JP5687466B2 - Contact parts made of thermoplastic resin composition with reduced squeaking noise - Google Patents

Description

  The present invention relates to a contact component, and more particularly, to a contact component made of a thermoplastic resin composition that greatly reduces the squeaking noise generated by contacting and rubbing with other components.

  ABS resins are widely used in the manufacture of contact parts such as automobile interior parts due to their excellent mechanical properties, heat resistance, moldability, and the like.

  However, in the case where the automobile interior parts made of ABS resin and the parts are in contact with and rubbed with chloroprene rubber, polyurethane, natural rubber, polyester or polyethylene lining sheets, foam, etc. due to vibration during automobile driving, Sound (friction) may be generated. For example, a ventilator made of ABS resin is equipped with a valve shutter that uses chloroprene rubber foam or the like as a sealing material to adjust the air volume, and seals when the valve shutter is rotated to adjust the air volume. The wood and the ventilator case rub against each other. As described above, a squeaking noise may be generated even under a usage situation in which an ABS resin automobile interior part functionally rubs against other parts.

  Also, since ABS resin and ASA resin are amorphous plastics, they have a higher coefficient of friction compared to crystalline plastics such as polyethylene, polypropylene, and polyacetal, and are used for air conditioner outlets and car stereo buttons in automobiles. As described above, it is well known that a stick-slip phenomenon (Non-Patent Document 1) occurs and abnormal noise (stagnation sound) occurs when mated with a component made of another resin. These squeaking noises are a major cause of impairing comfort and quietness when riding, and it has been strongly desired to reduce squeaking noises.

  Therefore, in order to prevent these squeaking noises, a method of applying Teflon (registered trademark) coating to the surface of the component, a method of mounting Teflon (registered trademark) tape, a method of applying silicone oil, etc. have been performed. The process such as coating is not only complicated and time-consuming, but also has a problem that the effect is not sustained when placed under high temperature.

  Further, as a method for modifying the material itself used for automobile interior parts, for example, a technique (Patent Document 1) in which an organosilicon compound is blended with a resin made of polycarbonate resin and ABS resin, flame retardant, difficult A technology for blending a fuel aid and silicone oil (Patent Document 2), a technology for blending silicone oil in ABS resin, MBS resin and HIPS (High Impact Polystyrene) resin (Patent Document 3), and an alkane in ABS resin The technique of blending a sulfonate surfactant (Patent Document 4) further blends ABS resin with a modified polyorganosiloxane having at least one reactive group selected from an epoxy group, a carboxyl group and an acid anhydride group. Disclosed is a technology (Patent Document 5) that uses water for parts in bathrooms and toilets to increase water It has been.

  However, the effect of reducing stagnation noise by these methods is not sufficient, and even if it shows a certain level of stagnation noise prevention effect immediately after molding, the effect is not long-lasting, especially when placed at high temperatures for a long time Had a problem that the effect was reduced.

Japanese Patent Publication No. 63-56267 Japanese Patent No. 2798396 Japanese Patent No. 2688619 Japanese Patent No. 2659467 JP 10-316833 A

Surface Science Vol.24, No.6, P328-333,2003.

  In view of such circumstances, the present invention significantly reduces the squeaking noise generated when the parts rub against each other, and maintains the squeaking noise reduction effect even when left under high temperature for a long time. An object of the present invention is to provide a contact component comprising a thermoplastic resin composition having excellent properties and surface appearance of a molded product.

  As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention have added a specific amount of a specific additive to a specific rubber-reinforced styrene resin or a rubber-reinforced styrene resin. It has been found that the generation is remarkably reduced and the effect of reducing the squeaking noise is maintained without deterioration even when it is placed at a high temperature for a long time, and the present invention has been completed.

That is, according to the present invention, the following contact parts are provided.
1. A thermoplastic resin composition comprising the following component (A), component (B) and component (C), wherein component (A) is 5 to 100 parts by mass, and component (B) is 0 to 95: The total of component (A) and component (B) is 100 parts by mass, and component (C) is polyorganosiloxane (a) and conjugated diene rubber polymer (d) in the thermoplastic resin composition. the weight ratio of (a) :( d) is 50 to 90: 50 to a 10, the contact parts, characterized in that contact with the component made of thermoplastic resin composition, or other thermoplastic resin:
(A) Monomer (b) comprising an aromatic vinyl compound or an aromatic vinyl compound and another vinyl monomer copolymerizable with the aromatic vinyl compound in the presence of the polyorganosiloxane (a) A polyorganosiloxane thermoplastic resin obtained by polymerizing
(B) a vinyl polymer obtained by polymerizing one or more vinyl monomers (c),
(C) An aromatic vinyl compound or an aromatic vinyl compound and another vinyl monomer copolymerizable with the aromatic vinyl compound in the presence of the conjugated diene rubbery polymer (d) (b) The rubber particle size of the component (d) is 50 to 800 nm in terms of volume average particle size, the component (d) is 5 to 80% by mass, the graft ratio is 30 to 200% by mass, and the acetone soluble component A conjugated diene rubber-based thermoplastic resin having an intrinsic viscosity [η] of 0.1 to 1.5 dl / g (measured in methyl ethyl ketone at 30 ° C.).
2. Further, olefin resin (E) (except low molecular weight polyethylene (F), ultra high molecular weight polyethylene (G), polytetrafluoroethylene resin (H)) , low molecular weight polyethylene (F), ultra high molecular weight polyethylene (G), polytetrafluoroethylene resin (H), silicone oil (I), and hydrogenated block copolymer (J). Contact parts as described.
3. Olefin resin (E) (excluding low molecular weight polyethylene (F), ultrahigh molecular weight polyethylene (G), polytetrafluoroethylene resin (H)) and hydrogenation with respect to 100 parts by mass of the thermoplastic resin composition 5 to 100 parts by mass of block copolymer (J), 0.1 to 30 parts by mass of low molecular weight polyethylene (F), ultrahigh molecular weight polyethylene (G) and polytetrafluoroethylene (H), silicone oil (I) Is 0.1 to 8 parts by mass. Contact parts as described.
4). Olefin resin (E) (excluding low molecular weight polyethylene (F), ultra high molecular weight polyethylene (G), polytetrafluoroethylene resin (H)) , low molecular weight polyethylene (F), ultra high molecular weight polyethylene (G ), Polytetrafluoroethylene-based resin (H), silicone oil (I), and hydrogenated block copolymer (J) in an amount of 0.1 to 100 parts by mass of the thermoplastic resin composition. 30 parts by mass is added, and Contact parts.
5. 1. Used for automotive interior parts, switch parts, office equipment parts, desk lock parts, residential interior parts, or indoor door opening / closing damper parts. ~ 4. The contact part according to any one of the above.
6). 4. The automobile interior part is an automobile ventilator, a plate blade of an air conditioner for a car, a valve shutter, a louver, a switch part, or an exterior part for car navigation. Contact parts.

According to the present invention, by blending the components (A) and (B) component (C) comprising a thermoplastic resin composition comprising, excellent impact resistance and molded article surface appearance, when the parts rub against each other It is possible to obtain a contact component in which the generated squeaking noise is remarkably reduced and the squeaking noise reduction effect does not deteriorate even when the squeaking noise is kept at a high temperature for a long time.

FIG. 1 is a schematic diagram showing a method for examining the occurrence of a stagnation sound.

Hereinafter, the present invention will be described in detail.
In the present specification, “(co) polymerization” means homopolymerization and copolymerization, and “(meth) acryl” means acrylic and / or methacrylic.

The component (A) of the present invention comprises an aromatic vinyl compound or an aromatic vinyl compound and another vinyl monomer copolymerizable with the aromatic vinyl compound in the presence of the polyorganosiloxane (a). It is a polyorganosiloxane thermoplastic resin obtained by polymerizing the monomer (b).
The polyorganosiloxane (a) used in the present invention is an organosiloxane (a-1) or, if necessary, a modified polyorganosiloxane obtained by co-condensing this with a graft crossing agent (a-2). However, the modified polyorganosiloxane is preferable from the viewpoint of impact resistance and appearance of the molded product surface. Here, as the organosiloxane (a-1), for example, the general formula R1nSiO (4-n) / 2 (wherein R1 is a substituted or unsubstituted monovalent hydrocarbon group, and n is 0 to 3). Any of those having a linear, branched or cyclic structure can be used, and an organosiloxane having a cyclic structure is preferred.

  Examples of the substituted or unsubstituted monovalent hydrocarbon group of the organosiloxane (a-1) include a methyl group, an ethyl group, a propyl group, a vinyl group, a phenyl group, and a halogen atom or a cyano group. Examples include substituted hydrocarbon groups.

  Specific examples of the organosiloxane (a) include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, and other cyclic compounds. A chain or branched organosiloxane can be mentioned. As the organosiloxane (a-1), a polyorganosiloxane condensed in advance, for example, having a weight average molecular weight in terms of polystyrene of about 500 to 10,000 can also be used. When the organosiloxane (a-1) is a polyorganosiloxane, the molecular end groups thereof are, for example, a hydroxyl group, an alkoxy group, a trimethylsilyl group, a dimethylvinylsilyl group, a methylphenylvinylsilyl group, a methyldiphenylsilyl group, etc. What is blocked can also be used.

As the graft crossing agent (a-2), for example, the following compounds can be used. That is, a graft crossing agent (a) having both an unsaturated group and an alkoxysilyl group represented by the following (a) CH ₂ = CR ³ -R ^2-
(Wherein R ² represents a phenyl group, R ³ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms)
Specific examples of this compound include p-vinylphenylmethyldimethoxysilane, 1- (p-vinylphenyl) methyldimethylisopropoxysilane, 2- (p-vinylphenyl) ethylenemethyldimethoxysilane, 3- (p-vinylphenoxy). ) Propylmethyldiethoxysilane, 1- (o-vinylphenyl) -1,1,2-trimethyl-2,2-dimethoxydisilane, and the like. These may be used alone or in combination of two or more. it can.

  Other graft crossing agents (a-2) include vinyl groups such as vinylmethyldimethoxysilane, tetravinyltetramethylcyclosiloxane, allylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, and γ-methacryloxypropylmethyldimethoxysilane. A silane compound having a mercapto group (thiol group), an amino group or the like can also be used. These other graft crossing agents may be used alone or in combination of two or more, or may be used in combination with the graft crossing agent described in (a) above. Preferred examples of the graft crossing agent (a-2) include p-vinylphenylmethyldimethoxysilane, 2- (p-vinylphenyl) ethylmethyldimethoxysilane, and 2- (p-vinylphenyl) ethylenemethyldimethoxysilane. Can be mentioned.

  The proportion of the graft crossing agent (a-2) used is 0 to 50% by mass, preferably 0.1 to 10% by mass, in the total amount of the component (a-1) and the component (a-2). More preferably, it is 0.3-5 mass%, Most preferably, it is 0.5-3 mass%. When the ratio of the graft crossing agent (a-2) exceeds 50% by mass, the graft ratio increases, but the molecular weight of the grafted (co) polymer decreases, and as a result, the impact strength tends to decrease.

The modified polyorganosiloxane (a) is obtained by shearing the organosiloxane (a-1) and the graft crossing agent (a-2) using a homomixer, a homogenizer or the like in the presence of an emulsifier such as an alkylbenzene sulfonic acid. It can be produced by mixing and condensing. In the production of the modified polyorganosiloxane (a), a crosslinking agent may be added as the third component for the purpose of improving the impact resistance of the resulting resin. As the crosslinking agent, trifunctional or tetrafunctional crosslinking agents such as methyltrimethoxysilane, phenyltrimethoxysilane, ethyltriethoxysilane, and tetraethoxysilane can be used.
As said crosslinking agent used here, it can be used individually or in combination of 2 or more types. The amount of the crosslinking agent used is usually 10% by mass or less, preferably 5% by mass or less, based on the total amount of the organosiloxane (a-1) and the graft crossing agent (a-2).

Here, the polystyrene-equivalent weight average molecular weight of the modified polyorganosiloxane (a) is usually 30,000 or more, preferably 30,000 to 1,000,000, more preferably 50,000 to 300,000. It is. Within this range, the thermoplastic resin composition of the present invention is excellent in the balance of impact resistance, fluidity and molded article surface appearance.

  As the aromatic vinyl compound used in the production of the component (A), styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, vinyltoluene, β-methylstyrene, ethylstyrene, p-tert-butyl Examples thereof include styrene, vinyl xylene, vinyl naphthalene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, and fluorostyrene. These can be used alone or in combination of two or more. Of these, styrene and α-methylstyrene are preferred.

  Other vinyl monomers copolymerizable with aromatic vinyl compounds include vinyl cyanide compounds, (meth) acrylic acid esters, maleimide compounds, and carboxyl groups, acid anhydride groups, hydroxyl groups, amino groups, amide groups. There are functional group-containing unsaturated compounds having one or more functional groups such as an epoxy group and an oxazoline group, and these can be used alone or in combination of two or more.

  Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile. These can be used alone or in combination of two or more. Of these, acrylonitrile is preferred.

  (Meth) acrylates include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, phenyl acrylate Acrylates such as benzyl acrylate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, methacrylic acid And methacrylic acid esters such as cyclohexyl, phenyl methacrylate, and benzyl methacrylate. These can be used alone or in combination of two or more. Of these, methyl methacrylate and butyl acrylate are preferred.

Examples of maleimide compounds include maleimide, N-methylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, and N-phenylmaleimide. These can be used alone or in combination of two or more. Of these, N-cyclohexylmaleimide and N-phenylmaleimide are preferable.
As a method for introducing the monomer comprising the maleimide compound into the polymer, a method in which maleic anhydride is copolymerized in advance and then imidized is also preferably used.

  Examples of the carboxyl group-containing unsaturated compound include acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, and cinnamic acid, and these are used alone or in combination of two or more. be able to. Of these, acrylic acid and methacrylic acid are preferred.

  Examples of the acid anhydride group-containing unsaturated compound include maleic anhydride, itaconic anhydride, citraconic anhydride and the like, and these can be used alone or in combination of two or more. Of these, maleic anhydride is preferred.

  Examples of the hydroxyl group-containing unsaturated compound include hydroxystyrene, 3-hydroxy-1-propene, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene, trans-4-hydroxy-2-butene, 3- Examples include hydroxy-2-methyl-1-propene, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, N- (4-hydroxyphenyl) maleimide, and these are used alone or in combination of two or more. can do. Of these, 2-hydroxyethyl methacrylate and 2-hydroxyethyl acrylate are preferred.

  Amino group-containing unsaturated compounds include aminoethyl acrylate, propylaminoethyl acrylate, dimethylaminomethyl acrylate, diethylaminomethyl acrylate, 2-dimethylaminoethyl acrylate, aminoethyl methacrylate, propylaminoethyl methacrylate, Dimethylaminomethyl methacrylate, diethylaminomethyl methacrylate, 2-dimethylaminoethyl methacrylate, phenylaminoethyl methacrylate, p-aminostyrene, N-vinyldiethylamine, N-acetylvinylamine, acrylicamine, methacrylamine, N-methyl An acrylic amine etc. are mentioned, These can be used individually or in combination of 2 or more types.

  Examples of the amide group-containing unsaturated compound include acrylamide, N-methylacrylamide, methacrylamide, and N-methylmethacrylamide. These can be used alone or in combination of two or more. Of these, acrylamide is preferred.

  Examples of the epoxy group-containing unsaturated compound include glycidyl acrylate, glycidyl methacrylate, and allyl glycidyl ether, and these can be used alone or in combination of two or more. Among these, glycidyl methacrylate is preferable.

  Examples of the oxazoline group-containing unsaturated compound include vinyl oxazoline and the like, and these can be used alone or in combination of two or more.

  The above-mentioned vinyl monomer is used in combination with the aromatic vinyl compound or the aromatic vinyl compound and the aromatic vinyl compound and other vinyl monomers copolymerizable with the aromatic vinyl compound. Preferred is the aromatic vinyl compound. And other vinyl monomers copolymerizable with the aromatic vinyl compound. More preferred combinations here are aromatic vinyl compounds / vinyl cyanide compounds, aromatic vinyl compounds / (meth) acrylic acid esters, aromatic vinyl compounds / vinyl cyanide compounds / (meth) acrylic acid esters, aromatic vinyl compounds. / Maleimide compounds, particularly preferably styrene / acrylonitrile (60-90 / 10-40; mass ratio), styrene / methyl methacrylate (10-90 / 10-90; mass ratio), styrene / phenylmaleimide (50- 95/5 to 50; mass ratio).

  Moreover, when combining a functional group containing unsaturated compound with the above-mentioned preferable monomer combination, it is 0-30 mass% normally with respect to 100 mass% of monomers whole quantity, Preferably it is 0-20 mass%, Furthermore, Preferably it is 0-15 mass%.

  The component (A) of the present invention is a polyorganosiloxane thermoplastic resin obtained by graft polymerization of the monomer (b) in the presence of the polyorganosiloxane (a). A graft copolymer in which the (co) polymer of the monomer component (b) is grafted to the component (a), and a (co) polymer of the component (b) not grafted to the component (a). included. However, this graft copolymer may contain (a) component which (b) component (co) polymer is not grafted.

  The charged composition when the monomer (b) is graft-polymerized to the polyorganosiloxane (a) is preferably 5 to 80% by mass, more preferably 10 to 80% by mass, and particularly preferably 10 to 10% by mass. 70% by mass. On the other hand, the component (b) is preferably 20 to 95% by mass, more preferably 20 to 90% by mass, and particularly preferably 30 to 90% by mass (provided that (a) + (b) = 100% by mass). When the range of the component (a) is less than 5% by mass and the range of the component (b) exceeds 95% by mass, the squeaking noise reduction and impact resistance tend to be inferior. On the other hand, if the range of the component (a) exceeds 80% by mass and the range of the component (b) is less than 20% by mass, the impact resistance and the molded product surface appearance tend to be inferior.

The graft ratio of the polyorganosiloxane thermoplastic resin (A) thus obtained is preferably 10% by mass or more, more preferably 20% by mass or more, and particularly preferably 30 to 150% by mass. When the graft ratio of the component (A) is less than 10% by mass, the resulting resin composition tends to be inferior in impact resistance and molded product surface appearance. The graft ratio can be obtained by the following formula, where X is the rubber component in 1 gram of component (A) and Y is the insoluble matter in methyl ethyl ketone in component (A).
Graft ratio (%) = [(Y−X) / X] × 100
In addition, the intrinsic viscosity [η] of acetone-soluble component (A) in component (A) (measured in methyl ethyl ketone at 30 ° C.) is preferably 0.1 to 1.5 dl / g, more preferably 0.3 to 1. 0 dl / g. When the intrinsic viscosity [η] is within this range, the balance between impact resistance and moldability is excellent.

  The volume average particle diameter of the polyorganosiloxane (a) used in the production of the polyorganosiloxane thermoplastic resin (A) is preferably 800 nm or less, more preferably 50 to 500 nm, and particularly preferably 80 to 300 nm. When the volume average particle diameter exceeds 800 nm, the surface appearance of the molded product tends to be inferior. Here, the volume average particle diameter can be measured by a known method such as a dynamic light scattering method.

The polyorganosiloxane-based thermoplastic resin (A) of the present invention can be produced by emulsion polymerization, solution polymerization, suspension polymerization, bulk polymerization, and a polymerization method that combines these. It is manufactured by emulsion polymerization from the balance of properties, impact resistance, and molded product surface appearance.
As the emulsifier, the solvent, the suspending agent, the polymerization initiator, the chain transfer agent and the like used in the above emulsion polymerization, solution polymerization, suspension polymerization and bulk polymerization, all known ones are used. Also, known polymerization conditions (polymerization temperature, stirring speed, stirring blade shape, etc.), polymerization method (main auxiliary material addition method, etc.), polymer recovery method, etc. can be used.

  The vinyl polymer as the component (B) of the present invention is a (co) polymer obtained by polymerizing one or more vinyl monomers (c), and the vinyl monomer used here As the body, all of the aromatic vinyl compound and other vinyl monomers copolymerizable with the aromatic vinyl compound described in the monomer (b) of the component (A) can be used.

  A preferable combination of vinyl monomers in the component (B) of the present invention is a combination of an aromatic vinyl compound and another vinyl monomer copolymerizable with the aromatic vinyl compound. More preferred combinations here are aromatic vinyl compounds / vinyl cyanide compounds, aromatic vinyl compounds / (meth) acrylic acid esters, aromatic vinyl compounds / vinyl cyanide compounds / (meth) acrylic acid esters, aromatic vinyl compounds. / Maleimide compounds, particularly preferably styrene / acrylonitrile (60-90 / 10-40; mass ratio), styrene / methyl methacrylate (10-90 / 10-90; mass ratio), styrene / phenylmaleimide (50- 95/5 to 50; mass ratio), α-methylstyrene / acrylonitrile / styrene (50 to 80/20 to 40/0 to 10; mass ratio), styrene / butyl acrylate / methyl methacrylate (0 to 40/5) ~ 30 / 30-95; mass ratio). Here, the copolymer composed of an aromatic vinyl compound / maleimide compound includes one obtained by imidizing an acid anhydride of an aromatic vinyl compound / maleic anhydride copolymer with an amine compound (for example, aniline). In this case, the acid anhydride may not be completely imidized and part of the acid anhydride may remain, but this is also included in the aromatic vinyl compound / maleimide compound copolymer.

  Moreover, when combining a functional group containing unsaturated compound with the above-mentioned preferable monomer combination, it is 0-30 mass% normally with respect to 100 mass% of monomers whole quantity, Preferably it is 0-20 mass%, Furthermore, Preferably it is 0-15 mass%.

The vinyl polymer (B) of the present invention can be produced by known polymerization methods such as emulsion polymerization, solution polymerization, bulk polymerization, suspension polymerization, and a polymerization method combining these.
The intrinsic viscosity [η] (measured in methyl ethyl ketone at 30 ° C.) of the component (B) of the present invention is usually 0.1 to 1.5 dl / g, preferably 0.2 to 1.0 dl / g. When the intrinsic viscosity [η] is within the above range, the balance between molding processability and impact resistance is excellent. The intrinsic viscosity can be adjusted by appropriately selecting the type and amount of chain transfer agent used during production, the type and amount of polymerization initiator, the polymerization temperature, and the like.

  The blending ratio of the component (A) and the component (B) in the thermoplastic resin composition of the present invention is such that the component (A) is 5 to 100 parts by mass, and the component (B) is 0 to 95 parts by mass. The blending ratio is determined so that the amount of polyorganosiloxane in the thermoplastic resin composition is preferably 5 to 40% by mass, more preferably 7 to 35% by mass, and particularly preferably 10 to 30% by mass. If the amount of polyorganosiloxane is less than 5% by mass, the squeaking noise reduction and impact resistance tend to be inferior, while if it exceeds 40% by mass, the surface appearance of the molded product tends to be inferior.

The component (C) of the present invention can be copolymerized with an aromatic vinyl compound or an aromatic vinyl compound and the aromatic vinyl compound in the presence of 5 to 80% by mass of the conjugated diene rubber polymer (d). It is a conjugated diene rubber-based thermoplastic resin obtained by graft polymerization of 20 to 95% by mass of the monomer (b) composed of other vinyl monomers.
The conjugated diene rubbery polymer (d) used here is a homopolymer such as polybutadiene or polyisoprene; a styrene / butadiene random copolymer, a styrene / butadiene / styrene block copolymer, or an acrylonitrile / butadiene random. Examples include butadiene-based copolymers such as copolymers; isoprene-based copolymers such as styrene / isoprene random copolymers and styrene / isoprene / styrene block copolymers. These can be used alone or in combination of two or more. The conjugated diene rubbery polymer (d) may be a crosslinked polymer or an uncrosslinked polymer. Particularly preferred component (d) is a polybutadiene homopolymer and a styrene-butadiene random copolymer. If necessary, it can be used in combination with an ethylene / α-olefin rubber polymer or an acrylic rubber polymer.

  As the monomer (b) used here, all the monomers (b) described in the component (A) can be used, and these can be used alone or in combination of two or more.

  What is preferable here is a combination of an aromatic vinyl compound and another vinyl monomer copolymerizable with the aromatic vinyl compound. More preferred combinations here are aromatic vinyl compounds / vinyl cyanide compounds, aromatic vinyl compounds / (meth) acrylic acid esters, aromatic vinyl compounds / vinyl cyanide compounds / (meth) acrylic acid esters, aromatic vinyl compounds. / Maleimide compounds, particularly preferably styrene / acrylonitrile (60-90 / 10-40; mass ratio), styrene / methyl methacrylate (10-90 / 10-90; mass ratio), styrene / phenylmaleimide (50- 95/5 to 50; mass ratio).

  Moreover, when combining a functional group containing unsaturated compound with the above-mentioned preferable monomer combination, it is 0-30 mass% normally with respect to 100 mass% of monomers whole quantity, Preferably it is 0-20 mass%, Furthermore, Preferably it is 0-15 mass%.

  The component (C) of the present invention is a graft polymer obtained by graft polymerization of the monomer (b) in the presence of the conjugated diene rubbery polymer (d). A graft copolymer in which the (co) polymer of the monomer component (b) is grafted to the component (d), and a (co) polymer of the (b) component that is not grafted to the component (d). included. However, this graft copolymer may contain (d) component which (b) component (co) polymer is not grafted.

The component (C) of the present invention can be produced by a known polymerization method such as emulsion polymerization, solution polymerization, suspension polymerization, bulk polymerization, and a combination thereof.
(C) component of this invention is mix | blended in order to further improve impact resistance, maintaining the squeaking noise reduction property and the molded article surface appearance which are the objectives of the present invention. Those produced by emulsion polymerization are preferred, and the rubber particle size of the conjugated diene rubbery polymer (d) latex used here is 50 to 800 nm, preferably 100 to 700 nm in terms of volume average particle size. It is preferable. Here, the volume average particle diameter can be measured by a known method such as a dynamic light scattering method. The gel content of the conjugated diene rubbery polymer (d) used in the emulsion polymerization is preferably 10 to 99%, more preferably 20 to 98%, particularly preferably 30 to 98%. When the content is in the above range, the balance of molding processability, impact resistance and molded product surface appearance is excellent.

In addition, the said gel content rate can be calculated | required with the following method.
First, 1 gram of the conjugated diene rubbery polymer (d) was put into 100 ml of toluene, allowed to stand at room temperature for 48 hours, and then filtered through a 100-mesh wire mesh (with a mass of W1 gram). Is vacuum-dried at 80 ° C. for 6 hours, weighed (mass W2 gram), and calculated by the following formula.

  Gel content (mass%) = (W2−W1) / 1 × 100

  In addition, the charged composition when the monomer (b) is graft-polymerized to the conjugated diene rubbery polymer (d) is preferably 5 to 80% by mass of the component (d), more preferably 10 to 80% by mass, Especially preferably, it is 10-70 mass%. On the other hand, the component (b) is preferably 20 to 95% by mass, more preferably 20 to 90% by mass, and particularly preferably 30 to 90% by mass (provided that (d) + (b) = 100% by mass). When the range of the component (d) is less than 5% by mass and the range of the component (b) exceeds 95% by mass, the impact resistance tends to be inferior. On the other hand, if the range of the component (d) exceeds 80% by mass and the range of the component (b) is less than 20% by mass, the impact resistance and the molded product surface appearance tend to be inferior.

  The graft ratio of the conjugated diene rubber-based thermoplastic resin (C) thus obtained is usually 30 to 200% by mass, preferably 40 to 100% by mass. When this graft ratio is less than 30% by mass and more than 200% by mass, impact resistance may be lowered. The graft ratio can be determined by the following formula.

  Graft ratio (mass%) = [(S−T) / T] × 100

  In the above formula, S represents 1 gram of the conjugated diene rubber thermoplastic resin (C) in 20 ml of acetone, shaken with a shaker for 2 hours under a temperature condition of 25 ° C., and then centrifuged at room temperature with a centrifuge (rotating Number: 23,000 rpm) for 60 minutes, and the mass (g) of insoluble matter obtained by separating the insoluble matter and the soluble matter. T is a conjugated diene system contained in 1 gram of component (C) It is the mass (gram) of the rubber-like polymer (d). The mass of the conjugated diene rubbery polymer (d) can be obtained by a method of calculating from a polymerization prescription and a polymerization conversion rate or a method of obtaining from an infrared absorption spectrum (IR).

  The intrinsic viscosity [η] (measured in methyl ethyl ketone at 30 ° C.) of the acetone-soluble component of the conjugated diene rubber-based thermoplastic resin (C) is usually 0.1 to 1.5 dl / g, preferably 0.8. 2 to 1.0 dl / g. When the intrinsic viscosity [η] is within the above range, the balance between physical properties of molding processability and impact resistance is excellent. Here, the intrinsic viscosity can be adjusted by appropriately selecting the type and amount of chain transfer agent used during production, the type and amount of polymerization initiator, the polymerization temperature, and the like.

Component (A) of the present invention, the mass of (B), (C) in the thermoplastic resin composition containing the component, polyorganosiloxane (a) and the conjugated diene-based rubbery polymer of the composition (d) The ratio (a) :( d) is preferably used in the range of 5 to 95:95 to 5 from the viewpoint of impact resistance, molded product surface appearance and squeaking noise reduction effect, more preferably 50 to 90:50 to 10, Most preferably, it is 60-88: 40-12. In addition, the total amount of the polyorganosiloxane (a) and the conjugated diene rubbery polymer (d) in the total 100 parts by mass of the component (A), if necessary, the component (B) and the component (C) is 3 to 3. 40 parts by mass is preferable from the viewpoint of impact resistance.

  The thermoplastic resin composition of the present invention further includes an olefin resin (E), a low molecular weight polyethylene oxide (F), an ultrahigh molecular weight polyethylene (G), a polytetrafluoroethylene resin (H), and a silicone oil (I). ) With respect to 100 parts by mass of the thermoplastic resin composition or the thermoplastic resin composition (D) (hereinafter, both compositions may be simply referred to as a thermoplastic resin composition). 0.1-30 mass parts can be mix | blended.

  As olefin type resin (E) used here, the olefin resin which consists of at least 1 sort (s) of C2-C10 olefin resin is mentioned, for example. This olefin resin (E) can be used alone or in combination of two or more.

Examples of olefins used for forming the olefin resin (E) include ethylene and propylene, butene-1, pentene-1, hexene-1, 3-methylbutene-1, 4-methylpentene-1, 3- Examples include α-olefins such as methylhexene-1 and cyclic olefins such as norbornene. These can be used alone or in combination of two or more. Of these, ethylene, propylene, butene-1, 3-methylbutene-1, 4-methylpentene-1, and norbornene are preferable.
Other monomers that can be used as necessary in the formation of the olefin resin (E) include 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 7-methyl-1, Non-conjugated dienes such as 6-octadiene and 1,9-decadiene are exemplified.

As the olefin resin (E), polymers mainly containing propylene units such as polypropylene and propylene / ethylene copolymers, polyethylene, and ethylene / norbornene copolymers are preferable, and these are used alone or in combination of two or more. May be. The propylene / ethylene copolymer includes a random copolymer and a block copolymer, and any of them can be used.
As the polyethylene, any of high density polyethylene, low density polyethylene, linear low density polyethylene, and the like can be used.
As the polyolefin-based resin used in the present invention, those obtained by removing the polymerization catalyst or those modified with an acid anhydride group, a carboxyl group and an epoxy group can be used.

It does not matter whether the olefin resin (E) has crystallinity, but it is preferable to use at least one of those having a crystallinity of 10% or more by X-ray diffraction at room temperature.
Moreover, it is preferable to use at least 1 type of melting | fusing point measured based on JISK7212 of olefin resin (E) 40 degreeC or more.
When a polypropylene resin is used as the component (E) of the present invention, the melt flow rate measured according to JIS K7210: 1999 (230 ° C., load 2.16 kg) is preferably 0.01 to 500 g / 10 min. More preferably, it is 0.05 to 100 g / 10 min. When a polyethylene resin is used, the melt flow rate measured according to JIS K6922-2 (190 ° C., load 2.16 kg) is preferably 0.00. The amount is from 01 to 500 g / 10 minutes, more preferably from 0.05 to 100 g / 10 minutes, and particularly preferably from 0.1 to 60 g / 10 minutes.
Furthermore, in order to more effectively achieve the stagnation noise reduction effect that is the object of the present invention, a polyethylene resin is used in the olefin resin, or a polyethylene resin is included.

  The olefin resin (E) is preferably 5 to 100 parts by mass, more preferably 5 to 80 parts by mass, and particularly preferably 10 to 60 parts by mass with respect to 100 parts by mass of the thermoplastic resin composition of the present invention. If the amount used is less than 5 parts by mass, the effect of improving the squeaking noise tends not to be obtained. On the other hand, if it exceeds 100 parts by mass, the effect of improving the squeaking noise is inferior.

When the olefin resin (E) is blended with the thermoplastic resin composition of the present invention, a polymer block mainly composed of styrene and butadiene are mainly composed for the purpose of improving the compatibility between the thermoplastic resin and the olefin resin. It is preferable to blend a block copolymer composed of the polymer block or a hydride (J) thereof. The structure of these block copolymers is particularly preferably a (hydrogenated) styrene-butadiene-styrene triblock copolymer.
The said (hydrogenated) block copolymer (J) can be used in 5-100 mass parts with respect to 100 mass parts of the thermoplastic resin composition of this invention.

Low molecular weight oxidized polyethylene (F) has a number average molecular weight modified with a carboxylic acid group and / or an acid anhydride group (measured by GPC method) of 800 to 10,000, preferably 800 to 6,000, more preferably. Is from 1,000 to 5,000, particularly preferably from 1,200 to 4,000. The acid value representing the addition amount of the acid component is usually 1 to 40 (mg KOH / g), preferably 10 to 40 (mg KOH / g), more preferably 10 to 35 (mg KOH / g), and particularly preferably 10 To 30 (mg KOH / g). If the molecular weight is less than 800, the effect of improving the stagnation sound is reduced. On the other hand, if it exceeds 10,000, the impact resistance may be inferior. Further, if the acid value is less than 1, the effect of improving the squeaking noise is small, and if it exceeds 40, appearance defects such as silver streaks may occur at the time of molding, which is not preferable.
The low molecular weight polyethylene oxide (F) is preferably 0.1 to 30 parts by mass, more preferably 0.3 to 5 parts by mass, and particularly preferably 0 to 100 parts by mass of the thermoplastic resin composition of the present invention. It is used in the range of 3 to 3 parts by mass, and if it is less than 0.1 part, the squeaking noise tends not to be reduced, and if it exceeds 30 parts by mass, the impact resistance and the surface appearance of the molded product tend to be inferior.

The ultra high molecular weight polyethylene (G) is polyethylene having an average molecular weight of 400,000 to 6.5 million measured by a melt viscosity method in accordance with ASTM D4020, and a preferable average molecular weight is 400,000 to 3.5 million, more preferably 400,000 to 2.5 million. Even when blended with the components (A) and (B) of the present invention and melt-kneaded, the ultrahigh molecular weight polyethylene (G) of the present invention exists in an unmelted state. Preferably, the average particle size measured by the Coulter counter method is preferably 50 μm or less, more preferably 5 to 40 μm.
The component (G) is preferably 0.1 to 30 parts by mass, more preferably 0.3 to 5 parts by mass, and particularly preferably 0.3 to 100 parts by mass with respect to 100 parts by mass of the thermoplastic resin composition of the present invention. It is used in the range of 3 parts by mass, and if it is less than 0.1 part, the squeaking noise tends not to be reduced.

The polytetrafluoroethylene resin (H) is usually used as a dry lubricant. Preferably, it is in the form of fine powder, and the particle diameter of the fine powder is an average of 0.1 to 100 μm by a method of measuring a dispersion dispersed in perchlorethylene by a light transmission method. The melting point of the polytetrafluoroethylene fine powder is preferably 320 ° C. or higher by DSC measurement. Since the polytetrafluoroethylene fine powder is easily re-agglomerated, some of it has been subjected to a treatment such as a baking treatment in order to make it difficult to re-agglomerate, and these can be preferably used.
The component (H) is preferably 0.1 to 30 parts by mass, more preferably 0.3 to 5 parts by mass, particularly preferably 0.3 to 100 parts by mass with respect to 100 parts by mass of the thermoplastic resin composition of the present invention. It is used in the range of 3 parts by mass, and if it is less than 0.1 part, the squeaking noise tends not to be reduced.

As the silicone oil as the component (I), a known one can be used as long as it has a polyorganosiloxane structure. These may be non-modified silicone oils such as dimethyl silicone oil, methylphenyl silicone oil, methyl hydrogen silicone oil, etc., or may be a part of the side chain in the polyorganosiloxane structure and / or the polyorganosiloxane structure. It may be a modified silicone oil in which various organic groups are introduced into one terminal part or both terminal parts of the polyorganosiloxane structure. Examples of the modified silicone oil include alkyl modified silicone oil, polyether modified silicone oil, fluorine modified silicone oil, higher alkoxy modified silicone oil, higher fatty acid modified silicone oil, methyl styryl modified silicone oil, methyl chlorinated phenyl silicone oil, methyl hydro Gen silicone oil, amino modified silicone oil, epoxy modified silicone oil, carboxyl modified silicone oil, acrylic acid modified silicone oil, methacrylic acid modified silicone oil, mercapto modified silicone oil, phenol modified silicone oil, carbinol modified silicone oil, etc. are used. be able to.
These silicone oils can be used alone or in combination of two or more.

  The kinematic viscosity at 23 ° C. of the silicone oil (I) used in the present invention is preferably 60 to 500.000 cSt, more preferably 500 to 350,000 cSt, particularly preferably 1,000 to 200,000 cSt, and this range. Outside, the effect of reducing itchiness is inferior, which is not preferable. The kinematic viscosity of the silicone oil was measured with an Ubbelohde viscometer according to ASTM D445-46T (JIS8803 is acceptable).

  The silicone oil (I) component is preferably 0.1 to 8 parts by mass, more preferably 0.5 to 5 parts by mass, particularly preferably 100 parts by mass of the thermoplastic resin composition of the present invention. 2.5 to 3.5 parts by mass. When the blending amount of the component (I) is less than 0.1 parts by mass, the effect of reducing the squeaking noise tends to be inferior, and when it exceeds 8 parts by mass, the surface appearance and impact resistance of the molded product tend to be inferior. In some cases, melt kneading may be difficult when producing the thermoplastic resin composition of the present invention.

  In the thermoplastic resin composition of the present invention, if necessary, a filler, a nucleating agent, a lubricant, a heat stabilizer, an antioxidant, an ultraviolet absorber, a flame retardant, an anti-aging agent, a plasticizer, an antibacterial agent, Various additives such as fungicides, colorants (pigments, dyes, etc.), antistatic agents and the like can be contained within a range not impairing the object of the present invention.

  Moreover, a well-known inorganic or organic filler can be mix | blended with the thermoplastic resin composition of this invention. The filler used here is glass fiber, glass flake, glass fiber milled fiber, glass powder, glass bead, hollow glass bead, carbon fiber, carbon fiber milled fiber, silver, copper, brass, iron, etc. Powder or fibrous material, carbon black, tin-coated titanium oxide, tin-coated silica, nickel-coated carbon fiber, multi-luke, calcium carbonate, calcium carbonate whisker, wollastonite, mica, kaolin, montmorillonite, hextrite, zinc oxide whisker, There are potassium titanate whisker, aluminum borate whisker, plate-like aluminum, plate-like silica and organically treated smectite, aramid fiber, phenyl resin, polyester fiber, etc., and these may be used alone or in combination of two or more. it can.

Furthermore, for the purpose of improving the dispersibility of the filler, those treated with a known coupling agent, surface treatment, sizing agent, etc. can be used. With known coupling agents, surface treatment agents, sizing agents, etc. It can be used after treatment, and known coupling agents include silane coupling agents, titanate coupling agents, aluminum coupling agents and the like.
The said inorganic or organic filler is normally used in 1-200 mass parts with respect to 100 mass parts of the thermoplastic resin composition of this invention.

  Furthermore, the thermoplastic resin composition of the present invention includes other polymers such as other polyolefin resins, thermoplastic aromatic polyester resins, thermoplastic aliphatic polyesters, thermoplastic polyurethanes, polycarbonates depending on the required performance. Polyphenylene sulfide, polyamide, polyamide elastomer, polyester elastomer, polyolefin elastomer, polyurethane elastomer and the like can be appropriately blended. These can be used alone or in combination of two or more.

  The thermoplastic resin composition of the present invention is prepared by mixing each component at a predetermined mixing ratio using a tumbler mixer, a Henschel mixer, etc. It can be produced by melt-kneading under suitable conditions using a mixer. A preferred kneading method is a method using an extruder. Furthermore, when each component is kneaded, each component may be kneaded in a lump or may be kneaded in multiple stages. In addition, after knead | mixing with a Banbury mixer, a kneader, etc., it can also pelletize with an extruder. Moreover, it is preferable to supply the fibrous material among the fillers from the middle of the extruder using an addition method such as a side feeder in order to prevent cutting during kneading. The melt kneading temperature is usually in the range of 180 to 300 ° C.

  The contact component of the present invention is obtained by molding the above thermoplastic resin composition. There is no limitation on the method for producing the contact component of the present invention comprising the thermoplastic resin composition, and injection molding, injection compression molding, gas assist molding, press molding, calender molding, T-die extrusion molding, and profile extrusion molding. It can be produced by a known method such as film molding.

There are no particular limitations on the other members with which the contact parts of the present invention come into contact. For example, thermoplastic resins, thermosetting resins, rubbers, organic materials, inorganic materials, metal materials, etc. containing the rubber-reinforced styrene-based resin of the present invention Is mentioned.
Here, examples of the thermoplastic resin include polyvinyl chloride, polyethylene, polypropylene, ABS resin, AES resin, ASA resin, polystyrene, impact-resistant polystyrene, ethylene-vinyl acetate copolymer, polyamide (PA), and polybutylene terephthalate. (PBT), polyethylene terephthalate, polycarbonate (PC), aliphatic polyester such as polylactic acid, PC and / or PBT / ABS resin, PC and / or PBT / AES resin, PA / ABS resin, PA / AES resin and the like. These can be used individually by 1 type or in combination of 2 or more types.

  Examples of the thermosetting resin include phenol resin, epoxy resin, urea resin, melamine resin, unsaturated polyester resin, and thermosetting polyurethane. These can be used alone or in combination of two or more.

  Rubbers include chloroprene rubber, polybutadiene rubber, ethylene / propylene rubber, styrene / butadiene block copolymer, hydrogenated styrene / butadiene block copolymer, styrene / isoprene block copolymer, hydrogenated styrene / isoprene system. Examples include various synthetic rubbers such as block copolymers, natural rubber, and the like.

  Examples of organic materials include insulation board, MDF (medium fiber board), hard board, particle board, lumbar core, LVL (single board laminate), OSB (orientation board), PSL (pararam), WB ( Wafer board), hard fiber board, soft fiber board, lumbar core plywood, special core-plywood, veneer core-veneer board, laminated sheet / board of paper impregnated with tap resin, (old) fine pieces / lines of crushed paper, etc. Examples thereof include a board obtained by mixing an adhesive with an adhesive and heat-compressing it, and various kinds of wood.

Examples of the inorganic material include calcium silicate board, flexible board, homocement board, gypsum board, sizing gypsum board, gypsum lath board, decorative gypsum board, composite gypsum board, various ceramics, and glass.
Furthermore, iron, aluminum, copper, various alloys, etc. are mentioned as a metal material.
Among the other members that come into contact with the contact parts of the present invention described above, the thermoplastic resin, the thermosetting resin, and the rubber are preferable, and the effect of reducing the squeaking noise that is the object of the present invention is preferable. Preferably, it is a composition with ABS resin, AES resin, ASA resin, and PC.

The contact component of the present invention can be suitably used for automobile interior parts, office equipment, house interior parts and the like having portions that contact, join, and fit with other members.
The automotive interior part of the present invention can greatly reduce the squeaking noise that occurs when it comes into contact with and rubs against other members. Furthermore, it is excellent in safety at the time of collision by performing ductile fracture. Such automobile interior parts include door trim, door lining, pillar garnish, console, door pocket, ventilator, duct, air conditioner, meter visor, instrument panel upper garnish, instrument panel garnish, A / T indicator, on / off switches (slide part, Slide plate), grill front defroster, grill side defroster, lid cluster, cover intro, masks (mask switch, mask radio, etc.), glove box, pockets (pocket deck, pocket card, etc.), steering wheel horn pad, switch Examples include parts and exterior parts for car navigation. Among them, it can be particularly suitably used as a ventilator for automobiles, plate blades of air conditioners for automobiles, valve shutters, louvers, switch parts, car navigation exterior parts, and the like.

  The parts for office equipment according to the present invention can greatly reduce the squeaking noise generated by contacting and rubbing with other members. Furthermore, it is excellent in safety, such as a collision, by performing ductile fracture. Such contact parts for office equipment can be suitably used for desk lock parts, desk drawers, and the like.

  The house interior part of the present invention can greatly reduce the squeaking noise generated by contacting and rubbing with other members. Furthermore, it is excellent in safety, such as a collision, by performing ductile fracture. Such house interior parts can be particularly suitably used as shelf doors, chair dampers, table folding leg movable parts, door opening / closing dampers, sliding door rails, curtain rails, and the like.

  The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples unless they exceed the gist of the present invention. In the examples, parts and% are Unless otherwise specified, it is based on mass.

(1) Evaluation method:
Various measurements in Examples and Comparative Examples were based on the following methods.

(1-1) Itching sound evaluation 1
Using an injection molding machine “J-100E” (model name) manufactured by Nippon Steel Co., Ltd., a thermoplastic resin composition described in Table 1 and a PC / ABS resin “CK43” (trade name) manufactured by Technopolymer Co., Ltd. An ISO dumbbell test piece consisting of Next, 5 ISO test pieces made of the thermoplastic resin composition shown in Table 1 and 5 ISO dumbbell test pieces made of “CK43” were alternately overlapped, and the both ends were twisted by hand to generate a squeaking sound. The occurrence situation was evaluated. Evaluation was performed 5 times, and determination was performed based on the following evaluation criteria.
(Double-circle): There was no generation | occurrence | production of a squeaking sound in all five evaluations.
O: The occurrence of itching was slight in all five evaluations.
(Triangle | delta): The case where generation | occurrence | production of a squeaking sound was remarkable was contained in five evaluations.
X: In all five evaluations, the generation of itching sound was significant.
(1-2) Itching sound evaluation 2:
The test piece obtained above was left in a gear oven at 80 ° C. for 400 hours. Using the test piece, the state of occurrence of the squeaking sound was evaluated by the same method as the squeaking sound evaluation 1 in (1-1) above.

(1-3) Impact resistance (falling weight impact strength):
Using an electric injection molding machine “Erject NEX30” (model) manufactured by Nissei Plastic Industrial Co., Ltd., 230 flat plate test pieces of 80 mm × 55 mm × 2.4 mm made of the thermoplastic resin composition described in Table 1 were used. Injection molded at ℃.
Next, using the Shimadzu hydro-shot / high-speed puncture impact tester “HITS-P10” (model name) manufactured by Shimadzu Corporation, the specimen was punched out under the following conditions, and the fracture energy (J) was measured.
Measurement temperature: 23 ° C
Punching speed: 5.6 mm / s
Strike tip r of punching test jig: 12.7 mm

(1-4) Molded product surface appearance:
The surface state of the test piece for measuring the falling weight impact strength was visually observed and evaluated according to the following criteria.
◯: Good with no appearance defects such as flow marks.
Δ: Some appearance defects such as flow marks are recognized, and the appearance is slightly inferior.
X: Appearance defects such as a flow mark are remarkable and appearance is inferior.

(2) (A) Component (2-1) Production Example 1: Modified polyorganosiloxane latex 1.5 parts of p-vinylphenylmethyldimethoxysilane and 98.5 parts of octamethylcyclotetrasiloxane were mixed and this was added to dodecylbenzene. Into 300 parts of distilled water in which 2.0 parts of sulfonic acid was dissolved, the mixture was stirred for 3 minutes with a homomixer and emulsified and dispersed. The mixture was transferred to a separable flask equipped with a condenser, a nitrogen inlet, and a stirrer, heated at 90 ° C. for 6 hours with stirring and mixed, and cooled at 5 ° C. for 24 hours to complete the condensation reaction. The condensation ratio of the resulting modified polyorganosiloxane was 92.8%. The modified polyorganosiloxane latex was neutralized with an aqueous sodium carbonate solution.
The resulting modified polyorganosiloxane latex had a volume average particle size of 280 nm.

(2-2) Production Example 2: Polyorganosiloxane thermoplastic resin A1 (polyorganosiloxane / styrene / acrylonitrile copolymer)
A glass flask having an internal volume of 7 liters equipped with a stirrer, 100 parts of ion exchange water, 1.5 parts of sodium dodecylbenzenesulfonate, 0.1 part of tert-dodecyl mercaptan, 40 parts of modified polyorganosiloxane (solid content), styrene 15 parts and 5 parts of acrylonitrile were added, and it heated up, stirring. When the temperature reaches 45 ° C., 0.1 part of sodium ethylenediaminetetraacetate, 0.004 part of ferrous sulfate heptahydrate, 0.2 part of sodium formaldehyde sulfoxylate dihydrate and ion-exchanged water An aqueous solution consisting of 15 parts and 0.1 part of diisopropylbenzene hydroperoxide were added and the reaction was continued for 1 hour. Thereafter, a continuous addition component consisting of 50 parts of ion-exchanged water, 1 part of sodium dodecylbenzenesulfonate, 0.1 part of tert-dodecyl mercaptan, 0.2 part of diisopropyl hydroperoxide, 30 parts of styrene and 10 parts of acrylonitrile is taken over 3 hours. The polymerization reaction was continued while adding to the polymerization system. After completion of the addition, stirring was further continued for 1 hour. At this time, the polymerization conversion rate was 97%. The polymerization was completed by adding 0.2 part of 2,2'-methylene-bis (4-methyl-6-tert-butylphenol). The reaction product latex was taken out from the flask, coagulated with an aqueous solution of 2 parts of calcium chloride, washed with water, and dried at 80 ° C. to obtain a white powder of polyorganosiloxane thermoplastic resin A1. The graft ratio of the resin A1 was 90%, and the intrinsic viscosity [η] was 0.47 dl / g.

(3-1) Production Example 3; Vinyl-based polymer B1 (styrene / acrylonitrile copolymer)
Two stainless steel autoclaves having a ribbon wing with an internal volume of 30 liters were connected and purged with nitrogen, and then 75 parts of styrene, 25 parts of acrylonitrile and 20 parts of toluene were continuously added to the first reaction vessel. A solution of 0.12 part of tert-dodecyl mercaptan and 5 parts of toluene as a molecular weight regulator, and 0.1 part of 1,1′-azobis (cyclohexane-1-carbonitrile) and 5 parts of toluene as a polymerization initiator The solution was continuously fed. The polymerization temperature of the first group was controlled at 110 ° C., the average residence time was 2.0 hours, and the polymerization conversion was 57%. The obtained polymer solution was continuously taken out from the first reaction vessel by the same amount as the styrene, acrylonitrile, toluene, molecular weight regulator and polymerization initiator supplied by the pump provided in the second reaction vessel. The reaction vessel was fed. The polymerization temperature of the second reaction vessel was 130 ° C., and the polymerization conversion was 75%. The copolymer solution obtained in the second reaction vessel was directly devolatilized from the unreacted monomer and solvent using a twin-screw, three-stage vented extruder, and the intrinsic viscosity [η] 0.48 dl / g of vinyl polymer B1 was obtained.

(4) Component (4-1) Production Example 4; Conjugated Diene Rubber Thermoplastic Resin C1 (Conjugated Diene Rubber / Styrene / Acrylonitrile Copolymer)
In a 7-liter glass flask equipped with a stirring blade, in a nitrogen stream, 95 parts of ion exchanged water, 0.5 part of potassium rosinate, 0.1 part of tert-dodecyl mercaptan, polybutadiene latex (average particle size 200 nm, Gel content 85%) 30 parts (solid content), butadiene / styrene random polymer latex (average particle size 600 nm, styrene content 25%) 10 parts (solid content), styrene 14.6 parts, acrylonitrile 5.4 parts In addition, the temperature was raised while stirring. When the internal temperature reached 45 ° C., a solution in which 0.2 parts of sodium pyrophosphate, 0.01 parts of ferrous sulfate heptahydrate and 0.2 parts of glucose were dissolved in 20 parts of ion-exchanged water was added. . Thereafter, 0.07 part of cumene hydroperoxide was added to initiate polymerization. After polymerization for 1 hour, 50 parts of ion-exchanged water, 0.7 parts of potassium rosinate, 29.2 parts of styrene, 10.8 parts of acrylonitrile, 0.05 parts of tert-dodecyl mercaptan, and cumene hydroperoxide 0.01 The polymer conversion after 98 parts was continuously added over 3 hours and the polymerization was continued for 1 hour was 98%. Thereafter, 0.2 part of 2,2′-methylene-bis (4-methyl-6-tert-butylphenol) was added to complete the polymerization. The obtained polymer latex was coagulated with an aqueous sulfuric acid solution, washed with water, and then dried to obtain a conjugated diene rubber thermoplastic resin C1.
The graft ratio of this resin C1 was 68%, and the intrinsic viscosity [η] was 0.45 dl / g with respect to the acetone soluble component.

(5) Component (E): Olefin resin The following ones manufactured by Nippon Polyethylene Co., Ltd. were used.
E1; Novatec HDHJ560 (trade name)
High density polyethylene, melt flow rate 7g / 10min

(6) Component (F): Low molecular weight polyethylene The followings manufactured by Sanyo Chemical Industries, Ltd. were used.
F1: Sun wax EP-250P (trade name)
Acid value 20 mgKOH / g, average molecular weight 2000

(7) Component G: Ultrahigh molecular weight polyethylene The followings manufactured by Mitsui Chemicals were used.
G1; Mipperon XM-221U (trade name)
Average molecular weight 2 million, average particle size 25 μm

(8) Component (H): Polytetrafluoroethylene resin The following were manufactured by Daikin Industries, Ltd.
H1; Lubron L-5 (trade name)
Average particle diameter of about 7μm

(9) Component (I): Silicone oil The followings manufactured by Shin-Etsu Silicone Co., Ltd. were used.
I1; KF-96H-10 thousand cSt (trade name)
Dimethyl silicone oil, kinematic viscosity at 25 ° C. 10,000 cSt

(10) Component (J): Hydrogenated block copolymer The followings manufactured by Asahi Kasei Chemicals Corporation were used.
J1; Tuftec H1041 (trade name)
Hydrogenated product of styrene-butadiene-styrene block copolymer having a styrene / butadiene ratio of 30/70, melt flow rate of 5.0 g / 10 min [according to JISK7210 (230 ° C., load 2.16 kgf)]

Examples 1-6 , Comparative Example 1
Each component is mixed by a Henschel mixer at the blending ratio shown in Table 1, and then melt-kneaded using a vented twin screw extruder (manufactured by Nippon Steel Works, TEX44, barrel setting temperature 240 ° C.) to form a thermoplastic resin composition. Product was obtained and pelletized. After sufficiently drying the obtained pellet, a test piece was molded by the above method using this pellet, and evaluated by the above method using the obtained test piece. The evaluation results are shown in Table 1.

As can be seen from Table 1, the thermoplastic resin compositions of the present invention represented by Examples 1 to 6 are reduced in the stagnation sound targeted by the present invention, and further have impact resistance and molded product surface appearance. We provide molded products with a good balance.
On the other hand, Comparative Example 1 is an example in which a butadiene-based rubbery polymer (d) is used in place of the polyorganosiloxane (a) of the present invention as the rubber type of the component (A) of the present invention, The effect of reducing itchiness is inferior.

Example 7
As shown in FIG. 1, the contact part A is composed of the thermoplastic resin composition of Example 1, a T-shaped part composed of the bottom part 1 and the rising part 2, and the other contact part B is a technopolymer. PC / ABS “CK43” (trade name) made of PC, which is made of a bottom part 3 and two rising parts 4, 4 for tightly holding the rising part 2, is manufactured. After being left in a gear oven at ℃ for 200 hours, the rising part 2 of the T-shaped part is assembled so as to be sandwiched between the two rising parts 4 and 4 of the sandwiched part, and is slid as indicated by the arrows. The presence or absence of itching sound was examined. As a result, no generation of itching sound was observed.

Comparative Example 2
Except for changing the thermoplastic resin composition of the T-shaped part to the thermoplastic resin composition of Comparative Example 1 as the contact part A, the presence or absence of stagnation noise was examined in the same manner as in Example 7 . As a result, it was recognized that stagnation was generated in all cases.

  As is apparent from the above, the thermoplastic resin composition contact parts of the present invention are used for automobile interior parts, office equipment, house interior parts and the like having portions that contact, join, and fit with other members. It turns out that it is suitable.

  The contact component according to the present invention significantly reduces the squeaking noise that occurs when the members rub against each other, and maintains the squeaking noise reduction effect even when left at high temperatures for a long time. It is possible to provide contact parts made of a thermoplastic resin composition having excellent properties, and is suitable for automobile interior parts, office equipment, house interior parts, etc. that have locations where they can contact, join and fit with other members. Can be used. As an automobile interior part, it is particularly suitable for an automobile ventilator or the like.

DESCRIPTION OF SYMBOLS 1 Bottom part 2 Rising part 3 Bottom part 4 Rising part

Claims (6)

A thermoplastic resin composition comprising the following component (A), component (B) and component (C), wherein component (A) is 5 to 100 parts by mass, and component (B) is 0 to 95: The total of component (A) and component (B) is 100 parts by mass, and component (C) is polyorganosiloxane (a) and conjugated diene rubber polymer (d) in the thermoplastic resin composition. the weight ratio of (a) :( d) is 50 to 90: 50 to a 10, the contact parts, characterized in that contact with the component made of thermoplastic resin composition, or other thermoplastic resin:
(A) Monomer (b) comprising an aromatic vinyl compound or an aromatic vinyl compound and another vinyl monomer copolymerizable with the aromatic vinyl compound in the presence of the polyorganosiloxane (a) A polyorganosiloxane thermoplastic resin obtained by polymerizing
(B) a vinyl polymer obtained by polymerizing one or more vinyl monomers (c),
(C) An aromatic vinyl compound or an aromatic vinyl compound and another vinyl monomer copolymerizable with the aromatic vinyl compound in the presence of the conjugated diene rubbery polymer (d) (b) The rubber particle size of the component (d) is 50 to 800 nm in terms of volume average particle size, the component (d) is 5 to 80% by mass, the graft ratio is 30 to 200% by mass, and the acetone soluble component A conjugated diene rubber-based thermoplastic resin having an intrinsic viscosity [η] of 0.1 to 1.5 dl / g (measured in methyl ethyl ketone at 30 ° C.). Further, olefin resin (E) (except low molecular weight polyethylene (F), ultra high molecular weight polyethylene (G), polytetrafluoroethylene resin (H)) , low molecular weight polyethylene (F), ultra high molecular weight polyethylene 2. The composition according to claim 1, comprising at least one selected from (G), polytetrafluoroethylene resin (H), silicone oil (I), and hydrogenated block copolymer (J). Contact parts. Olefin resin (E) (excluding low molecular weight polyethylene (F), ultrahigh molecular weight polyethylene (G), polytetrafluoroethylene resin (H)) and hydrogenation with respect to 100 parts by mass of the thermoplastic resin composition 5 to 100 parts by mass of block copolymer (J), 0.1 to 30 parts by mass of low molecular weight polyethylene (F), ultrahigh molecular weight polyethylene (G) and polytetrafluoroethylene (H), silicone oil (I) The contact component according to claim 2, wherein is 0.1 to 8 parts by mass. Olefin resin (E) (excluding low molecular weight polyethylene (F), ultra high molecular weight polyethylene (G), polytetrafluoroethylene resin (H)) , low molecular weight polyethylene (F), ultra high molecular weight polyethylene (G ), Polytetrafluoroethylene-based resin (H), silicone oil (I), and hydrogenated block copolymer (J) in an amount of 0.1 to 100 parts by mass of the thermoplastic resin composition. The contact component according to claim 2, wherein 30 parts by mass is blended.   The contact part according to any one of claims 1 to 4, which is used for an automobile interior part, a switch part, an office equipment part, a desk lock part, a house interior part, or an indoor door opening / closing damper part.   6. The contact part according to claim 5, wherein the automobile interior part is an automobile ventilator, a plate blade of an air conditioner for a car, a valve shutter, a louver, a switch part, or an exterior part for car navigation.

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