JPH07216240A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic resin composition containing a thermoplastic resin and a specific polysiloxane group-containing polymer, excellent in mechanical properties, heat resistance, oil resistance, sliding property and moldability and processability and useful for automobile parts, etc. CONSTITUTION:This thermoplastic resin composition is obtained by melt mixing (A) preferably 85-99wt.% of a thermoplastic resin such as PE with (B) preferably 1-15wt.% of a polysiloxane group-containing polymer, e.g. a copolymer obtained by chemically bonding a polysiloxane group-containing polymer (segment) obtained by copolymerizing 5-85wt.% of one or a mixture of two or more kinds of compounds of formula I [R1 is H or methyl; R2 is methyl, ethyl, phenyl, etc.; R3 is H, phenyl, etc.; R4 is methyl, ethyl or phenyl; (n) is >1] or compounds of formula II with 15-95wt.% of one or a mixture of two or more kinds of vinyl monomers to a vinyl polymer segment not containing a polysiloxane group.

Description

Detailed Description of the Invention

[0001]

This invention relates to mechanical properties, heat resistance,
The present invention relates to a thermoplastic resin composition having excellent oil resistance, slidability, molding processability, etc., and its molded products are used in a wide range of fields such as automobile parts, electric and electronic device parts, and industrial parts. .

[0002]

2. Description of the Related Art Thermoplastic resins such as polyamide resins, polyester resins, polyacetal resins and polyarylene sulfide resins have excellent mechanical properties,
It is used in many fields because of its heat resistance. However, polyamide-based resins, polyester-based resins, polyacetal-based resins, and polyarylene sulfide-based resins are required to have higher impact resistance and slidability. Therefore, attempts have been made to improve impact resistance and slidability by adding tetrafluoroethylene resin, silicone oil, ultra high molecular weight polyethylene, polyolefin graft copolymer, etc. to these thermoplastic resins. .

For example, Japanese Patent Application Laid-Open No. 60-144351 discloses a composition obtained by adding ultra high molecular weight polyethylene to a polyamide resin. In addition, JP-A-63-2
Japanese Patent No. 13551 discloses a composition in which a tetrafluoroethylene resin is added to a polyester resin. Further, Japanese Patent Application Laid-Open No. 1-271453 discloses a composition obtained by adding a polyolefin graft copolymer to a polyacetal resin.

[0004]

However, since the polarities of the polyamide resin or polyester resin and the ultrahigh molecular weight polyethylene or tetrafluoroethylene resin are very different, there is no compatibility between them, so that the mechanical properties of the molded article are high. There is a problem that the physical properties and the appearance of the surface of the molded product deteriorate. Further, a thermoplastic resin composition obtained by adding a polyolefin-based graft copolymer to a polyacetal-based resin has an effect of improving impact resistance and the like, but has a problem that molding processability is lowered, and its improvement is required. There is.

The present invention has been made in view of the problems existing in such conventional techniques. It is an object of the invention to provide a thermoplastic resin composition which is excellent in physical properties such as mechanical properties, heat resistance, oil resistance, and slidability of a molded product to be obtained, and is also excellent in molding processability.

[0006]

As a result of intensive studies to solve the above problems, the present inventors have found that a specific polysiloxane group-containing polymer can be used as a polyamide resin, a polyester resin, a polyacetal resin and a polyarylene sulfide. It was found that a thermoplastic resin composition blended with a thermoplastic resin such as a base resin has excellent impact resistance and slidability while maintaining heat resistance, molding processability, etc., and completed the present invention.

That is, the invention of the thermoplastic resin composition according to claim 1 is characterized in that it comprises a thermoplastic resin (I) as a main component and a polysiloxane group-containing polymer (II) shown below. To do.

Polysiloxane group-containing polymer (II): 5-85% by weight of one or a mixture of two or more compounds represented by the general formula 1 or 3, and one vinyl monomer. Alternatively, a polysiloxane group-containing polymer obtained by copolymerizing 15 to 95% by weight of a mixture of two or more kinds, or the polysiloxane group-containing polymer segment and a vinyl polymer segment containing no polysiloxane group are chemically formed. A copolymer bound to.

Further, in the invention described in claim 2, in the invention described in claim 1, the thermoplastic resin (I) and the polysiloxane group-containing polymer (II) are melt-mixed.

Next, the components of the present invention will be described in detail. Examples of the thermoplastic resin (I) used in the present invention include engineering plastics such as polyamide-based resin, polyester-based resin, polyacetal-based resin, polycarbonate-based resin, polyphenylene ether-based resin, polyarylene sulfide-based resin, and polyarylate-based resin. Further, general-purpose resins such as polystyrene, high-impact polystyrene, styrene-based resins such as ABS, acrylic resins, vinyl chloride-based resins and the like can be mentioned.

Among these resins, polyamide resins, polyester resins, polyacetal resins and polyarylene sulfide resins, which are crystalline resins, are particularly preferable because they have a high effect of improving impact resistance and slidability. . Further, an amorphous resin such as a polycarbonate resin, a polyphenylene ether resin, a polyarylate resin, a styrene resin, or a vinyl chloride resin is preferable because it has a great improvement effect on molding processability.

The polysiloxane group-containing polymer used in the present invention is 5 to 85% by weight of a mixture of one or more of the compounds represented by the general formula 1 or 3,
15-95 a mixture of one or more vinyl monomers
A polysiloxane group-containing polymer obtained by copolymerizing the polysiloxane group with 1% by weight, or a copolymer in which the polysiloxane group-containing polymer segment and a vinyl polymer segment containing no polysiloxane group are chemically bonded.

The number average molecular weight of the compound represented by the above general formula 1 or formula 3 constituting the polysiloxane group-containing polymer is 500 to 50,000, and 1,000 to 30,000.
Is preferred. If the number average molecular weight is 500 or less, the effect of improving impact resistance is insufficient, and conversely, if it exceeds 50,000, moldability and workability are deteriorated, which is not preferable.

The compound of the general formula 1 is commercially available. For example, "FM0711", "FM071"
5 ”,“ FM0721 ”,“ FM0725 ”(all are trade names manufactured by Chisso Corporation) and the like correspond to this compound. Further, the compound represented by the general formula 3 can be obtained by a generally known reaction. For example, the commercial product "PS
Series ”(trade name, manufactured by Chisso Co., Ltd.), to 1 mol of silanolpolysiloxane having both terminals at both ends, a compound 2 represented by the following general formula 4 under a basic catalyst such as triethylamine and pyridine. It is obtained by reacting moles at a temperature from room temperature to about 60 ° C.

[0015]

[Chemical 4]

(In the formula, R ₁ represents a hydrogen atom or a methyl group, and R ₂ and R ₃ represent a methyl group, an ethyl group or a phenyl group, respectively.) The compound represented by the general formula 4 is known. It is a compound and can be obtained by the reaction of (meth) acrylic acid allyl ester with a silicon compound.

Specific examples of the vinyl monomer to be copolymerized with the compound represented by the general formula 1 or 3 include styrene, nucleus-substituted styrene such as methylstyrene, dimethylstyrene, ethylstyrene, isopropylstyrene,
Aromatic vinyl monomers such as chlorostyrene and α-substituted styrenes such as α-methylstyrene and α-ethylstyrene,
Acrylic acid or methacrylic acid, alkyl ester of acrylic acid or methacrylic acid having 1 to 8 carbon atoms, for example, (meth) acrylic acid such as methyl-, ethyl-, propyl-, butyl-, glycidyl-, 2-hydroxypropyl-, etc. of (meth) acrylic acid Acid ester monomer, vinyl cyanide monomer such as acrylonitrile or methacrylonitrile, vinyl ester monomer such as vinyl acetate and vinyl propionate, (meth) acrylamide monomer such as acrylamide and methacrylamide, maleic anhydride Examples thereof include acids, maleimides such as phenylmaleimide and cyclohexylmaleimide, and vinyl monomers such as maleic acid mono- and diesters.

Among these, aromatic vinyl monomers,
A (meth) acrylic acid ester monomer and a vinyl cyanide monomer are preferably used because they have good compatibility with a thermoplastic resin and good moldability.

When the mixture of one or more kinds of the compounds represented by the general formula 1 or 3 is copolymerized with one or two or more kinds of the vinyl monomer, the ratio is as described above. One or a mixture of two or more compounds represented by formula 1 or formula 3 is 5 to 85% by weight, preferably 10
~ 50% by weight. Therefore, the proportion of one kind or a mixture of two or more kinds of vinyl monomers is 15 to 95% by weight, preferably 90 to 50% by weight. If the amount of one or more of the compounds represented by the general formula 1 or 3 is 5% by weight or less, the effect of improving the slidability is low, and 8
If it exceeds 5% by weight, the appearance of the molded product is deteriorated, which is not preferable.

A mixture of one or more mixtures of the compounds represented by the above general formula 1 or 3, which is a polysiloxane group-containing polymer, and one or more mixtures of vinyl monomers. The number average molecular weight of the polymer is 1,000 to 10.
00000, preferably 3000-500000, more preferably 5000-200000. If the number average molecular weight is less than 1000, the impact resistance improving effect is insufficient, and if it exceeds 1,000,000, the molding processability is poor, which is not preferable.

Polysiloxane group-containing polymer constituting a copolymer in which a polysiloxane group-containing polymer segment as a polysiloxane group-containing polymer and a vinyl polymer segment containing no polysiloxane group are chemically bonded. A segment has the following meaning. That is, one or two of the compounds represented by the above general formula 1 or formula 3
A copolymer segment of a mixture of one or more kinds and a mixture of one or more kinds of vinyl monomers and a vinyl polymer segment containing no polysiloxane group are like block copolymers or graft copolymers. Is a copolymer bound to the end of the molecular chain or in the molecular chain.

The ratio of the polysiloxane group-containing polymer segment to the polysiloxane group-free vinyl polymer segment is 5 for the polysiloxane group-containing polymer segment.
˜95% by weight, preferably 10 to 90% by weight, more preferably 30 to 80% by weight. Therefore, the vinyl polymer segment containing no polysiloxane group is 95-
It is 5% by weight, preferably 90 to 10% by weight, more preferably 20 to 70% by weight. When the content of the polysiloxane group-containing polymer segment is less than 5% by weight, the effect of improving the slidability is insufficient, and when it exceeds 95% by weight, the appearance of the molded article is deteriorated, which is not preferable.

The polysiloxane group-containing polymer segment and the polysiloxane group-free vinyl polymer segment are chemically bonded, but the site of bonding is not necessarily the end of each segment. That is,
It may be a block copolymer or a graft copolymer. The vinyl polymer segment containing no polysiloxane group has good compatibility with the thermoplastic resin.
Then, the polysiloxane group-containing polymer segment and the vinyl polymer segment containing no polysiloxane group are chemically bonded, thereby improving the dispersibility of the polysiloxane group-containing polymer in the thermoplastic resin, It is possible to improve mechanical properties and heat resistance.

The polysiloxane group-containing polymer in the present invention can be synthesized by a known method. For example, one of the compounds represented by the general formula 1 or 3
The polysiloxane group-containing polymer obtained by copolymerizing one kind or a mixture of two or more kinds with one kind or a mixture of two or more kinds of vinyl monomers is synthesized by a usual radical polymerization method. Further, the copolymer in which the polysiloxane group-containing polymer segment and the vinyl polymer containing no polysiloxane group are chemically bonded can be obtained by two-step polymerization using, for example, polymeric peroxide as a polymerization initiator. That is, for example, a polymer peroxide as shown in the following general formula 5 is used to polymerize one kind or a mixture of two or more kinds of vinyl monomers.

[0025]

[Chemical 5]

At this time, a polymer containing a peroxy bond can be obtained by stopping the polymerization when about 50% of the active oxygen of the polymeric peroxide remains. Further, using this compound as a polymerization initiator, one or a mixture of two or more compounds represented by the general formula 1 or 3 which can be a polysiloxane group-containing polymer segment, and one vinyl monomer Alternatively, it can be synthesized by copolymerizing with a mixture of two or more kinds.

The thermoplastic resin composition of the present invention comprises a thermoplastic resin (I) as a main component and a polysiloxane group-containing polymer (II). Specifically, the mixing ratio of the thermoplastic resin (I) and the polysiloxane group-containing polymer (II) is preferably 50 to 9 for the thermoplastic resin (I).
9.9% by weight, more preferably 70 to 99.5% by weight, particularly preferably 85 to 99% by weight. Therefore,
The polysiloxane group-containing polymer (II) is preferably 0.1
-50% by weight, more preferably 0.5-30% by weight,
It is particularly preferably 1 to 15% by weight. If the content of the polysiloxane group-containing polymer is less than 0.1% by weight, the slidability improving effect is not sufficient, and if it exceeds 50% by weight, the mechanical properties and heat resistance of the molded article obtained from the composition deteriorate. Not preferable.

In the present invention, thermoplastic elastomers such as ethylene-propylene polymers and styrene-butadiene-styrene copolymers and hydrogenated products thereof, polyolefins such as polyethylene and polypropylene, polyethylene glycol, polypropylene glycol, tetrafluoride. Ethylene, silicone oil, etc. can be added. The addition amount thereof is preferably 50 parts by weight or less with respect to 100 parts by weight of the components (I) + (II). Thereby, impact resistance and slidability of the molded product can be improved. If the blending amount of these resins exceeds 50% by weight, the appearance of the molded product deteriorates, which is not preferable.

In the present invention, 100 parts by weight or less of an inorganic filler can be added to 100 parts by weight of the resin component in order to improve the mechanical properties and heat resistance of the molded product from the resin composition. . If the blending amount of the inorganic filler exceeds 100% by weight, the fluidity of the thermoplastic resin composition is lowered and the appearance of the molded product is deteriorated, which is not preferable.

Examples of the inorganic filler include powdery, flat, scale-like, needle-like, spherical, hollow or fibrous shapes. Specifically, calcium sulfate, calcium silicate, clay, diatomaceous earth, talc, alumina, silica sand, glass powder, iron oxide, metal powder, graphite, silicon carbide, silicon nitride, silica, boron nitride, aluminum nitride, carbon black, etc. Powder / granular fillers; metal foils such as glass plates, sericite, pyrophyllite, aluminum flakes, etc. flat or scale-like fillers such as graphite; hollow fillers such as shirasu balloons, metal balloons, glass balloons and pumice stones. Glass fibers, carbon fibers, mineral fibers such as asbestos and wstonite, and the like.

The surface of the filler is stearic acid,
Surface treatment is preferably performed using oleic acid, palmitic acid or metal salts thereof, paraffin wax, polyethylene wax, or modified products thereof, organic silanes, organic boranes, organic titanates and the like. By this surface treatment, the function of the inorganic filler can be more effectively exhibited.

The resin composition of the present invention has a temperature of 120 to 3
Melt the thermoplastic resin (I) and the polysiloxane group-containing polymer (II) at 50 ° C., preferably 150 to 330 ° C.
It is preferably produced by mixing. This melting / mixing prevents phase separation and delamination of the molded product. If the temperature is lower than 120 ° C., the melting is incomplete, the melt viscosity is high, the mixing is insufficient, and phase separation or layered peeling appears in the molded product, which is not preferable. Also,
If it exceeds 350 ° C, the resin to be mixed is decomposed or gelated, which is not preferable.

As a method of melting and mixing, a method using a kneading machine which is usually used, such as a Banbury mixer, a heating kneader, a kneading extruder, a twin-screw extruder, and a roll is adopted. Further, the resin composition of the present invention can be molded by any of the injection molding method, the extrusion molding method, the vacuum molding method and the blow molding method to obtain a desired molded product. Molded products obtained by these molding methods are used in a wide range of fields such as automobile parts, electric and electronic device parts, and industrial parts.

In addition to the above-mentioned components, the following additives or other thermoplastic resins may be added to the thermoplastic resin composition of the present invention. Examples of the additives include inorganic flame retardants such as magnesium hydroxide and aluminum hydroxide, organic flame retardants such as halogen-based and phosphorus-based, organic fillers such as wood powder, antioxidants, UV inhibitors, lubricants and dispersants. , Coupling agents, foaming agents, cross-linking agents, coloring agents and the like.

[0035]

The present invention will be described more specifically below with reference to Reference Examples, Examples and Comparative Examples. Reference Example 1, Production of Polysiloxane Group-Containing Polymer (IIA) 2500 g of pure water was placed in a reactor equipped with a thermometer, a stirrer, and a reflux condenser, and 2.5 g of polyvinyl alcohol was dissolved as a suspending agent. Let In this, 1050 g of styrene, 450 g of acrylonitrile, 500 g of the compound of the following general formula 6 and "Perloyl 3" as a polymerization initiator
55 "(trade name, manufactured by NOF Corporation) and 2 g of" NOFMER MSD "(trade name, manufactured by NOF Corporation) as a molecular weight modifier were added and stirred.

[0036]

[Chemical 6]

However, the number average molecular weight (Mn) is 5,000. Next, the temperature was raised to 70 ° C., polymerization was carried out at that temperature for 5 hours, washing with water and drying were carried out to obtain a fine powder of the polysiloxane group-containing polymer (IIA). The number average molecular weight was 120,000 as measured by gel permeation chromatography (GPC). Reference Example 2, Production of Polysiloxane Group-Containing Polymer (IIB) 2500 g of pure water was placed in a reactor equipped with a thermometer, a stirrer, and a reflux condenser, and 2.5 g of polyvinyl alcohol was dissolved as a suspending agent. Let In this, 350 g of styrene, 150 g of acrylonitrile, the above-mentioned general formula 6
And 500 g of the compound of the following general formula 7 as an initiator.

[0038]

[Chemical 7]

Next, the temperature was raised to 70 ° C., polymerization was carried out at that temperature for 3 hours, and then cooled to 40 ° C. Furthermore, by adding 700 g of styrene and 300 g of acrylonitrile,
After stirring at 70 ° C for 1 hour, the temperature was raised again to 70 ° C, polymerization was performed at that temperature for 5 hours, washing with water and drying were performed to obtain a polysiloxane group-containing polymer segment and a polysiloxane group-free vinyl-based polymer segment. A fine powder of a polysiloxane group-containing polymer (IIB) which is a block copolymer of When the number average molecular weight was measured by GPC, it was 1
It was 50,000. Reference Example 3, Production of Polysiloxane Group-Containing Polymer (IIC) 2500 g of pure water was placed in a reactor equipped with a thermometer, a stirrer, and a reflux condenser, and 2.5 g of polyvinyl alcohol was dissolved as a suspending agent. Let In this, 350 g of styrene, 150 g of acrylonitrile, the above-mentioned general formula 6
Of the compound of the general formula 5 as a polymerization initiator, and the mixture was stirred.

Next, the temperature is raised to 70 ° C., and at that temperature, 3
After polymerizing for an hour, it was cooled to 40 ° C. Further, 1000 g of styrene was added, and the mixture was stirred at 40 ° C. for 1 hour, then heated again to 70 ° C., polymerized at that temperature for 6 hours, washed with water and dried to obtain a polysiloxane group-containing polymer segment and a polysiloxane group. A fine powder of a polysiloxane group-containing polymer (IIC), which is a block copolymer composed of a vinyl-based polymer segment containing no styrene, was obtained. The number average molecular weight measured by GPC was 130000. (Reference Example 4, polyethylene-based graft copolymer (IID)
Production) 2500 g of pure water was placed in a reactor equipped with a thermometer, a stirrer, and a reflux condenser, and 2.5 g of polyvinyl alcohol was dissolved as a suspending agent. In this, ethylene-glycidyl methacrylate copolymer "Nisseki Lexpearl RA3150 (trade name, manufactured by Nippon Petrochemical Co., Ltd.)"
700 g, 210 g of styrene which is a vinyl monomer, 90 g of acrylonitrile, 5 g of t-butylperoxymethacryloyloxyethyl caobonate which is a radical-polymerizable organic peroxide represented by the general formula 7, and 3 as a radical polymerization initiator. 3 g of 5,5-trimethylhexanoyl peroxide "Perloyl 355" (trade name, manufactured by NOF CORPORATION) was added and stirred.

Then, the reactor is heated to 60 to 65 ° C.,
The mixture was impregnated into the particles of the vinyl monomer ethylene-glycidyl methacrylate copolymer containing the radical-polymerizable organic peroxide and the radical polymerization initiator by stirring for 2 hours. Next, the temperature is raised to 70 to 75 ° C.
Polymerization was completed by maintaining for a period of time, washed with water and dried to obtain a graft precursor. The styrene-acrylonitrile copolymer in this graft precursor was extracted with ethyl acetate to obtain GP
When the number average molecular weight was measured by C, it was 105,000.
Met.

Further, this grafted precursor was applied to a Labo Plastomill uniaxial extruder (manufactured by Toyo Seiki Co., Ltd.) for 20 times.
A polyethylene graft copolymer (IID) was obtained by extruding at 0 ° C. and carrying out a grafting reaction. (Examples 1 to 8) Polyamide (IA) "UBE Nylon 1013B" (trade name, manufactured by Ube Industries, Ltd.) (displayed as PA in the table), and the polysiloxane group-containing weight obtained in Reference Example 1 or 2 The combination (IIA) or (IIB) was dry blended. Then, the mixture was supplied to a coaxial twin-screw extruder having a screw diameter of 30 mm set to a cylinder temperature of 250 ° C., and granulated after extrusion. The granulated resin was dried at 110 ° C., and then a test piece was prepared by injection molding, and the following test was conducted. The results are shown in Table 1. Size of test piece: Izod impact test piece 13mm × 65mm × 6mm (with notch) Deflection temperature test piece 13mm × 130mm × 6mm Bending test piece 10mm × 130mm × 4mm Dynamic friction coefficient test piece 30mm × 30mm × 3mm Test method Was performed by the method shown below. (1) Izod impact value (with notch): JIS K7110 (2) Deflection temperature under load: JIS K7207 (3) Bending test: JIS K6758 (4) Dynamic friction coefficient test EFM-II friction wear tester manufactured by Orientec Co., Ltd.
The dynamic friction coefficient was determined using IF (high speed type). The mating material and the test conditions at this time are as follows.

Mating material: Cylindrical material having an inner diameter of 20 mm and an outer diameter of 25.6 mm Material S45C Test conditions: load 5 kg / cm ² , linear velocity 30 cm / sec (PA, PBT, POM, PC, ABS) load 5 kg / cm ² , Linear velocity 80 cm / sec (PPS, PPE) (5) Fluidity (spiral flow) Molds with spiral grooves of width 4 and thickness 2 in injection molding machine at molding temperatures of 220 ° C, 260 ° C and 300 ° C, respectively. Mounted, injection speed 95%, injection pressure 100
Injection molding was performed under the conditions of 0 kg / cm ² and a mold temperature of 60 ° C., and the length of the molded spiral was measured and used as an index of fluidity. (6) Appearance of molded product Regarding the appearance of the molded product, the presence or absence of delamination was visually determined and ranked as follows.

State of layered peeling ⊚: No layered peeling at all, ○: Slightly layered peeling, ×:
Delamination throughout

[0045]

[Table 1]

As shown in Table 1, the compositions of Examples 1 to 8 are thermoplastic resin compositions in which polyamide as a thermoplastic resin and a polysiloxane group-containing polymer are mixed, and Izod impact value and Excellent in mechanical properties such as bending strength. Also, it has excellent heat resistance as shown by the deflection temperature under load, and has excellent slidability as shown by the dynamic friction coefficient. Furthermore, as shown by the spiral flow, the fluidity is good and the moldability is excellent. In addition, the appearance of the molded product is also good. (Examples 9 to 17) Polybutylene terephthalate (I
B) "Toray PBT resin 1401X06" (trade name, manufactured by Toray Industries, Inc.) (displayed as PBT in the table), polyacetal (IC) "Tenac 4510" (trade name, manufactured by Asahi Kasei Corporation), or polyphenylene sulfide (ID) "Fortron KPS" (trade name, manufactured by Polyplastics Co., Ltd.) and the polysiloxane group-containing polymers (IIA) to (IIC) obtained in Reference Examples 1 to 3 were used, and the same as Example 1. Then, a test piece of the resin molded product was prepared, and the same test was conducted. The results are shown in Table 2.

[0047]

[Table 2]

As shown in Table 2, the resin compositions of Examples 9 to 17 were prepared by adding polybutylene terephthalate (IB), polyacetal (IC) or polyphenylene sulfide (ID) as a thermoplastic resin, and a polysiloxane group-containing weight. Blended together. Therefore, in each example,
It has excellent mechanical properties, heat resistance and slidability, as well as good fluidity and excellent moldability. Moreover, the appearance of the molded product is good. (Examples 18 to 26) Polycarbonate (IE) "Panlite L-1250" (trade name, manufactured by Teijin Chemicals Ltd.)
(Displayed as PC in the table), polyphenylene ether (IF) "Noryl 534J-801" (trade name, manufactured by GE Plastics Co., Ltd.) (displayed as PPE in the table), or ABS resin (IG) "stylist". Rack AB
S 283 "(trade name, manufactured by Asahi Kasei Corporation) (ABS
In the table) was used to prepare a test piece in the same manner as in Example 1, and the same test was performed. The results are shown in Table 3.

[0049]

[Table 3]

As shown in Table 3, each of the resin compositions of Examples 18 to 26 contained polycarbonate (IE), polyphenylene ether (IF) or AB as a thermoplastic resin.
The polysiloxane group-containing polymer is blended with the S resin (IG). Therefore, in each example, the mechanical properties, heat resistance and slidability are good, and the flowability is good,
It also has excellent moldability. Moreover, the appearance of the molded product is good. (Examples 27 to 36) SE was added to the resin composition of the above example.
BS "Clayton G1650" (trade name, manufactured by Shell Chemical Co., Ltd.), silicone oil "Shin-Etsu Silicone KF"
96H 10000 "(Shin-Etsu Chemical Co., Ltd.) (displayed as SO in the table) or glass fiber (average fiber length 0.3 m
m, diameter 10 μm) was tested on the composition. The results are shown in Table 4.

[0051]

[Table 4]

However, SEBS and SO in Table 4 represent parts by weight based on 100 parts by weight of the total amount of the resin (I) and the resin (II). As shown in Table 4, in Examples 27 to 36, the thermoplastic resin is blended with the polysiloxane group-containing polymer and further blended with SEBS or silicone oil. Therefore, impact resistance and slidability are particularly improved. (Examples 37 to 42) Similar to Examples 27 to 36, tests were conducted on compositions obtained by adding SEBS or SO to the resin compositions of the above Examples. The results are shown in Table 5.

[0053]

[Table 5]

However, SEBS and SO in Table 5 represent parts by weight based on 100 parts by weight of the total amount of the resin (I) and the resin (II). As shown in Table 5, in Examples 37 to 42, the thermoplastic resin was blended with the polysiloxane group-containing polymer and further blended with SEBS or silicone oil. Therefore, impact resistance and slidability are particularly improved. (Comparative Examples 1 to 39) The polysiloxane group-containing polymers (IIA) to (IIC) used in the above Examples are not used, or instead, Silycorn Oil "Shin-Etsu Silicone K".
F96H10000 "(Shin-Etsu Chemical Co., Ltd.) (displayed as SO in the table), styrene-acrylonitrile copolymer (70/30) (displayed as AS in the table), ultra high molecular weight polyethylene" Lubmer L5000 "(trade name, Examples using Mitsui Petrochemical Industry Co., Ltd. (indicated as HMPE in the table) or the polyethylene-based graft copolymer (IID) obtained in Reference Example 4 are shown in Tables 6 to 9.

[0055]

[Table 6]

In Comparative Examples 4 and 6 in Table 6, the surface of the molded product was sticky and the appearance was poor. As shown in Comparative Examples 1 to 9 in Table 6, when the polysiloxane group-containing polymer is not blended or when the thermoplastic resin is not the main component, mechanical properties such as impact resistance are low. In some cases, the slidability, the molding workability, etc. are deteriorated, and the appearance of the molded product becomes poor.

[0057]

[Table 7]

Comparative Examples 11, 12, 16 and 17 in Table 7
In No. 1, the surface of the molded product was sticky and the appearance was poor. As shown in Comparative Examples 10 to 19 in Table 7,
When the polysiloxane group-containing polymer is not blended, mechanical properties are low, slidability and molding processability are deteriorated, and the appearance of the molded product may be poor.

[0059]

[Table 8]

Comparative Examples 21, 22, 26 and 27 in Table 8
In No. 1, the surface of the molded product was sticky and the appearance was poor. As shown in Comparative Examples 20 to 29 in Table 8,
When the polysiloxane group-containing polymer is not blended, mechanical properties, slidability, molding processability, etc. are low, and the appearance of the molded product may be poor.

[0061]

[Table 9]

Comparative Examples 31, 32, 36 and 37 in Table 9
In No. 1, the surface of the molded product was sticky and the appearance was poor. As shown in Comparative Examples 30 to 39 in Table 9,
If the polysiloxane group-containing polymer is not blended, the mechanical properties, slidability, molding processability, etc. may deteriorate and the appearance of the molded product may become poor.

From the above results, the polysiloxane group-containing polymer (II) has the effect of improving the impact resistance and slidability of the crystalline thermoplastic resin (I) such as polyamide, polyester, polyacetal and polyphenylene sulfide. Demonstrate. Further, it exerts a great effect on the improvement of molding processability and slidability of an amorphous thermoplastic resin such as polycarbonate, polyphenylene ether, ABS and the like. Therefore, the thermoplastic resin composition of the present invention shown in each of the examples has impact resistance, slidability, molding processability, and appearance while maintaining bending strength and heat resistance as compared with those of the comparative examples. Can be improved.

[0064]

As described above in detail, the polysiloxane group-containing polymer (II) used in the present invention has a high impact resistance of the thermoplastic resin (I) such as engineering plastics,
It has a great effect on improving slidability and moldability. Therefore, the thermoplastic resin composition of the invention according to claim 1 in which these are combined is excellent in physical properties such as mechanical properties, heat resistance, oil resistance, slidability, and appearance of the obtained molded article,
It also has excellent moldability. Further, according to the invention described in claim 2, phase separation and delamination of the molded product can be effectively prevented. Therefore, the molded article obtained from the thermoplastic resin composition of the present invention is widely used for automobile parts, electric / electronic parts, industrial parts and the like, and is industrially useful.

Claims (2)

[Claims] 1. A thermoplastic resin composition comprising a thermoplastic resin (I) as a main component and a polysiloxane group-containing polymer (II) shown below. Polysiloxane group-containing polymer (II): 5-85% by weight of a mixture of one or more compounds represented by the following general formula 1 or 3, and one or two vinyl monomers. A polysiloxane group-containing polymer obtained by copolymerizing 15 to 95% by weight of the above mixture, or the polysiloxane group-containing polymer segment and a vinyl polymer segment containing no polysiloxane group are chemically bonded. Copolymer. [Chemical 1] (In the formula, R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a methyl group, an ethyl group, a phenyl group or the following general formula 2,
R ₃ is a hydrogen atom, a phenyl group or a _{C P H 2P + 1, R} 4
Each represents a methyl group, an ethyl group or a phenyl group, n is an integer of 1 or more, and p is an integer of 1 to 10. ) [Chemical 2] (In the formula, R ₅ is a hydrogen atom, a phenyl group or C _{PH 2P + 1.}
R ₆ represents a methyl group, an ethyl group or a phenyl group, m is an integer of 1 or more, and p is an integer of 1 to 10. ) [Chemical 3] (In the formula, R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a methyl group, an ethyl group, a phenyl group or the above general formula 2,
R ₃ is a hydrogen atom, a phenyl group or C _{PH 2P + 1} , n is an integer of 1 or more, and p is an integer of 1 to 10. ) 2. The thermoplastic resin composition according to claim 1, which is obtained by melting and mixing the thermoplastic resin (I) and the polysiloxane group-containing polymer (II).