less. 11. The polycarbonate resin composition according to claim 9, wherein the kinematic viscosity of the silicone oil (BL) at 25 ° C. is 10,000 mm ² / s or less. 12. The polycarbonate resin composition according to claim 9, wherein the silicone oil (BL) is a silicone oil having a phenyl group. 13. The polycarbonate resin composition according to claim 9, wherein the weight ratio of the silicone oil (BH) to the silicone oil (BL) is 5/1 to 150/1. object. 14. The weight ratio of silicone oil (BH) to silicone oil (BL) is 10/1 to 100/1.
The polycarbonate resin composition according to any one of claims 9 to 13, wherein