JP5647480B2 - 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 alkane in ABS resin A technique for 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 is used for water-related parts in bathrooms and toilets. To have.

  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 problems, the present inventors have found that a specific amount of a rubber-reinforced styrene resin or a specific amount of a vinyl polymer or the like is blended in the rubber-reinforced styrene resin. It has been found that the generation of sound is remarkably reduced, and that 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 5 to 100 parts by mass of the following (A) component and 0 to 95 parts by mass of (B) component, and the total of the (A) component and the (B) component is 100 parts by mass. Ri Do from the object, the thermoplastic resin composition or other heat consists thermoplastic resin component and the contact to the contact parts, characterized in Rukoto:
(A) 1-40% by mass of polymer block A having an aromatic vinyl compound of 90% by mass or more,
Polymer block B 30 having a 1,2-vinyl bond content of 25 to 70% and a polymer of butadiene and an aromatic vinyl compound, wherein the ratio of aromatic vinyl compound / butadiene is 1 to 40/99 to 60% by mass. 80% by mass of olefinic unsaturated bonds of the block copolymer (I) each having 1 to 80 % by mass and one or more polymer blocks C of 10 to 50% by mass of butadiene having a 1,2-vinyl bond content of less than 25% In the presence of a hydrogenated rubbery polymer (II) formed by hydrogenating at least%,
Monomer comprising an aromatic vinyl compound, or an aromatic vinyl compound and another vinyl monomer selected from a vinyl cyanide compound copolymerizable with the aromatic vinyl compound, a (meth) acrylic acid ester, and a maleimide compound A rubber-reinforced styrene-based resin obtained by graft polymerization of the body (a),
(B) A vinyl polymer obtained by polymerizing one or more vinyl monomers (b).
2. Monomer (a) is 60-90 / 10-40 mass ratio of styrene / acrylonitrile, 10-90 / 10-90 mass ratio of styrene / methyl methacrylate, 50-95 / 5-50 mass of styrene / phenylmaleimide. 2. The contact component according to 1 above, which is a ratio.
3. Further, a polybutadiene rubber-based styrene resin (Li) is blended, and the ratio of (i) component hydrogenated rubber polymer (II) / (Li) component butadiene rubber polymer is 40 to 90. 3. The contact component according to 1 or 2 above, which is / 60 to 10% by mass.
4 . Furthermore, (iii) an olefinic resin, (d) a low molecular weight polyethylene oxide, (e) ultra-high molecular weight polyethylene, (f) a polytetrafluoroethylene-based resin, (g) said at least one selected from silicone oil 1 A contact component comprising 0.1 to 30 parts by mass with respect to 100 parts by mass of the thermoplastic resin composition according to any one of .
5. (4) The above 4 characterized by comprising 5-100 parts by mass of (h) (hydrogenated) styrene-butadiene block copolymer with 100 parts by mass of the thermoplastic resin composition together with the olefinic resin. Contact parts as described.
6 . The contact part according to any one of 1 to 5 above, which is used for automobile interior parts, switch parts, office equipment parts, desk lock parts, house interior parts, or indoor door opening / closing damper parts.
7 . 7. The contact part according to 6 above, 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.

According to the present invention, (a) component, or a thermoplastic resin composition comprising (a) component and (b) component, and further (ha) to (g) and (h) components are blended as necessary. It is made of a thermoplastic resin composition that is excellent in impact resistance and surface appearance of molded products, significantly reduces the squeaking noise that occurs when parts rub against each other, and squeaks even when left at high temperatures for a long time. Contact parts that do not reduce the reduction effect can be obtained.

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 a polymer block A having an aromatic vinyl compound of 90% by mass or more, a polymer block B of butadiene and an aromatic vinyl compound having a 1,2-vinyl bond content of 25 to 70%, and Hydrogenated rubber obtained by hydrogenating 80% or more of the olefinically unsaturated bonds of the block copolymer (I) each having one or more butadiene polymer blocks C each having a 1,2-vinyl bond content of less than 25% Monomer (a) consisting of an aromatic vinyl compound or an aromatic vinyl compound and another vinyl monomer copolymerizable with the aromatic vinyl compound in the presence of the polymer (II) This is a rubber-reinforced styrene resin.

  Examples of the aromatic vinyl compound used in the block copolymer (I) component include styrene, paramethylstyrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene, and the like. Or it can use combining 2 or more types. Particularly preferred is styrene.

The polymer block A is a polymer containing 90% by mass or more of the aromatic vinyl compound or a copolymer with butadiene containing 90% by mass or more of the aromatic vinyl compound.
The content of the polymer block A in the block copolymer (I) before hydrogenation is preferably 1 to 40% by mass, more preferably 3 to 35% by mass. If it is less than 1% by mass, the surface appearance of the molded product tends to be inferior. On the other hand, if it exceeds 40% by mass, the impact resistance tends to decrease. Furthermore, the number average molecular weight of the polymer block A is preferably 5,000 to 70,000 from the viewpoint of impact resistance. Further, when the content of the aromatic vinyl compound in the polymer block A is less than 90% by mass, the impact resistance is lowered.

The polymer block B is a random copolymer of butadiene and an aromatic vinyl compound. The content of the polymer block B in the block copolymer (I) before hydrogenation is preferably 30 to 80% by mass, more preferably 35 to 70% by mass. If it is less than 30% by mass or more than 80% by mass, the mechanical strength of the resin tends to be lowered.
The ratio of the butadiene / aromatic vinyl compound in the polymer block B is preferably 99 to 60/1 to 40% by mass, more preferably 98/2 to 65/35% by mass, and particularly preferably 96/4 to 70/30. % By mass. Here, if the aromatic vinyl compound is less than 1% by weight, the glossiness of the resin is hardly exhibited, which is not preferable. On the other hand, if it exceeds 40% by mass, impact resistance tends to decrease.

  The 1,2-vinyl bond content of the polybutadiene before hydrogenation of the polymer block B is 25 to 70%, preferably 30 to 60%. When the 1,2-vinyl bond content is less than 25%, hydrogenation is performed. Sometimes polyethylene chains are formed, rubber properties are lost and impact resistance is reduced. On the other hand, if it exceeds 70%, the glass transition temperature after hydrogenation becomes high, and the impact resistance and the squeaking noise reduction are reduced. The polymer block B has a number average molecular weight of 30,000 to 300,000 due to impact resistance.

The polymer block C is polybutadiene, and the content of the polymer block C in the block copolymer (I) before hydrogenation is preferably 10 to 50% by mass, more preferably 15 to 45% by mass. If it is less than 10% by mass, the squeaking property tends to be inferior, and if it exceeds 50% by mass, the impact resistance tends to be lowered. The 1,2-vinyl bond content of the polybutadiene before hydrogenation of the polymer block C is less than 25%, preferably 3 to 20%. When the 1,2-bond content exceeds 25%, the squeaking noise reduction tends to be inferior. Further, polybutadiene having a 1,2-vinyl bond of less than 3% tends to be difficult to produce.
The polymer block C preferably has a number average molecular weight of 10,000 to 300,000 in terms of impact resistance.

The block copolymer (I) is a block copolymer having one or more polymer blocks A, B and C, respectively, or the block copolymer unit is polymer block A, B via a coupling agent residue. And C is a block copolymer bonded to a polymer unit comprising at least one polymer block.
The polymer molecular chain of the block copolymer (I) may be either linear or branched. The number average molecular weight of the block copolymer (I) is usually 40,000 to 700,000, and if it is less than 40,000, the impact resistance tends to decrease, and if it exceeds 700,000, the moldability tends to be inferior.

  The block copolymer (I) is acid-modified with an acid anhydride of α, β-unsaturated carboxylic acid such as maleic anhydride, itaconic anhydride, fumaric anhydride, or glycidyl (meth) acrylate, allyl glycidyl ether. Further, it may be used after being modified with an unsaturated compound having an epoxy group such as vinyl glycidyl ether. In this case, the compatibility when blended with other resins such as polyamide resin, polyester resin, polycarbonate resin, and PPS resin can be improved, and the performance may be improved.

  The molecular weight distribution (Mw / Mn) of the block copolymer (I) is preferably 10 or less in view of the balance of squeaking noise, impact resistance, and molded product surface appearance.

  The block copolymer (I) can be obtained, for example, by performing anion living polymerization in a hydrocarbon solvent using an organic lithium initiator. The branched polymer can be obtained by adding a necessary amount of a tri- or higher functional coupling agent at the end of the polymerization and performing a coupling reaction.

In order to control the vinyl bond content such as 1,2- and 3,4-bonds, ether ethers, tertiary amine compounds, alkali metal alkoxides such as sodium and potassium, phenoxides and sulfonates are used.
Moreover, n-butyllithium, sec-butyllithium, tert-butyllithium or the like is used as the organic lithium initiator, and as the hydrocarbon solvent, hexane, heptane, methylcyclopentane, cyclohexane, benzene, toluene, Xylene, 2-methylbutene-1, 2-methylbutene-2, etc. are used. These may be used alone or in combination of two or more.

  The polymerization may be a batch system or a continuous system, the polymerization temperature is usually in the range of 0 to 120 ° C., preferably 20 to 100 ° C., and the polymerization temperature is carried out in the range of 10 minutes to 3 hours. The coupling agent is a tri- or higher functional coupling agent, examples of which are tetrachlorosilicon, butyltrichlorosilicon, tetrachlorotin, butyltrichlorotin, tetrachlorogermanium, bis (trichlorosilyl) ethane, divinylbenzene, adipic acid Examples include diester, epoxidized liquid polybutadiene, epoxidized soybean oil, epoxidized linseed oil, tolylene diisocyanate, diphenylmethane diisocyanate, 1,2,4-benzene triisocyanate, and the like. These may be used alone or in combination of two or more.

The hydrogenated rubbery polymer (II) is obtained by hydrogenating the block copolymer (I) thus polymerized. The hydrogenated rubbery polymer (II) needs to be hydrogenated with at least 80% or more, preferably 90% or more of olefinic unsaturated bonds, and if it is less than 80%, the squeaking noise reduction property is poor.
The hydrogenation reaction is performed by dissolving the block copolymer (I) in a hydrocarbon solvent and in the presence of a hydrogenation catalyst at 20 to 150 ° C. under pressurized hydrogen of 1 to 100 kg / cm ² .

  Hydrogenation catalysts include catalysts in which noble metals such as palladium, ruthenium, rhodium and platinum are supported on silica, carbon, diatomaceous earth, etc., complex catalysts such as rhodium, ruthenium and platinum, organic carboxylic acids such as cobalt and nickel, and organic aluminum Alternatively, a catalyst composed of organic lithium, a titanium compound such as dicyclopentadienyl titanium dichloride, dicyclodienyl diphenyl titanium, dicyclopentadienyl titanium dibenzyl, and an organometallic compound composed of lithium, aluminum, and magnesium are used. These may be used alone or in combination of two or more.

The rubber-reinforced styrene resin (I) 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 the hydrogenated rubbery polymer (II). It can be obtained by graft polymerization of the monomer (a) comprising other vinyl monomers.
As the aromatic vinyl compound used here, styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, vinyltoluene, β-methylstyrene, ethylstyrene, p-tert-butylstyrene, vinylxylene, Examples include 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 preferred.
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 monomer (a) is used in combination with the aromatic vinyl compound, or a combination of the aromatic vinyl compound and the aromatic vinyl compound and the other vinyl monomer copolymerizable with the aromatic vinyl compound. 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 (a) of the present invention is a rubber-reinforced styrene resin obtained by graft polymerization of the monomer (a) in the presence of the hydrogenated rubbery polymer (II). The graft copolymer in which the (co) polymer of the monomer component (a) is grafted to the hydrogenated rubbery polymer (II) component and the hydrogenated rubbery polymer (II) component are grafted. (A) component (co) polymers are not included. However, this graft copolymer may contain a hydrogenated rubbery polymer (II) component to which the (co) polymer of the component (a) is not grafted.

The rubber-reinforced styrene-based resin that is the component (a) of the present invention can be produced by a known polymerization method such as solution polymerization, bulk polymerization, suspension polymerization, emulsion polymerization, and a polymerization method combining these.
In addition, all known materials can be used as the auxiliary material, polymerization conditions, polymerization method, and method for recovering the polymer after polymerization.
Among the above polymerization methods, solution polymerization, bulk polymerization, and bulk / suspension polymerization are preferable in terms of productivity.

The intrinsic viscosity [η] (measured at 30 ° C.) of the methyl ethyl ketone soluble part of the rubber-reinforced styrene resin (A) obtained by the above production method is preferably 0.2 dl / g or more, more preferably 0.22 to 0.22. The amount is 1.5 dl / g, particularly preferably 0.24 to 1.2 dl / g.
The dispersed particle size of the hydrogenated rubbery polymer (II) dispersed in the rubber-reinforced styrene resin (ii) is preferably in the range of 50 to 1,000 nm, more preferably 100 to 700 nm in terms of number average particle size. It is a range.
Furthermore, the graft ratio of the rubber-reinforced styrene resin (a) of the present invention is preferably 20 to 90% by mass, more preferably 25 to 85% by mass, and particularly preferably 30 to 80% by mass. When the graft ratio is less than 20% by mass, the weld strength of the injection-molded product is lowered, and the appearance of the weld part is easily noticeable. On the other hand, when the graft ratio exceeds 90% by mass, the balance between impact resistance and moldability tends to be inferior.

The graft ratio can be determined by the following formula.
Graft rate (mass%) = [(S−T) / T] × 100

  In the above formula, 1 g of rubber-reinforced styrenic resin (I) is added to 20 ml of acetone, shaken with a shaker at 25 ° C. for 2 hours, and then centrifuged at 25 ° C. under the temperature condition. This is the mass (gram) of insoluble matter obtained by centrifuging for 60 minutes with a separator (rotation speed: 23,000 rpm) and separating the insoluble matter and the soluble matter, and T is a rubber-reinforced styrene resin (ii) It is the mass (gram) of the hydrogenated rubbery polymer (II) contained in 1 gram. The mass of the hydrogenated rubbery polymer (II) can be obtained by a method calculated from the polymerization prescription and the polymerization conversion rate, a method using an infrared absorption spectrum (IR), or the like.

  The content of the hydrogenated rubber polymer (II) in the rubber-reinforced styrene resin (a) can be arbitrarily selected according to the purpose, but impact resistance, squeaking noise reduction, and appearance of the molded product surface From the balance, it is preferably 5 to 70% by mass, more preferably 10 to 65% by mass. If the hydrogenated rubber polymer (II) is less than 5% by mass, the impact resistance and the squeaking noise reduction tend to be inferior, and if it exceeds 70% by mass, the surface appearance of the molded product tends to be inferior.

  Further, in combination with the hydrogenated rubbery polymer (II) of the present invention, another hydrogenated block copolymer (III) is replaced with a hydrogenated rubbery polymer (II) and a hydrogenated block copolymer (III). By using in the range of 0 to 50% by mass in a total of 100% by mass, the balance of squeaking noise reduction, impact resistance and molded product surface appearance may be improved.

  Hydrogenated block copolymer (III) is a hydrogen of a block copolymer having a polymer block (III-1) mainly composed of an aromatic vinyl compound and a polymer block (III-2) mainly composed of a conjugated diene compound. It is at least one polymer selected from the group consisting of chemical compounds, and further enhances the compatibility of the components (a) and (b) of the present invention, reducing squeaking noise, impact resistance, and surface appearance of molded products. It is used as the main purpose to improve.

Examples of the aromatic vinyl compound used in the component (III-1) among the components (III) of the present invention include styrene, α-methylstyrene, hydroxystyrene and the like, preferably styrene and α-methylstyrene. Particularly preferred is styrene. Furthermore, the component (III-1) may partially contain a conjugated diene compound.
Examples of the conjugated diene compound include butadiene, isoprene, hexadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and preferably butadiene and isoprene. These can be used alone or in combination of two or more. Further, among the components (III), the component (III-2) may be a block in which two or more conjugated diene compounds are used and are combined in a random, block, or tapered form. The component (III-2) may contain 1 to 10 aromatic vinyl compounds and gradually increasing taper blocks, and contains a vinyl bond derived from the conjugated diene compound of the component (III-2). Polymer blocks having different amounts may be appropriately copolymerized.

A preferred structure of the component (III) of the present invention is a hydride of a block polymer represented by the following formulas (IIIa) to (IIIc).
_{(A-B) Y (IIIa} )
(AB) _Y- X (IIIb)
A- (BA) _Z (IIIc)
In the structural formulas (IIIa) to (IIIc), A is a polymer block mainly composed of an aromatic vinyl compound. If the polymer block is substantially composed of an aromatic vinyl compound, a part of the conjugated diene compound is included. It may be. The polymer block preferably contains 90% by mass or more, more preferably 99% by mass or more of the aromatic vinyl compound. B is a homopolymer of a conjugated diene compound or a copolymer of a conjugated diene compound with another monomer such as an aromatic vinyl compound, X is a residue of a coupling agent, and Y is 1-5. An integer and Z each represents an integer of 1 to 5. When B is a copolymer of another monomer such as an aromatic vinyl compound and a conjugated diene compound, the content of the other monomer in B is the conjugated diene compound and the other monomer. It is preferable that it is 50 mass% or less with respect to the sum total.

The ratio of the aromatic vinyl compound and the conjugated diene compound in the component (III) of the present invention is preferably within the range of aromatic vinyl compound / conjugated diene compound = 10-80 / 20 to 90% by mass, more preferably 25 to 25%. It is 70 / 30-75 mass%, Most preferably, it is the range of 20-60 / 40-80 mass%.
The block copolymer comprising an aromatic vinyl compound and a conjugated diene compound is known in the technical field of anionic polymerization. For example, Japanese Patent Publication No. 47-28915, Japanese Patent Publication No. 47-3252, Japanese Patent Publication No. 48-2423. And the Japanese Patent Publication No. 48-20038. A method for producing a polymer block having a tapered block is disclosed in JP-A-60-81217.

The vinyl bond content (1,2- and 3,4-bond) content derived from the conjugated diene compound of the component (III) of the present invention is preferably in the range of 5 to 80%. The number average molecular weight of the component is preferably 10,000 to 1,000,000, more preferably 20,000 to 500,000, particularly preferably 20,000 to 200,000. Among these, adjustment of the vinyl bond amount of the B part represented by the above (IIIa) to (IIIc) is N, N, N ′, N′-tetramethylethylenediamine, trimethylamine, diazocyclo (2,2,2) octamine, etc. Amines, tetrahydrofuran, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, and other ethers, thioethers, phosphines, phosphoamides, alkylbenzene sulfonates, potassium and sodium alkoxy, and the like.
A polymer in which a polymer molecular chain is extended or branched via a coupling agent residue using a coupling agent after the polymer is obtained by the above method is also preferably included in the component (III) of the present invention. Coupling agents used here include diethyl adipate, divinylbenzene, methyldichlorosilane, silicon tetrachloride, butyltrichlorosilicon, tetrachlorotin, butyltrichlorotin, dimethylchlorosilicon, tetrachlorogermanium, 1,2- Examples include dibromoethane, 1,4-chloromethylbenzene, bis (trichlorosilyl) ethane, epoxidized linseed oil, tolylene diisocyanate, 1,2,4-benzene triisocyanate, and the like. These can be used alone or in combination of two or more.

  Further, as the component (III), one obtained by partially or completely hydrogenating the carbon-carbon double bond of the conjugated diene portion of the block copolymer can be used. From the appearance of the molded product surface of the obtained composition, it is preferable to use a partially hydrogenated product and / or a completely hydrogenated product in which 50% or more is hydrogenated.

  Hydrogenation reaction of block copolymer (III) containing polymer block (III-1) mainly composed of aromatic vinyl compound and polymer block (III-2) mainly composed of conjugated diene compound obtained by the above method Can be carried out by a known method, and the target polymer can be obtained by adjusting the hydrogenation rate by a known method. Specific methods include JP-B-42-8704, JP-B-43-6636, JP-B-63-4841, JP-B-63-5401, JP-A-2-133406, JP-A-1 -297413.

  The vinyl polymer as the component (b) of the present invention is a (co) polymer obtained by polymerizing one or more vinyl monomers (b), and the vinyl polymer used here. As the monomer, the aromatic vinyl compound described in the component (a) monomer (a) and other vinyl monomers copolymerizable with the aromatic vinyl compound 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 compound, particularly preferably styrene / acrylonitrile (60-90 / 10-40; mass%), styrene / methyl methacrylate (10-90 / 10-90; mass%), styrene / phenylmaleimide (50- 95/5 to 50; mass%), α-methylstyrene / acrylonitrile / styrene (50 to 80/20 to 40/0 to 10; mass%), styrene / butyl acrylate / methyl methacrylate (0 to 40/5). -30/30 to 95; mass%). 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 combination of 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.

  In the thermoplastic resin composition of the present invention, the blending ratio of the component (a) and the component (b) is (b) the component is 5 to 100 parts by mass, and the component (b) is 0 to 95 parts by mass. The amount of the hydrogenated rubbery polymer (II) 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. Is done. If the amount of the hydrogenated rubbery polymer (II) is less than 5% by mass, the squeaking noise reduction and impact resistance tend to be inferior, whereas if it exceeds 40% by mass, the surface appearance of the molded product tends to be inferior.

The thermoplastic resin composition of the present invention has an olefin resin (c), low molecular weight oxidized polyethylene (d), ultrahigh molecular weight polyethylene (e), and polytetrafluoroethylene resin for the purpose of further improving the squeaking property. At least one selected from (f) is used in the range of 0.1 to 30 parts by weight, preferably 0.2 to 25 parts by weight, with respect to 100 parts by weight of the thermoplastic resin composition of the present invention. . If the amount used is less than 0.1 parts by mass, the effect of improving the squeaking noise reduction cannot be obtained, and if it exceeds 30 parts by mass, the impact resistance and the surface appearance of the molded product are inferior.
When low molecular weight oxidized polyethylene (d) is used, it is more preferably 0.3 to 5 parts by mass, particularly preferably 0.3 to 3 parts by mass. When using ultra high molecular weight polyethylene (e), it is more preferably 1 to 20 parts by mass, particularly preferably 5 to 20 parts by mass. When the polyolefin resin (c) or the polytetrafluoroethylene resin (f) is used, it is more preferably 1 to 25 parts by mass, particularly preferably 3 to 20 parts by mass.

  Examples of the olefin resin (c) used here include olefin resins composed of at least one olefin resin having 2 to 10 carbon atoms. These olefin resins (c) can be used alone or in combination of two or more.

Examples of olefins used for the formation of the olefin resin (c) 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 (c) include 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 7-methyl-1 Non-conjugated dienes such as 1,6-octadiene and 1,9-decadiene.

As the olefin resin (c), a polymer mainly containing a propylene unit such as polypropylene and a propylene / ethylene copolymer, a polyethylene and an ethylene / norbornene copolymer 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 resin used in the present invention, one obtained by removing the polymerization catalyst or one modified with an acid anhydride group, a carboxyl group and an epoxy group can be used.

It does not matter whether the olefin resin (C) has crystallinity, but it is preferable to use at least one resin having a crystallinity of 10% or more by X-ray diffraction at room temperature.
In addition, it is preferable to use at least one of the olefin resins (c) having a melting point measured in accordance with JISK7212 of 40 ° C. or higher.
When a polypropylene resin is used as the component (c) 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.

When the olefin resin (c) is blended with the thermoplastic resin composition of the present invention, a polymer block mainly composed of styrene and butadiene are added for the purpose of improving the compatibility between the thermoplastic resin and the olefin resin. It is preferable to blend a block copolymer consisting of a polymer block as a main component or a hydride (h) thereof. The structure of these block copolymers is particularly preferably a (hydrogenated) styrene-butadiene-styrene triblock copolymer.
The (hydrogenated) block copolymer (h) is preferably used in the range of 5 to 100 parts by mass, more preferably 5 to 50 parts by mass with respect to 100 parts by mass of the thermoplastic resin composition of the present invention. .

  The low molecular weight polyethylene oxide (d) 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 ultra-high molecular weight polyethylene (e) is polyethylene having an average molecular weight of 400,000 to 6.5 million as measured by a melt viscosity method according to 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 of the present invention exists in an unmelted state. The average particle size measured by the counter method is preferably 50 μm or less, more preferably in the range of 5 to 40 μm.

The polytetrafluoroethylene resin (f) 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 (f) is preferably from 0.1 to 30 parts by weight, more preferably from 0.3 to 5 parts by weight, particularly preferably from 0.3 to 100 parts by weight, based on 100 parts by weight of the thermoplastic resin composition of the present invention. If it is used in the range of 3 parts by mass and less than 0.1 part, the squeaking noise is not reduced, and if it exceeds 30 parts by mass, the impact resistance and the surface appearance of the molded product are inferior.

Any known silicone oil (g) 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 (g) used in the present invention is preferably 60 to 500.000 cSt, more preferably 500 to 350,000 cSt, and particularly preferably 1,000 to 200,000 cSt. Outside, the squeakiness is inferior. The kinematic viscosity of the silicone oil was measured with an Ubbelohde viscometer according to ASTM D445-46T (JIS8803 is acceptable).

  The silicone oil (g) 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. If the blending amount of the component (g) is less than 0.1 parts by mass, the effect of reducing the squeaking noise tends to decrease, and if it exceeds 8 parts by mass, the surface appearance and the impact resistance of the molded product tend to be inferior. Moreover, melt kneading at the time of producing the thermoplastic resin composition of the present invention may be difficult.

The thermoplastic resin composition of the present invention has a butadiene-based rubbery polymer latex of 5 to 70% by mass (for the purpose of improving impact resistance while maintaining the squeaking noise reduction and the molded product surface appearance). Polybutadiene rubber system obtained by graft polymerization of an aromatic vinyl compound or a monomer component composed of the aromatic vinyl compound and another vinyl monomer copolymerizable with the aromatic vinyl compound in the presence of a solid content) Styrenic resin (Li) can be blended.
The ratio of the above-mentioned (Li) component is preferably 40 to 90/60 to 10% by mass, more preferably a hydrogenated rubber polymer (II) of the component (II) / butadiene rubber polymer of the (Li) component. Determines the blending amount of component (A) and component (R) so as to be in the range of 50-88 / 50-12% by mass.

  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.

  The thermoplastic resin composition of the present invention is prepared by mixing each component at a predetermined blending 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 alone or in combination of two or more.

  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. These can be used alone or in combination of two or more.

  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) small 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 automotive interior parts include door trims, door linings, pillar garnishes, consoles, door pockets, ventilators, ducts, air conditioners, instrument visors, instrument panel upper garnishes, instrument panel garnishes, A / T indicators, on / off switches (slide parts, 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) Analysis of block copolymer (I) and hydrogenated rubbery polymer (II) (1-1) Bonded aromatic vinyl compound content Based on absorption of phenyl group at 679 cm ⁻¹ , infrared analysis method Measured with
(1-2) Vinyl bond content of butadiene (co) polymer It was calculated by the Hampton method using infrared analysis.
(1-3) Hydrogenation rate It calculated from a 100 MHz and ¹ H-NMR spectrum using an ethylene tetrachloride solution.
(1-4) Number average molecular weight It calculated | required in polystyrene conversion using the gel permeation chromatography (GPC) in 135 degreeC using a trichlorobenzene solvent.
(2) Evaluation of molded product (2-1) Evaluation of stagnation sound: 1:
Using an injection molding machine “J-100E” (model name) manufactured by Nippon Steel Co., Ltd., a thermoplastic resin composition described in Table 3 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.
(2-2) 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 noise was evaluated by the same method as in the (2-1) squeaking noise evaluation-1.

(2-3) 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

(2-4) Surface appearance of molded product:
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.
X: Appearance defects such as a flow mark are remarkable and appearance is inferior.

(3) (A) Component (3-1) Production Example 1: Block Copolymer (I) (I-1)
After charging 25,000 parts of degassed and dehydrated cyclohexane and 800 parts of 1,3-butadiene in a 50 liter autoclave, 1.0 part of n-butyllithium was added, and isothermal polymerization was carried out at a polymerization temperature of 50 ° C. After the conversion rate was almost 100%, 30.0 parts of tetrahydrofuran, 2400 parts of 1,3-butadiene, and 200 parts of styrene were added, and the temperature rising polymerization was performed at 50 to 80 ° C. After the polymerization conversion rate was almost 100%, 600 parts of styrene was added and polymerization was carried out for 15 minutes. The polymerization conversion was almost 100%. The molecular characteristics of the obtained ABC triblock copolymer (I-1) are shown in Table 1.

(3-2) Production Example 2; Hydrogenated Rubber Polymer (II) (II-1) (I-1 Hydrogenation)
In a separate container, 15.0 parts of titanocene dichloride was dispersed in 240 parts of cyclohexane and reacted with 20 parts of triethylaluminum at room temperature. The obtained dark blue uniform solution was added to the polymer solution obtained in Production Example 1, and a hydrogenation reaction was performed at 50 ° C. under a hydrogen pressure of 50 kg / cm ² for 2 hours. Then, after decontacting and precipitating the polymer with methanol / hydrochloric acid, 2,6-di-tert-butylcatechol was added and dried under reduced pressure to obtain an ABC triblock copolymer (I- 1) was subjected to a hydrogenation reaction to obtain a hydrogenated rubbery polymer (II-1). The molecular properties are shown in Table 1.

(3-3) Production Example 3; block copolymer (I-2 to 7), hydrogenated rubbery polymer (II-2 to 7)
The block copolymer (I-2 to 7) shown in Table 1 was obtained by changing the monomer composition, polymerization conditions and the like in Production Example 1. Thereafter, these block copolymers (I-2 to 7) were subjected to a hydrogenation reaction under different hydrogenation conditions to obtain hydrogenated rubbery polymers (II-2 to 7). . The molecular properties are shown in Table 1.

(3-4) Production Example 4; rubber-reinforced styrene-based resin (A) (A-1)
30 parts of hydrogenated rubber polymer (II-1) previously made into a uniform solution in a 10 liter stainless steel autoclave equipped with a ribbon type stirring blade, 51 parts of styrene, 19 parts of acrylonitrile, 120 parts of toluene and tert- Charge 0.1 parts of dodecyl mercaptan, heat up while stirring, add 50 parts of benzoyl peroxide and 0.1 part of dicumyl peroxide at 50 ° C., further heat up to reach 80 ° C. Thereafter, the polymerization reaction was carried out at 200 rpm while stirring at a constant temperature of 80 ° C. After completion of the reaction, 0.2 part of 2,2-methylenebis-4-methyl-6-tert-butylphenol was added, and then the reaction mixture was extracted from the autoclave and unreacted substances and the solvent were distilled off by steam distillation and finely pulverized. The 40% vented extruder (220 ° C., 700 mmHg vacuum) was used to substantially distill off volatile components and pelletize the rubber-reinforced styrene resin (I-1). The graft ratio of the rubber-reinforced styrene resin (I-1) was 53%, and the intrinsic viscosity [η] of the acetone soluble component was 0.45 dl / g.

(3-5) Production Example 5: Rubber-reinforced styrene resin (I) (I-2)
A rubber-reinforced styrene resin (I-2) was obtained in the same manner as in Production Example 4 except that the monomers (styrene, acrylonitrile) used in Production Example 4 were replaced with 35 parts of methyl methacrylate and 35 parts of styrene. The graft ratio of the rubber-reinforced styrene resin (I-2) was 48%, and the intrinsic viscosity [η] of the acetone-soluble component was 0.32 dl / g.

(3-6) Production Example 6; rubber-reinforced styrene-based resin (A) (A-3 to A-8)
In place of the hydrogenated rubbery polymer (II-1) used in Production Example 4, the same (II-2), (II-3), (II-4), (II-5), (II-6) ), (II-7), and rubber reinforced styrene resins (A-3), (A-4), (A-5), (A-6), (A-7), (A- 8) was obtained. The graft ratio of each polymer and the intrinsic viscosity [η] of the acetone-soluble component were as follows.
Rubber Reinforced Styrene Resin (I) Graft Ratio (%) Intrinsic Viscosity [η]
(Dl / g)
(I-3) 50 0.46
(A-4) 50 0.46
(A-5) 54 0.48
(A-6) 50 0.46
(I-7) 53 0.45
(A-8) 62 0.47
Table 2 shows the structures of the rubber-reinforced styrene resins (E1) to (E8).

(B) Component (3-1) Production Example 7: Vinyl polymer (Raw 1) (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 (B-1) was obtained.

(3-2) Production Example 8: Vinyl polymer (B-2) (methyl methacrylate / styrene copolymer)
Except for using 50 parts of styrene and 50 parts of methyl methacrylate in place of styrene and acrylonitrile used in Production Example 7, a polymerization reaction was carried out under the conditions of Production Example 7, and a vinyl system having an intrinsic viscosity [η] of 0.46 dl / g. A polymer (B-2) was obtained.

(4) Component (c): Olefin resin The following products manufactured by Nippon Polyethylene Co., Ltd. were used.
(C-1); Novatec HDHJ560 (trade name)
High density polyethylene, melt flow rate 7g / 10min

(5) Component (d): Low molecular weight oxidized polyethylene The followings manufactured by Sanyo Chemical Industries, Ltd. were used.
(D-1); Sun Wax EP-250P (trade name)
Acid value 20 mgKOH / g, average molecular weight 2000

(6) Component (e): Ultra high molecular weight polyethylene The followings manufactured by Mitsui Chemicals, Inc. were used.
(E-1); Mipperon XM-221U (trade name)
Average molecular weight 2 million, average particle size 25 μm

(7) Component (f): Polytetrafluoroethylene resin The following were manufactured by Daikin Industries, Ltd.
(F-1); Lubron L-5 (trade name)
Average particle diameter of about 7μm

(8) (g) Component: Silicone oil The followings manufactured by Shin-Etsu Silicone Co., Ltd. were used.
(G-1); KF-96H-10 thousand cSt (trade name)
Dimethyl silicone oil, kinematic viscosity at 25 ° C. 10,000 cSt

(9) Component (H): Hydrogenated block copolymer The following products manufactured by Asahi Kasei Chemicals Corporation were used.
(H-1); 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)]

(10) (Li) Component (10-1) Production Example 9: Polybutadiene rubber-based styrene resin (Re-1) (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 latex of polymer h-1 was coagulated with an aqueous sulfuric acid solution, washed with water, and then dried to obtain a polybutadiene rubber-based styrene resin (Li-1).
The graft ratio of this polybutadiene rubber-based styrene resin (Li-1) was 68%, and the intrinsic viscosity [η] was 0.45 dl / g in the acetone-soluble component.

Examples 1-17, Comparative Examples 1-6
Each component is mixed by a Henschel mixer at the blending ratio shown in Table 3, and then melt-kneaded using a vented twin-screw extruder (manufactured by Nippon Steel Works, TEX44, barrel setting temperature 230 ° C.). 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 3.

As is apparent from Table 3, the thermoplastic resin compositions of the present invention represented by Examples 1 to 17 are reduced in the squeaking noise intended by the present invention, and further have impact resistance and molded article surface appearance. We provide molded products with a good balance.
On the other hand, Comparative Example 1 uses a butadiene-based rubbery polymer (Li) instead of the specific hydrogenated rubbery polymer (II) of the present invention in the component (a) of the present invention. This is an example, and the squeaking noise reduction is poor.
Comparative Example 2 is an example using the hydrogenated rubbery polymer (II-3) in which the polymer block A of the present invention does not exist in the component (A), and the surface appearance is inferior.
Comparative Example 3 is an example using a hydrogenated rubbery polymer (II-4) in which the amount of 1,2-vinyl in the polybutadiene component of the polymer block B is outside the scope of the present invention in the component (a). There is inferior itchiness reduction.
Comparative Example 4 is an example using a hydrogenated rubbery polymer (II-5) in which the amount of 1,2 vinyl in the polybutadiene component of the polymer block B is small and outside the scope of the present invention in the component (a). Impact resistance is inferior.
Comparative Example 5 is an example using a hydrogenated rubbery polymer (II-6) in which the amount of 1,2-vinyl in the polybutadiene of the polymer block C is outside the scope of the present invention in the component (a). The squeaking noise reduction is inferior.
Comparative Example 6 is an example using the hydrogenated rubbery polymer (II-7), which has a low hydrogenation rate of the hydrogenated block copolymer and is outside the scope of the present invention, and is poor in squeaking noise reduction.

Example 18
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 Examples 7 and 8
Except for changing the thermoplastic resin composition of the T-shaped part to the thermoplastic resin composition of Comparative Examples 1 and 5 as the contact part A, the presence or absence of squeaking noise was examined in the same manner as in Example 18. It was. 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.

  According to the present invention, the squeaking noise generated when the members rub against each other is remarkably reduced, and even when placed at a high temperature for a long time, the squeaking noise reduction effect is maintained without deteriorating, and further the impact resistance is improved. A contact component made of an excellent thermoplastic resin composition can be provided, and is suitably used for automobile interior parts, office equipment, house interior parts, etc. having locations where they can contact, join and fit with other members. be able to. 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 (7)

A thermoplastic resin composition comprising 5 to 100 parts by mass of the following (A) component and 0 to 95 parts by mass of (B) component, and the total of the (A) component and the (B) component is 100 parts by mass. Ri Do from the object, the thermoplastic resin composition or other heat consists thermoplastic resin component and the contact to the contact parts, characterized in Rukoto:
(A) 1-40% by mass of polymer block A having an aromatic vinyl compound of 90% by mass or more,
Polymer block B 30 having a 1,2-vinyl bond content of 25 to 70% and a polymer of butadiene and an aromatic vinyl compound, wherein the ratio of aromatic vinyl compound / butadiene is 1 to 40/99 to 60% by mass. 80% by mass of olefinic unsaturated bonds of the block copolymer (I) each having 1 to 80 % by mass and one or more polymer blocks C of 10 to 50% by mass of butadiene having a 1,2-vinyl bond content of less than 25% In the presence of a hydrogenated rubbery polymer (II) formed by hydrogenating at least%,
Monomer comprising an aromatic vinyl compound, or an aromatic vinyl compound and another vinyl monomer selected from a vinyl cyanide compound copolymerizable with the aromatic vinyl compound, a (meth) acrylic acid ester, and a maleimide compound A rubber-reinforced styrene-based resin obtained by graft polymerization of the body (a),
(B) A vinyl polymer obtained by polymerizing one or more vinyl monomers (b). Monomer (a) is 60-90 / 10-40 mass ratio of styrene / acrylonitrile, 10-90 / 10-90 mass ratio of styrene / methyl methacrylate, 50-95 / 5-50 mass of styrene / phenylmaleimide. The contact component according to claim 1, which is a ratio. Further, a polybutadiene rubber-based styrene resin (Li) is blended, and the ratio of (i) component hydrogenated rubber polymer (II) / (Li) component butadiene rubber polymer is 40 to 90. The contact component according to claim 1, wherein the contact component is / 60 to 10% by mass. And (c) at least one selected from olefinic resins, (d) low molecular weight polyethylene oxide, (e) ultrahigh molecular weight polyethylene, (f) polytetrafluoroethylene resin, and (g) silicone oil. A contact component comprising 0.1 to 30 parts by mass with respect to 100 parts by mass of the thermoplastic resin composition according to any one of 1 to 3 . (C) 5-100 parts by mass of (h) (hydrogenated) styrene-butadiene block copolymer is blended with 100 parts by mass of the thermoplastic resin composition together with the olefin resin. 4. The contact part according to 4. The contact part according to any one of claims 1 to 5, 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. The contact part according to claim 6, 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.

Images