JPH093313A - Sliding resin composition and molded product formed from the same - Google Patents

Abstract

(57) [Abstract] [Purpose] A slidable resin composition containing an aromatic polycarbonate which has excellent abrasion resistance and abrasion properties and is excellent in molding processability and impact resistance of a thin portion, and formed from the same. To provide molded products. [Structure] Aromatic polycarbonate resin (a component), polytetrafluoroethylene resin (b component), and thermoplastic graft copolymer (c component) obtained by grafting a vinyl cyanide compound and an aromatic vinyl compound on a diene rubber component. The ratio of the a component, the b component, and the c component is 40 to 40% when the total of them is 100% by weight.
94% by weight, b component 3 to 30% by weight, and c component 3
A slidable resin composition having a content of ˜57% by weight and a molded article formed therefrom.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a slidable resin composition and a molded product formed from the same, and more specifically, it has excellent friction resistance and wear resistance, and also has a thin portion for molding processability and impact resistance. The present invention relates to a slidable resin composition containing an excellent aromatic polycarbonate and a molded article formed therefrom.

[0002]

2. Description of the Related Art Aromatic polycarbonate resins are excellent in mechanical strength and electrical properties, and are used as engineering plastics in various fields such as electric fields, electronic equipment fields and automobile fields. Widely used in

Recently, there have been increasing cases of using materials having excellent sliding characteristics for sliding parts of OA equipment. Conventionally, there were cases where grease, oil, etc. were applied to improve sliding characteristics, but when grease and oil are applied and used in recent precision machines, the fine particles of grease and oil may adversely affect internal parts. Therefore, a resin having improved sliding characteristics has been demanded. Conventionally, a method of adding polytetrafluoroethylene to improve the sliding characteristics of an aromatic polycarbonate resin, a method of adding silicone oil (Japanese Patent Publication No. 36-7641), and a combination of polytetrafluoroethylene and polyolefin (Japanese Patent Laid-open No. Sho-76-7641) 48-4084
9) etc. have been proposed and used. But recent OA
Sliding aromatic polycarbonate resins having excellent molding processability and impact resistance of thin-walled parts have been demanded for light, thin, short and small devices, but conventional techniques have not been sufficient.

[0004]

SUMMARY OF THE INVENTION When polytetrafluoroethylene is added to an aromatic polycarbonate resin for the purpose of improving slidability, molding processability or impact properties are deteriorated, and improvements have been demanded. . In particular, in the case of injection molding a thin product, high pressure and high speed molding are required, and a material having poor moldability has a problem in dimensional accuracy (particularly warpage) of the molded product, and improvement has been required.

The object of the present invention is to provide a slidable resin composition containing an aromatic polycarbonate which has excellent friction resistance and wear characteristics, and is excellent in molding processability and impact resistance of a thin portion, and to be formed from the same. To provide molded products.

[0006]

Means for Solving the Problems As a result of earnest studies to achieve the above object, the present inventor has added a thermoplastic graft copolymer to a resin composition obtained by adding polytetrafluoroethylene to an aromatic polycarbonate resin. It has been found that a resin composition having excellent moldability of the thin-walled part, resulting in excellent dimensional accuracy, and excellent impact strength and slidability can be obtained. That is, according to the present invention, a thermoplastic graft copolymer obtained by grafting a vinyl cyanide compound and an aromatic vinyl compound onto an aromatic polycarbonate resin (a component), a polytetrafluoroethylene resin (b component), and a diene rubber component. (Component c), the ratio of component a, component b, and component c is 40 to 94% by weight, component b is 3 to 30% by weight, and component c is 100% by weight. Provided is a slidable resin composition containing 3 to 57% by weight of a component, and a molded article formed therefrom.

The a-component aromatic polycarbonate resin used in the present invention is usually produced by reacting a dihydric phenol with a carbonate precursor by a solution method or a melting method. The basic means of these manufacturing methods will be briefly described.

In the reaction using phosgene as the carbonate precursor, the reaction is usually carried out in the presence of an acid binder and a solvent. As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine is used. As the solvent, for example, a halogenated hydrocarbon such as methylene chloride or chlorobenzene is used. A catalyst such as a tertiary amine or a quaternary ammonium salt may be used to accelerate the reaction. At that time, the reaction temperature is usually 0 to 40 ° C., and the reaction time is several minutes to 5 hours.

The transesterification reaction using a carbonic acid diester as a carbonate precursor is a method in which an aromatic dihydroxy component in a predetermined ratio is stirred with a carbonic acid diester while heating in an inert gas atmosphere to distill the produced alcohol or phenol. Done by. The reaction temperature varies depending on the boiling point of the produced alcohol or phenol, and is usually in the range of 120 to 300 ° C. From the initial stage of the reaction, the reaction is completed while reducing the pressure to distill off the produced alcohol or phenols. Further, a catalyst usually used in transesterification reaction may be used to accelerate the reaction. Examples of the carbonic acid diester used in the transesterification reaction include diphenyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate and dibutyl carbonate. Of these, diphenyl carbonate is particularly preferred.

Typical examples of the above dihydric phenol include 2,2-bis (4-hydroxyphenyl) propane [bisphenol A], bis (4-hydroxyphenyl) methane, and 1,1 bis (4hydroxyphenyl). ) Ethane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2- (4-hydroxy-3-)
Methylphenyl) propane, bis (4-hydroxyphenyl) sulfone and the like. A preferred dihydric phenol is a bis (4-hydroxyphenyl) alkane, particularly bisphenol A as a main raw material. Examples of the carbonate precursor include carbonyl halide, carbonyl ester, haloformate, and the like, and specific examples thereof include phosgene, diphenyl carbonate, dihaloformate of dihydric phenol, and a mixture thereof. In producing the polycarbonate resin, the dihydric phenol may be used alone or in combination of two or more kinds. In addition, suitable molecular weight regulators, branching agents, catalysts for accelerating the reaction, and the like can be used. Two or more kinds of the aromatic polycarbonate resins thus obtained may be mixed.

The component b polytetrafluoroethylene resin used in the present invention is usually used as a dry lubricant. Preferably, it is in the form of fine powder, and the particle size of the fine powder is 0.1 to 100 μm on average by a method of measuring a dispersion liquid dispersed in perchlorethylene by a light transmission method.
m. The melting point of the polytetrafluoroethylene fine powder is preferably 320 ° C. or higher as measured by the DSC method. Since the fine powder of polytetrafluoroethylene is easily re-aggregated, there are some that have been subjected to a treatment such as a firing treatment in order to make it difficult to re-aggregate, and these can also be preferably used. These are Lubron L-5 and L-2 from Daikin Industries, Ltd.
In addition, L15 from Asahi Aishi-i Fluoropolymers Co., Ltd.
0J, L169J, L170J, L172J, and Teflon T from Mitsui DuPont Fluorochemicals Co., Ltd.
It is commercially available as LP-10F-1 and is easily available.

As the thermoplastic graft copolymer used as the component c in the present invention, a resin usually called ABS resin can be used. As the diene rubber component forming the thermoplastic graft copolymer, for example, a rubber having a glass transition point of 10 ° C. or less, such as polybutadiene, polyisoprene, and styrene-butadiene copolymer, is used, and the ratio thereof is in the component c. It is preferably from 5 to 80% by weight. Examples of the vinyl cyanide compound grafted to the diene rubber component include acrylonitrile and methacrylonitrile, and the content ratio of the vinyl cyanide compound in the component c is preferably 50 to 5% by weight. Examples of the aromatic vinyl compound grafted to the diene rubber component include acrylonitrile and methacrylonitrile. The content ratio of the vinyl cyanide compound in the component c is preferably 50 to 5% by weight. Examples of the aromatic vinyl compound grafted to the diene rubber component include styrene, α-methylstyrene and nucleus-substituted styrene. The content of the aromatic vinyl compound is 50 to 95% by weight in the component c. Is preferred. Furthermore, methyl (meth) acrylate, ethyl acrylate, maleic anhydride, N-substituted maleimide and the like can be mixed and used. The thermoplastic graft copolymer (component (c)) may be produced by any of bulk polymerization, suspension polymerization or emulsion polymerization, and the copolymerization may be carried out in a single step or in a multi-step manner. May be copolymerized with. Further, the component b can be used not only in one kind but also in a mixture of two or more kinds.

The blending ratio of the components a to c is 40 to 94% by weight of the component a when the total amount thereof is 100% by weight,
It is in the range of b component 3 to 30% by weight and c component 3 to 57% by weight. When the content of the component a is less than 40% by weight, heat resistance (particularly the deflection temperature under load) is lowered, which is not preferable. 94% by weight
If it exceeds, the fluidity is lowered and the moldability is lowered.
If the amount of component b is less than 3% by weight, sufficient friction resistance and wear properties cannot be obtained, and if it exceeds 30% by weight, the mechanical strength (impact resistance) is remarkably reduced. Further, if the c component is less than 3% by weight, sufficient moldability cannot be obtained, and if it exceeds 57% by weight, heat resistance (deflection temperature under load) and mechanical strength (impact resistance).
Is reduced.

Examples of the scale-like inorganic filler of the component d used in the present invention include talc and mica. The inorganic filler of the component d is required to be scaly in order to achieve the object of the present invention, and other fillers such as glass fiber do not achieve the object. The average particle size of the inorganic filler as the component d is preferably about 1.2 to 3.5 μm.

The mixing ratio is 3 to 50 parts by weight with respect to 100 parts by weight of the slidable resin composition according to claim 1. If it is less than 3 parts by weight, the rigidity is insufficient, and if it exceeds 50 parts by weight, mechanical strength (particularly impact resistance) is lowered. If a fibrous inorganic filler such as glass fiber or carbon fiber is used in addition to the scale-like inorganic filler, rigidity is obtained, but the appearance is deteriorated and the molded product is warped, which is not preferable.

The elastic copolymer of the component e used in the present invention is selected from the group consisting of methacrylic acid ester, acrylic acid ester and aromatic vinyl compound in the presence of a rubber containing a repeating unit derived from butadiene. It is obtained by copolymerizing two or more kinds of monomers.
Examples of the rubber containing a repeating unit derived from butadiene include polybutadiene, a butadiene-styrene copolymer, a butadiene-acrylonitrile copolymer, and a butadiene-acrylic acid ester copolymer. Examples of the methacrylic acid ester include methyl methacrylate, ethyl methacrylate, butyl methacrylate, and octyl methacrylate. Examples of the acrylate ester include methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate and the like. Further, examples of the aromatic vinyl compound include styrene, α-methylstyrene, p-methylstyrene, alkoxystyrene, halogenated styrene and the like.

The above-mentioned elastic copolymer is a bulk polymerization, a solution polymerization,
It may be produced by either suspension polymerization or emulsion polymerization, and the copolymerization method may be either one-stage grafting or multi-stage grafting. Further, it may be a mixture with a copolymer containing only a graft component produced as a by-product during the production. Such elastic copolymers are commercially available and can be easily obtained. For example, Kaneace Chemical Co., Ltd.'s Kane Ace B series, Mitsubishi Rayon Co., Ltd.'s Metabrene C series, Kureha Chemical Co., Ltd.'s EXL series, HIA series, BTA series, KCA series, etc. are mentioned.

The f component used in the present invention is one or two kinds of the composite rubber having a structure in which the polyorganosiloxane rubber component and the polyalkyl (meth) acrylate rubber component are intertwined with each other so that they cannot be separated. It is a composite rubber-based graft copolymer obtained by graft-polymerizing the above vinyl-based monomers. To obtain the composite rubber-based graft copolymer used in the present invention, first, various cyclic organosiloxanes having three or more membered rings, such as hexamethylcyclotrisiloxane and octamethylcyclotetrasiloxane,
Decamethylcyclopentasiloxane, etc., and a cross-linking agent and / or
Alternatively, a latex of polyorganosiloxane rubber is prepared by emulsion polymerization using a graft crossing agent, and then the latex of polyorganosiloxane rubber is impregnated with an alkyl (meth) acrylate monomer, a crosslinking agent and a graft crossing agent. Obtained by polymerizing. As the alkyl (meth) acrylate monomer used here,
Examples thereof include alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate, and alkyl methacrylates such as hexyl methacrylate and 2-ethylhexyl methacrylate, but it is particularly preferable to use n-butyl acrylate. preferable.

Examples of the vinyl-based monomer to be graft-polymerized on the composite rubber include aromatic vinyl compounds such as styrene and α-methylstyrene, vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, methyl methacrylate and 2-ethylhexyl methacrylate. Examples thereof include methacrylic acid esters such as, and acrylic acid esters such as methyl acrylate, ethyl acrylate, and butyl acrylate. These may be used alone or in combination of two or more. Among them, particularly preferable ones are METBRENE S-2001 or R from Mitsubishi Rayon Co., Ltd.
Examples thereof include those marketed under the trade names of K-120 and RK-200.

The mixing ratio is 1 to 20 parts by weight of the e component and / or 1 to 20 parts by weight of the f component with respect to 100 parts by weight of the slidable resin composition according to the first aspect. In addition, the total amount of the e component and the f component does not exceed 20 parts by weight. If the amount of the e component and / or the f component is less than 1 part by weight, the impact improvement is insufficient, and if the total amount of the e component and the f component exceeds 20 parts by weight, the heat resistance and the rigidity are deteriorated.

The g-component flame retardant used in the present invention may be a halogen-based or phosphorus-based flame retardant that can be used in an aromatic polycarbonate resin or an ABS resin. For example, halogen-based flame retardants include aromatic halogen compounds, halogenated epoxy resins, halogenated polycarbonate resins, halogenated aromatic vinyl polymers, halogenated cyanurate resins, halogenated polyphenyl ethers, halogenated polyphenyl thioethers, etc. And preferably decabromodiphenyl oxide, brominated bisphenol epoxy resin, brominated bisphenol phenoxy resin, brominated bisphenol polycarbonate resin, brominated polystyrene resin, brominated crosslinked polystyrene resin, brominated bisphenol cyanurate resin, brom Polyphenylene oxide, polydibromophenylene oxide, decabromodiphenyl oxide bisphenol condensate (tetrabromobisphenol A, Oligomer, or the like). As the phosphorus-based flame retardant, non-halogen phosphate such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxycotyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, etc. Ester, tris (chloroethyl) phosphate, tris (dichloropropyl) phosphate, bis (2,3dibromopropyl) 2,3-dichloropropylphosphate, tris (2,3-dibromopropyl) phosphate, bis (chloropropyl) monooctylphosphate And halogen-containing phosphoric acid ester.

The blending ratio of the g component in the present invention is 100 parts by weight of the slidable resin composition according to claim 1, or claim 2
100 parts by weight of the high-rigidity sliding resin composition described in claim 3, or 100 parts by weight of the high-impact sliding resin composition described in claim 3, or 100 parts of the high-rigidity high-impact sliding resin composition in claim 4.
It is 1 to 30 parts by weight with respect to parts by weight. If the g component is less than 1 part by weight, the flame retardant effect is insufficient, and if it exceeds 30 parts by weight, the thermal stability during molding is lowered.

In the present invention, a flame retardant aid having an effect of further increasing the effect of the flame retardant can be used, and examples thereof include molybdenum compounds and antimony compounds, and particularly preferably, Sodium antimonate and antimony trioxide.

In the present invention, polytetrafluoroethylene having a fibril forming ability can be added in order to further improve the flame retardancy. Polytetrafluoroethylene having a fibril-forming ability is classified into Type III in the ASTM standard. Polytetrafluoroethylene having fibril forming ability is UL
Since polytetrafluoroethylene having the ability to form fibrils has the property of preventing dripping during the burning test of the test piece in the standard vertical burning test, it further imparts the flame retardant effect. These polytetrafluoroethylenes capable of forming fibrils are commercially available, for example, as Teflon 6J from Mitsui DuPont Fluorochemical Co., Ltd. or as polyflon from Daikin Chemical Industries, Ltd.

The addition amount of polytetrafluoroethylene having fibril forming ability is preferably 0.1 to 1 part by weight with respect to 100 parts by weight of the flame-retardant slidable resin composition of claim 5. If it is less than 0.1 part by weight, the melt-dripping prevention performance is not sufficient, and if it exceeds 1 part by weight, the appearance is deteriorated.

The resin composition of the present invention can be produced by mixing the above components with a mixer such as a tumbler, a V-type blender, a Nauter mixer, a Banbury mixer, a kneading roll and an extruder. Further, other resins such as polyester, polyamide, polyphenylene ether, etc. within a range that does not impair the object of the present invention, and the resin composition of the present invention, if necessary, various additives in an amount in which the effect is exhibited,
For example, stabilizers, release agents, UV absorbers, dyes and pigments may be included. For example, phosphite ester-based and phosphoric acid ester-based heat stabilizers are particularly preferable. The resin composition thus obtained can be easily molded by methods such as extrusion molding, injection molding and compression molding, and can also be applied to blow molding, vacuum molding, etc., making it ideal as a sliding part for electronic / electricity / OA. Is.

[0027]

EXAMPLES The present invention will be specifically described with reference to the following examples.

[Examples 1 to 12 and Comparative Examples 1 to 4] The components shown in Table 1 were mixed in a blending ratio shown in Table 1 in a V-type blender, and then a vent type twin-screw extruder having a diameter of 30 mm [Japan] Cylinder temperature 2 by TEX30XSST manufactured by Japan Steel Works
Pelletized at 40 ° C. This pellet at 100 ℃ 5
Injection molding machine [T-150 manufactured by FANUC Co., Ltd.]
D], various test pieces were prepared at a cylinder temperature of 250 ° C. and a mold temperature of 60 ° C., and evaluated by the following methods. Rigidity: Flexural modulus was measured according to ASTM D-790. Impact resistance: The impact with Izod notch was measured according to ASTM D-256. Heat resistance: 18.6 according to ASTM D-648
The deflection temperature under load was measured under a load of kgf / cm ² . Molding processability: Cylinder temperature 260 ° C, injection pressure 10
The flow length was measured with an Archimedes type spiral flow (thickness: 2 mm) at 00 kgf / cm ² . A thin moldability of 25 cm or more is good. If it was 25 cm or more, it was evaluated as ◯, and if less than 25 cm, it was evaluated as x. Appearance: A 50 × 80 × 2 mmt square plate was visually measured. The good ones with little influence of the inorganic filler are indicated by ◯, and the bad ones due to the influence by the inorganic filler are indicated by x. Flammability: A flammability test was performed according to UL standard 94V. Friction / Abrasion Property: A cylindrical test piece having an outer diameter of 25 mm and an inner diameter of 20 mm was formed, and a thrust friction wear test was performed using a friction tester [Friktron friction wear tester manufactured by Orientec Co., Ltd.]. Carbon steel for machine structure (S-
45C) was performed in a non-lubricated state, and the dynamic friction coefficient was measured. The sliding speed was 20 cm / sec. In addition, the symbol which shows each component of Table 1 is as follows. (A) PC: Aromatic polycarbonate resin (a component)
[L-1225 manufactured by Teijin Chemicals Ltd., viscosity average molecular weight 22
500] (B) PTFE: polytetrafluoroethylene resin (b
Component) [Lubron L-5 manufactured by Daikin Industries, Ltd., average particle size about 7 μm] (C) ABS: thermoplastic graft copolymer (component c)
ABS resin Santac UT-6 manufactured by Mitsui Toatsu Chemicals, Inc.
1] (D) Talc: Scale-like inorganic filler (d component) [Talc P-3 manufactured by Nippon Talc Co., Ltd., average particle size about 2.8 μm] CS: Chopped glass fiber [3PE- manufactured by Nitto Boseki Co., Ltd.]
941, diameter 13 μm, cut length 6 mm] (E) MBS: elastic polymer (e component) [Paraloid EXL-2602 manufactured by Kureha Chemical Industry Co., Ltd.] (F) S agent: composite rubber graft copolymer (f component) )
[Metablene S-2001 manufactured by Mitsubishi Rayon Co., Ltd.] (G) FR-1: Halogen-based flame retardant (g component) which is a carbonate oligomer of tetrabromobisphenol A.
[FG-7000 manufactured by Teijin Chemicals Ltd.] (G) FR-2: phosphorus-based flame retardant (g component) that is triphenyl phosphate [TPP manufactured by Daihachi Chemical Co., Ltd.] FR-3: fibril forming ability. Polytetrafluoroethylene having [Polyflon F-20 manufactured by Daikin Industries, Ltd.
1L]

[0029]

[Table 1]

[0030]

The resin composition of the present invention can be applied to any molding method such as injection molding. Also, shock resistance,
It is a resin composition that is excellent in rigidity, abrasion resistance, and wear characteristics, and is optimal as a sliding component for OA equipment and home electric appliances, which are becoming lighter, thinner, shorter, and smaller.

Continuation of front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display area // (C08L 69/00 55:02 27:18)

Claims (6)

[Claims] 1. A thermoplastic graft copolymer (c) obtained by grafting an aromatic polycarbonate resin (a component), a polytetrafluoroethylene resin (b component), and a diene rubber component with a vinyl cyanide compound and an aromatic vinyl compound. Component), and the ratio of the a component, the b component, and the c component is 40 to 94% by weight, the b component is 3 to 30% by weight, and the c component is A slidable resin composition which is 3 to 57% by weight. 2. The slidable resin composition 100 according to claim 1.
A highly rigid slidable resin composition comprising 3 to 50 parts by weight of a flaky inorganic filler (d component) with respect to parts by weight. 3. The slidable resin composition 100 according to claim 1.
Obtained by copolymerizing two or more kinds of monomers selected from the group consisting of methacrylic acid ester, acrylic acid ester and aromatic vinyl compound in the presence of a rubber containing a repeating unit derived from butadiene, based on parts by weight. 1 to 20 parts by weight of the elastic copolymer (e component) and / or a kind of composite rubber having a structure in which the polyorganosiloxane rubber component and the polyalkyl (meth) acrylate rubber component are intertwined with each other so that they cannot be separated from each other. Alternatively, 1 to 20 parts by weight of a composite rubber-based graft copolymer (f component) obtained by graft-polymerizing two or more vinyl-based monomers is blended, and a total of 20 parts by weight of the e component and the f component is added. A high-impact sliding resin composition, characterized in that it is blended in an amount that does not exceed. 4. The e-components 1 to 20 according to claim 3, relative to 100 parts by weight of the high-rigidity sliding resin composition according to claim 2.
1 to 20 parts by weight of the component f and / or the component f, and an amount not exceeding 20 parts by weight in total of the components e and f, which are high rigidity and high impact slidability. Resin composition. 5. The slidable resin composition 100 according to claim 1.
Parts by weight, or the high-rigidity sliding resin composition 1 according to claim 2.
00 parts by weight, or 100 parts by weight of the high-impact sliding resin composition according to claim 3, or 100 parts by weight of the high-rigidity, high-impact sliding resin composition according to claim 4, the flame retardant (g component) )
A flame-retardant slidable resin composition comprising 1 to 30 parts by weight. 6. A molded product formed from the slidable resin composition according to any one of claims 1 to 5.