JP6110423B2 - Thermoplastic resin composition and molded article - Google Patents

Description

  The present invention relates to a thermoplastic resin composition and a molded article, and more particularly to a thermoplastic resin composition and a molded article in which the squeaking noise generated by contacting and rubbing with other members is greatly reduced.

  ABS resins are widely used in the manufacture of automotive interior parts due to their excellent mechanical properties, heat resistance, and moldability.

  However, due to vibrations during automobile travel, ABS interior parts made of ABS resin may be used together with other parts and other parts such as polyvinyl chloride, chloroprene rubber, polyurethane, natural rubber, polyester or polyethylene lining sheets, foam, etc. In the case where the members come into contact with each other and rub against each other, a squeaking noise (friction noise) may be generated. For example, a ventilator made of ABS resin has 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 material and the ventilator case rub against each other. As described above, a squeaking noise may be generated even under a use situation in which an ABS resin automobile interior part rubs against other members.

In addition, since ABS resin and ASA resin are amorphous resins, they have a higher coefficient of friction compared to crystalline resins 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 when fitting with a member made of other resin, the stick-slip phenomenon as shown in FIG. Yes. The stick-slip phenomenon occurs when two objects rub against each other. When the object M connected by a spring is placed on a driving table that moves at a driving speed V as shown in the model of FIG. The object M first moves to the right as shown in FIG. 2 (b) together with the table moving at the driving speed V by the action of the static friction force. When the force to be restored by the spring becomes equal to the static friction force, the object M starts to slide in the direction opposite to the driving speed V. At this time, the object M receives a dynamic frictional force, so that the sliding stops at the time of FIG. 2C when the dynamic force of the spring becomes equal to the dynamic frictional force, that is, adheres to the drive base. It moves in the same direction as the driving speed V (FIG. 2 (d)). This is called a stick-slip phenomenon, and it is said that if the difference Δμ between the static friction coefficient μs and the μl at the lower end of the sawtooth waveform is large as shown in FIG. The dynamic friction coefficient is an intermediate value between μs and μl.
These squeaking noises are a major cause of impairing comfort and quietness when riding, and there is a strong demand for reduction of squeaking noises.

  On the other hand, it is known that the stick-slip phenomenon appears prominently when the friction speed dependency of the friction coefficient obtained by Ammonton-Coulomb law takes a negative value (see Non-Patent Document 1). Therefore, by making the dependency of the friction coefficient on the friction speed close to zero or a positive value not less than zero, it is possible to suppress the occurrence of the stick-slip phenomenon and reduce the generation of the squeaking noise.

  Therefore, in order to prevent such squeaking noise, a method of applying a Teflon (registered trademark) coating to the surface of the member, a method of mounting a 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 maintained when it is placed at a high temperature for a long time.

  Further, as a method for modifying the material itself used for automobile interior parts, a method of blending silicone oil with ABS resin, a method of blending an epoxy-containing olefin copolymer with ABS resin, and the like have been proposed. For example, a technique of blending an organosilicon compound into a resin made of polycarbonate resin and ABS resin (see Patent Document 1), and a technique of blending a flame retardant, a flame retardant aid and silicone oil into ABS resin (see Patent Document 2) ), A technique of blending silicone oil into ABS resin, MBS resin and HIPS (high impact polystyrene) resin (see Patent Document 3), and a technique of blending alkanesulfonate surfactant into ABS resin (Patent Document 4). In addition, a modified polyorganosiloxane containing at least one reactive group selected from an epoxy group, a carboxyl group and an acid anhydride group is added to the ABS resin to increase water repellency and increase the water in the bathroom and toilet. A technique (see Patent Document 5) used for a rotating part is disclosed.

  However, the stagnation noise reduction effect by these methods is not sufficient, and even if it shows a certain level of stagnation noise prevention effect immediately after molding, the effect persists poorly, especially when placed at high temperatures for a long time Has a problem that its effect is greatly 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, PP 328-333, 2003

In view of such circumstances, the present invention significantly reduces the occurrence of squeaking noise that occurs when the members rub against each other, and maintains the squeaking noise reduction effect even when placed under high temperature for a long time, and Provides a thermoplastic resin composition [X] excellent in impact resistance and molded appearance, a molded product thereof, and a fitting product obtained by assembling the molded product and a molded product of a specific thermoplastic resin [Y]. With the goal.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the thermoplastic resin composition [X] containing a specific rubber-reinforced vinyl resin has a squeaking sound generated when the members rub against each other. Can be significantly reduced, and even when placed at high temperatures for a long time, the effect of reducing squeaking noise is maintained without deterioration, and further, it is possible to provide a molded product excellent in impact resistance and molded appearance. The fitting product composed of the thermoplastic resin composition [X] molded product of the present invention and the molded product of the thermoplastic resin [Y] was significantly reduced in the generation of squeaking noise and was placed at a high temperature for a long time. In some cases, it was found that the stagnation noise reduction effect is maintained without degrading, and the present invention has been completed.

According to the present invention, the following fitting product is provided. That is,
1. A molded article of the following thermoplastic resin composition [X] and a molded article of the thermoplastic resin [Y] selected from the following groups Y1 to Y4, and molded of the thermoplastic resin composition [X] Product and a molded product of the thermoplastic resin [Y] are assembled:
Thermoplastic resin composition [X]:
Rubber reinforced vinyl resin [A1] obtained by polymerizing vinyl monomer [b1] containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of ethylene / α-olefin rubber polymer [a1] And a rubber-reinforced vinyl resin [A2] obtained by polymerizing a vinyl monomer [b2] containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of a diene rubber polymer [a2] And a thermoplastic resin composition comprising a (co) polymer [B] of a vinyl monomer [b3] containing an aromatic vinyl compound and a vinyl cyanide compound An object [X],
The total amount of the ethylene / α-olefin rubbery polymer [a1] and the diene rubbery polymer [a2] is 5 to 30% by mass with respect to 100% by mass of the entire thermoplastic resin composition [X]. Yes,
The mass ratio [a1]: [a2] of the ethylene / α-olefin rubbery polymer [a1] and the diene rubbery polymer [a2] is 90 to 34:10 to 66, Thermoplastic resin composition with reduced squeaking noise.
Molded product of thermoplastic resin [Y]:
A molded product selected from the following Y1 to Y4.
Y1: Polycarbonate / rubber reinforced styrene resin alloy with HDT of 85 ° C. or higher,
Y2: Styrenic resin having an HDT of 85 ° C. or higher (excluding Y1 above),
Y3: polyolefin resin having an HDT of 85 ° C. or higher, and
Y4: Methacrylic resin having an HDT of 85 ° C. or higher.
2. 2. The fitting product according to 1 above, wherein HDT is 85 ° C. or higher.
3. 3. The fitting according to 1 or 2 above, wherein the ethylene / α-olefin rubbery polymer [a1] has an ethylene: α-olefin mass ratio of 5 to 95:95 to 5.
4). 4. The fitting product according to any one of 1 to 3, wherein the ethylene / α-olefin rubbery polymer [a1] is an ethylene / propylene copolymer.
5. Any one of the above 1-4, wherein 100 parts by mass of the thermoplastic resin composition [X] is blended with 0.1-8 parts by mass of a silicone oil [C] having a kinematic viscosity at 25 ° C. of 10-100,000 cSt. The fitting according to item 1 .
6). 6. The fitting product according to 5 above, wherein the silicone oil [C] is methylphenyl silicone oil.
7 . The fitting product according to any one of 1 to 6 above, which is an automobile interior part.
8 . 8. The fitting product according to 7 above, wherein the automobile interior part is an automobile ventilator.
9 . The above 7 Symbol mounting of the fitting parts automotive interior component is an air conditioner for a motor vehicle.

The thermoplastic resin composition [X] comprising the specific rubber-reinforced vinyl resin of the present invention is greatly reduced in the squeaking noise generated when the members rub against each other, and when placed at a high temperature for a long time. The effect of reducing the squeaking noise is maintained without deterioration, and further, a molded product excellent in impact resistance and molded appearance is provided, and the molded product and a molded product of a specific thermoplastic resin [Y] are assembled. As a result, it is possible to obtain a fitting product in which the squeaking noise generated when the members rub against each other is remarkably reduced and the squeaking noise reduction effect is maintained without being lowered even when the member is placed at a high temperature for a long time. Become.

FIG. 1 is an explanatory diagram of the stick-slip phenomenon. FIGS. 2A, 2B, 2C, and 2D are stick-slip model diagrams.

Hereinafter, the present invention will be described in detail.
The thermoplastic resin composition of the present invention is a rubber-reinforced vinyl resin [A1] obtained by polymerizing a vinyl monomer [b1] in the presence of an ethylene / α-olefin rubber polymer [a1]. A rubber-reinforced vinyl resin [A2] obtained by polymerizing a vinyl monomer [b2] in the presence of a diene rubber polymer [a2], and a vinyl monomer [b3] ( A thermoplastic resin composition [X] comprising a (co) polymer [B],
The total amount of the ethylene / α-olefin rubbery polymer [a1] and the diene rubbery polymer [a2] is 5 to 30% by mass with respect to 100% by mass of the entire thermoplastic resin composition [X]. Yes,
The mass ratio [a1]: [a2] of the ethylene / α-olefin rubbery polymer [a1] and the diene rubbery polymer [a2] is 90-15: 10-85, To do.

In this specification, HDT (thermal deformation temperature) is a value (unit: ° C.) measured under the condition of a load of 1.80 MPa according to ISO75.
In addition, “(co) polymerization” means homopolymerization and copolymerization, “(meth) acryl” means acryl and / or methacryl, and “(meth) acrylate” means acrylate and / or Or means methacrylate.

1. Rubber-reinforced vinyl resin [A] (hereinafter also referred to as “component [A]”):
The component [A] used in the present invention is a rubber-reinforced vinyl resin [A1] obtained by polymerizing a vinyl monomer [b1] in the presence of an ethylene / α-olefin rubber polymer [a1]. Alone and, if necessary, a mixture with a rubber-reinforced vinyl resin [A2] obtained by polymerizing a vinyl monomer [b2] in the presence of a diene rubber polymer [a2], and Further, if necessary, it is a rubber-reinforced vinyl resin comprising a mixture of a vinyl monomer [b3] and a (co) polymer [B]. The (co) polymer [B] is obtained by polymerizing the vinyl monomer [b3] in the absence of the rubbery polymer.

The rubbery polymer contained in the rubber-reinforced vinyl resin [A] is an ethylene / α-olefin rubbery polymer [a1] and, if necessary, a diene rubbery polymer [a2]. It is.
1-1. Ethylene / α-olefin rubbery polymer [a1] (hereinafter also referred to as “component [a1]”):
Examples of the ethylene / α-olefin rubbery polymer [a1] include an ethylene / α-olefin copolymer and an ethylene / α-olefin / non-conjugated diene copolymer. Examples of the α-olefin constituting the component [a1] include α-olefins having 3 to 20 carbon atoms, specifically, propylene, 1-butene, 1-pentene, 1-hexene, 4- Examples include methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene, 1-eicosene and the like. These α-olefins can be used alone or in admixture of two or more. The carbon number of the α-olefin is preferably 3 to 20, more preferably 3 to 12, and still more preferably 3 to 8. When the number of carbon atoms exceeds 20, the copolymerizability is lowered and the surface appearance of the molded product may not be sufficient. The mass ratio of ethylene: α-olefin is usually 5 to 95:95 to 5, preferably 50 to 90:50 to 10, more preferably 60 to 88:40 to 12. When the α-olefin mass ratio exceeds 95, the weather resistance is not sufficient. On the other hand, when it is less than 5, the rubber elasticity of the rubbery polymer is not sufficient, so that sufficient impact resistance may not be exhibited. .
Among these, from the viewpoint of reducing squeaking noise, an ethylene / α-olefin copolymer is preferable, and an ethylene / propylene copolymer is particularly preferable.

Non-conjugated dienes include alkenyl norbornenes, cyclic dienes and aliphatic dienes, with 5-ethylidene-2-norbornene and dicyclopentadiene being preferred. These non-conjugated dienes can be used alone or in admixture of two or more. The ratio of the nonconjugated diene to the total amount of the rubbery polymer is usually 0 to 30% by mass, preferably 0 to 20% by mass, and more preferably 0 to 10% by mass. If the proportion of the non-conjugated diene exceeds 30% by mass, the molded appearance and weather resistance may not be sufficient. In addition, the amount of unsaturated groups in component [a1] is preferably in the range of 4 to 40 in terms of iodine value. If the iodine value exceeds 40, the molding appearance and weather resistance of the molded product may not be sufficient, and if the iodine value is less than 4, the impact resistance of the molded product may not be sufficient.
Moreover, the Mooney viscosity (ML1 _{+ 4} , 100 degreeC; based on JISK6300) of component [a1] is 5-80 normally, Preferably it is 10-65, More preferably, it is 15-45. When the Mooney viscosity exceeds 80, the fluidity of the resulting rubber-reinforced vinyl resin is insufficient, and when the Mooney viscosity is less than 5, the resulting molded article may have insufficient impact resistance.

  The ethylene / α-olefin rubbery polymer [a1] is a polymer obtained by hydrogenating a block (co) polymer obtained by using a conjugated diene compound such as butadiene or isoprene (of a conjugated diene moiety). The hydrogenation rate of the double bond is preferably 90% or more from the viewpoint of weather resistance. The polymer may be a crosslinked polymer or an uncrosslinked polymer.

1-2. Diene rubbery polymer [a2] (hereinafter also referred to as “component [a2]”):
The diene rubbery polymer [a2] may be a homopolymer such as polybutadiene or polyisoprene; a styrene / butadiene copolymer, a styrene / butadiene / styrene copolymer, an acrylonitrile / styrene / butadiene copolymer, or an acrylonitrile / butadiene. Butadiene copolymers such as copolymers; styrene / isoprene copolymers, styrene / isoprene / styrene copolymers, isoprene copolymers such as acrylonitrile / styrene / isoprene copolymers, and the like. These can be used alone or in combination of two or more. The diene rubbery polymer [a2] may be a crosslinked polymer or an uncrosslinked polymer.

1-3. Vinyl monomers [b1] to [b3]:
The vinyl monomers [b1], [b2] and [b3] are not particularly limited as long as they are all polymerizable compounds having an unsaturated bond.
The vinyl monomers [b1], [b2] and [b3] usually contain an aromatic vinyl compound and a vinyl cyanide compound. In addition, if necessary, other copolymerizable vinyl monomers such as (meth) acrylic acid ester and maleimide compound, carboxyl group, acid anhydride group, hydroxyl group, amino group, amide group, epoxy group A functional group-containing vinyl monomer having at least one functional group such as an oxazoline group may be used in combination. The vinyl monomers [b1] and [b2] used for forming the rubber-reinforced vinyl resins [A1] and [A2] may be the same as or different from each other.
The vinyl monomer [b3] used for forming the (co) polymer [B] may be the same as or different from the vinyl monomer [b1] and / or [b2]. May be.

  The aromatic vinyl compound is not particularly limited as long as it is a compound having at least one vinyl bond and at least one aromatic ring. Examples include styrene, α-methyl styrene, o-methyl styrene, p-methyl styrene, vinyl toluene, β-methyl styrene, ethyl styrene, pt-butyl styrene, vinyl xylene, vinyl naphthalene, monochlorostyrene, dichloromethane. Examples thereof include styrene, monobromostyrene, dibromostyrene, and fluorostyrene. These can be used alone or in combination of two or more. Of these, styrene and α-methylstyrene are preferred.

  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.

  Examples of the (meth) acrylic acid ester include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, acrylic acid Acrylic esters such as phenyl and 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 octadecyl acid, cyclohexyl methacrylate, phenyl methacrylate, and benzyl methacrylate. These can be used alone or in combination of two or more. Of these, methyl methacrylate is preferred.

Examples of the maleimide compound 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 a monomer unit comprising this maleimide compound into a polymer, there is a method in which maleic anhydride is copolymerized in advance and then imidized.

  Among the functional group-containing vinyl monomers, examples of the unsaturated compound having a carboxyl group include acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, and cinnamic acid. . These can be used alone or in combination of two or more.

Examples of the unsaturated compound having an acid anhydride group include maleic anhydride, itaconic anhydride, and citraconic anhydride. These can be used alone or in combination of two or more.
Examples of unsaturated compounds having a hydroxyl group include hydroxystyrene, 3-hydroxy-1-propene, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene, trans-4-hydroxy-2-butene, 3 -Hydroxy-2-methyl-1-propene, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, N- (4-hydroxyphenyl) maleimide and the like. These can be used alone or in combination of two or more.

As unsaturated compounds having an amino group, 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- Examples include methylacrylamine. These can be used alone or in combination of two or more.
Examples of the unsaturated compound having an amide group include acrylamide, N-methylacrylamide, methacrylamide, N-methylmethacrylamide and the like. These can be used alone or in combination of two or more.

  Examples of the unsaturated compound having an epoxy group include glycidyl acrylate, glycidyl methacrylate, and allyl glycidyl ether. These can be used alone or in combination of two or more.

  Examples of the unsaturated compound having an oxazoline group include vinyl oxazoline. These can be used alone or in combination of two or more.

  The vinyl monomers [b1], [b2] and [b3] are selected according to their purpose, usage, etc., and their types and amounts used. The total amount of the aromatic vinyl compound and the vinyl cyanide compound is as follows: The total amount of vinyl monomers is 100 to 100% by mass, usually 30 to 100% by mass, preferably 50 to 100% by mass, and more preferably 70 to 100% by mass. The content of the other copolymerizable vinyl monomer is usually 0 to 70% by mass, preferably 0 to 50% by mass, more preferably 0 to 30% with respect to 100% by mass of the whole vinyl monomer. % By mass. The content of the functional group-containing vinyl monomer is usually 0 to 40% by mass, preferably 0 to 30% by mass, more preferably 0 to 20% by mass with respect to 100% by mass of the total amount of the vinyl monomer. %. The use ratio of the aromatic vinyl compound and the vinyl cyanide compound (aromatic vinyl compound / vinyl cyanide compound) is usually 40 to 85% by mass / 15 to 60% by mass when the total of these is 100% by mass. Preferably, it is 45-85 mass% / 15-55 mass%.

1-4. Method for producing the rubber-reinforced vinyl resin [A]:
The rubber-reinforced vinyl resin [A] is a polymer component containing an ethylene / α-olefin rubber polymer [a1] and, if necessary, a diene rubber polymer [a2]. The containing form is not particularly limited.
In the rubber-reinforced vinyl resin [A], a graft copolymer in which a (co) polymer of a vinyl monomer is grafted to a rubber polymer, and a rubber polymer are not grafted. (Co) polymers of vinyl monomers are included. However, this graft copolymer may contain a rubbery polymer to which a (co) polymer of a vinyl monomer is not grafted.
Examples of the content when the ethylene / α-olefin rubbery polymer [a1] and the diene rubbery polymer [a2] are used are exemplified below.
(1) The case where both the ethylene / α-olefin rubber polymer [a1] and the diene rubber polymer [a2] are contained as a graft copolymer.
(2) The case where either one of the ethylene / α-olefin rubber polymer [a1] and the diene rubber polymer [a2] is contained as a graft copolymer.
(3) A case where both the ethylene / α-olefin rubber polymer [a1] and the diene rubber polymer [a2] are contained as an ungrafted rubber polymer.
Of these, (1) is particularly preferred.

Examples of the rubber-reinforced vinyl resin [A] of the above aspect (1) are as follows.
[I] Rubber reinforced vinyl resin [A1] obtained by polymerizing vinyl monomer [b1] in the presence of the ethylene / α-olefin rubber polymer [a1], or the rubber A mixture comprising a reinforced vinyl resin [A1] and a rubber reinforced vinyl resin [A2] obtained by polymerizing a vinyl monomer [b2] in the presence of the diene rubber polymer [a2]. .
[Ii] A mixture comprising the above mixture [i] and a (co) polymer of the vinyl monomer [b3] (hereinafter also referred to as “(co) polymer [B]”).
[Iii] Obtained by polymerizing a vinyl monomer [b1] or [b2] in the presence of the ethylene / α-olefin rubber polymer [a1] and the diene rubber polymer [a2]. Rubber-reinforced vinyl resin [A3].
[Iv] A mixture comprising the rubber-reinforced vinyl resin [A3] and the (co) polymer [B].
Among these, [i] and [ii] are preferable from the viewpoint of productivity, and [ii] is particularly preferable.
The rubber-reinforced vinyl resin [A] may be a combination of two or more of the above [i], [ii], [iii] and [iv].

Next, a method for producing the rubber-reinforced vinyl resins [A1], [A2] and [A3] will be described.
Examples of the polymerization method include known polymerization methods such as emulsion polymerization, solution polymerization, suspension polymerization, and bulk polymerization. In any case, in the presence of the rubbery polymer, the vinyl monomer may be charged all at once, and may be reacted, or may be divided or continuously added for reaction. Further, the rubbery polymer may be added or reacted in the whole or in part during the polymerization with the vinyl monomer.
In addition, the usage-amount of a rubber-like polymer is 5-80 mass% normally when the sum total of a rubber-like polymer and a vinyl-type monomer is 100 mass%, Preferably it is 10-70 mass%.

The production method of the rubber-reinforced vinyl resin [A1] is preferably solution polymerization and bulk polymerization, more preferably solution polymerization. The production method of the rubber-reinforced vinyl resin [A2] is emulsion polymerization or suspension polymerization. The method for producing the rubber-reinforced vinyl resin [A3] is preferably emulsion polymerization, solution polymerization, suspension polymerization, and bulk polymerization, and may be a combination of these methods.
When the above rubber-reinforced vinyl resins [A1], [A2] and [A3] are produced by emulsion polymerization, a polymerization initiator, a chain transfer agent, an emulsifier, water and the like are usually used. In addition, when the said rubbery polymer is not a latex form but a solid form, it can be used as a latex form by re-emulsification.

As the polymerization initiator, a combination of an organic peroxide such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramentane hydroperoxide and a reducing agent represented by a sugar-containing pyrophosphate formulation, a sulfoxylate formulation, etc. Redox polymerization initiators by: persulfates such as potassium persulfate; peroxides such as benzoyl peroxide (BPO), lauroyl peroxide, t-butyl peroxylaurate, t-butyl peroxymonocarbonate; Examples thereof include azo polymerization initiators such as 2′-azobis (isobutyronitrile). These can be used alone or in combination of two or more. The amount of the polymerization initiator used is usually 0.05 to 5% by mass, preferably 0.1 to 1% by mass, based on the total amount of the vinyl monomer [b1] or [b2].
The polymerization initiator is usually added all at once or continuously to the reaction system.

  Examples of chain transfer agents include mercaptans such as octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, t-tetradecyl mercaptan; terpinolenes, α -Methylstyrene dimer, tetraethylthiuram sulfide, acrolein, methacrolein, allyl alcohol, 2-ethylhexylthioglycol and the like. These can be used alone or in combination of two or more. The amount of the chain transfer agent used is usually 0.05 to 2% by mass with respect to the total amount of the vinyl monomer [b1] or [b2].

  Examples of the emulsifier include anionic surfactants and nonionic surfactants. Examples of the anionic surfactant include sulfates of higher alcohols; alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate; aliphatic sulfonates such as sodium lauryl sulfate; rosinates and phosphates. Examples of nonionic surfactants include polyethylene glycol alkyl ester compounds and alkyl ether compounds. These can be used alone or in combination of two or more. The usage-amount of the said emulsifier is 0.3-5 mass% normally with respect to the whole quantity of the said vinylic monomer [b1] or [b2].

  Emulsion polymerization can be performed under known conditions according to the type and amount of the vinyl monomer [b1] or [b2] used, the polymerization initiator, and the like. The latex obtained by the above emulsion polymerization is usually purified by coagulating with a coagulant to form a polymer component in powder form, and then washing with water and drying. Examples of the coagulant include inorganic salts such as calcium chloride, magnesium sulfate, magnesium chloride, and sodium chloride; inorganic acids such as sulfuric acid and hydrochloric acid; organic acids such as acetic acid, lactic acid, and citric acid. These can be used alone or in combination of two or more. Further, depending on the required performance, washing may be carried out after adding an alkali component or an acid component after solidification to neutralize it.

When the above rubber-reinforced vinyl resins [A1], [A2] and [A3] are produced by solution polymerization, usually a solvent, a polymerization initiator, a chain transfer agent and the like are used.
Examples of the solvent include inert polymerization solvents used in known radical polymerization, for example, aromatic hydrocarbons such as ethylbenzene and toluene; ketones such as methyl ethyl ketone and acetone; halogenated hydrocarbons such as dichloromethylene and carbon tetrachloride. Acetonitrile, dimethylformamide, N-methylpyrrolidone and the like can be used. These can be used alone or in combination of two or more.

Examples of the polymerization initiator include organic peroxides such as ketone peroxide, dialkyl peroxide, diacyl peroxide, peroxy ester, and hydroperoxide. These can be used alone or in combination of two or more.
Examples of chain transfer agents include mercaptans, terpinolenes, α-methylstyrene dimers, and the like. These can be used alone or in combination of two or more.

  Solution polymerization can be carried out under known conditions depending on the type of vinyl monomer [b1] or [b2] used, the polymerization initiator, and the like. The polymerization temperature is usually in the range of 80 to 140 ° C. In addition, in the case of solution polymerization, it can also manufacture without using a polymerization initiator.

  Also in the case of bulk polymerization and suspension polymerization, known methods can be applied. The polymerization initiator, chain transfer agent and the like used in these methods are not particularly limited, but the same compounds as those exemplified in the solution polymerization can be used.

1-5. Physical properties of rubber-reinforced vinyl resin [A]:
The graft ratios of the rubber-reinforced vinyl resins [A1], [A2] and [A3] obtained as described above are usually 10 to 150% by mass, preferably 20 to 120% by mass. When the graft ratio is less than 10% by mass, the interfacial strength between the graft copolymer and the (co) polymer of the vinyl monomer [b1] or [b2] is inferior, and the impact resistance may not be sufficient. . On the other hand, if it exceeds 150% by mass, the layer made of the (co) polymer of the vinyl monomer [b1] or [b2] on the surface of the rubber polymer becomes thick, and the rubber polymer is grafted inside. Since the layer made of the (co) polymer is developed, the rubber elasticity is lowered, and as a result, the 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 rubber-reinforced vinyl resin in 20 ml of acetone (acetonitrile when the rubbery polymer is an acrylic rubber) and shakes with a shaker for 2 hours at 25 ° C. After that, the mass (g) of insoluble matter obtained by centrifuging for 60 minutes with a centrifuge (rotation speed: 23,000 rpm) under a temperature condition of 5 ° C. to separate the insoluble matter and the soluble matter. Yes, T is the mass (g) of the rubbery polymer contained in 1 gram of rubber-reinforced vinyl resin. The mass of the rubbery polymer can be obtained by a method of calculating from a polymerization prescription and a polymerization conversion rate, a method of obtaining from an infrared absorption spectrum (IR), and the like.

  In addition, the intrinsic viscosity [η] (measured in methyl ethyl ketone at 30 ° C.) of the acetone-soluble components of the rubber-reinforced vinyl resins [A1], [A2] and [A3] is usually 0.1 to 1. 0.5 dl / g, preferably 0.2 to 1.0 dl / g. When the intrinsic viscosity [η] is within the above range, the physical property balance between molding processability and impact resistance is excellent.

The intrinsic viscosity [η] was measured by the following method. First, acetone-soluble components of the rubber-reinforced vinyl resins [A1], [A2], and [A3] were dissolved in methyl ethyl ketone, and five different concentrations were prepared. The intrinsic viscosity [η] was determined from the results of measuring the reduced viscosity of each concentration at 30 ° C. using an Ubbelohde viscosity tube. The unit is dl / g.
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.

  As described above, the rubber-reinforced vinyl resin [A] according to the present invention is a rubber-reinforced vinyl resin [A1] prepared separately or a mixture of [A1] and [A2]. The rubber-reinforced vinyl system obtained by polymerizing the vinyl monomer [b1] in the presence of the ethylene / α-olefin rubber polymer [a1] and the diene rubber polymer [a2]. A resin [A3] may be used. Therefore, when using a plurality of rubber-reinforced vinyl resins such as the former, a mixture of resins obtained in each manufacturing process may be used, but as another method, for example, each resin is obtained by emulsion polymerization. Can be obtained by mixing latexes and then coagulating them.

1-6. Production method of (co) polymer [B]:
The (co) polymer [B] is obtained by polymerizing the vinyl monomer [b3] by a method such as solution polymerization, bulk polymerization, emulsion polymerization or suspension polymerization in the presence of a polymerization initiator or the like. Or by thermal polymerization without using a polymerization initiator, both can be produced under known conditions.

1-7. Physical properties of (co) polymer [B]:
The intrinsic viscosity [η] (measured in methyl ethyl ketone at 30 ° C.) of the polymer [B] 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 physical property balance between molding processability and impact resistance is excellent.

The intrinsic viscosity [η] was measured by the following method. First, the above (co) polymer [B] was dissolved in methyl ethyl ketone to prepare 5 samples having different concentrations. The intrinsic viscosity [η] was determined from the results of measuring the reduced viscosity of each concentration at 30 ° C. using an Ubbelohde viscosity tube. The unit is dl / g.
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.

2. Silicone oil [C] (hereinafter also referred to as “component [C]”):
The silicone oil as the component [C] used in the present invention is not particularly limited except the kinematic viscosity at 25 ° C. Any known oil can be used as long as it has a polyorganosiloxane structure. The silicone oil [C] may be a non-modified silicone oil such as dimethyl silicone oil, methylphenyl silicone oil, methyl hydrogen silicone oil, or a part of the side chain in the polyorganosiloxane structure and / or the polyorgano It may be a modified silicone oil in which various organic groups are introduced into one terminal part of the siloxane structure 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 Diene silicone oil, amino modified silicone oil, epoxy modified silicone oil, carboxyl modified silicone oil, acrylic modified silicone oil, methacryl modified silicone oil, mercapto modified silicone oil, phenol modified silicone oil, carbinol modified silicone oil, etc. may be used. it can.
When the silicone oil [C] used in the present invention is methylphenyl silicone oil, the generation of squeaking noise is remarkably reduced, and the squeaking noise reduction effect is not lowered even when left at high temperatures for a long time. A thermoplastic resin composition and a molded article that are maintained and further excellent in impact resistance and molded appearance can be obtained.
Further, when the silicone oil [C] used in the present invention is an alkyl / aralkyl-modified silicone oil or an amino-modified silicone oil, the generation of squeaking noise is remarkably reduced and even when it is left at a high temperature for a long time. It is possible to obtain a thermoplastic resin composition and a molded article that are maintained without deterioration of the squeaking noise reduction effect, and further excellent in impact resistance and molded appearance. These silicone oils may be used alone or in combination of two or more.

  The methylphenyl silicone oil used in the present invention is a non-reactive straight silicone oil in which part of the side chain of the polysiloxane is a phenyl group.

  The alkyl / aralkyl-modified silicone oil used in the present invention is a non-reactive modified silicone oil in which an alkyl group and an aralkyl group are introduced into a part of the side chain of the silicone oil.

  The amino-modified silicone oil used in the present invention is one in which an amino group is introduced into a part of the side chain of polysiloxane, and the amino modification may be either monoamine modification or diamine modification.

  The kinematic viscosity at 25 ° C. of the silicone oil [C] used in the present invention is usually 10 to 100,000 cSt, preferably 10 to 50,000 cSt, more preferably 15 to 50,000 cSt, and particularly preferably 20 to 30. , 000 cSt. When the kinematic viscosity at 25 ° C. of the silicone oil [C] is less than 10 cSt, the effect of reducing the squeaking noise may be insufficient. On the other hand, when the kinematic viscosity exceeds 100,000 cSt, the rubber-reinforced vinyl resin [A ], The dispersibility of the silicone oil [C] is deteriorated, the impact resistance and the squeaking noise reduction effect are not sufficiently exhibited, and the extrusion processability at the time of kneading may be insufficient.

  The kinematic viscosity of the silicone oil was measured by an Ubbelohde viscometer according to ASTM D445-46T (JIS 8803 is acceptable).

3. Thermoplastic resin composition [X]:
The thermoplastic resin composition [X] in the present invention is obtained by mixing the above-mentioned component [A], the above-mentioned component [B], and optionally the above-mentioned component [C] at a predetermined blending ratio, and melt-kneading. .

  The above silicone oil [100] with respect to 100 parts by mass of the thermoplastic resin composition [X] comprising the rubber-reinforced vinyl resin [A] (including [A1] and [A2]) and the (co) polymer [B]. C] is usually 0.1 to 8 parts by mass, preferably 0.2 to 6 parts by mass, more preferably 0.5 to 5 parts by mass, and particularly preferably 2.5 to 3.5 parts by mass. is there. If the amount of the component [C] is less than 0.1 parts by mass, the effect of reducing the squeaking noise may not be sufficiently obtained. On the other hand, when the compounding amount of the component [C] exceeds 8 parts by mass, the appearance and impact resistance of the molded product may be insufficient, or melt mixing may become difficult.

  The total amount of the ethylene / α-olefin rubber polymer [a1] or the [a1] and the diene rubber polymer [a2] in the component [A] is the same as that of the rubber-reinforced vinyl resin [ A] The total amount is 5 to 30% by mass, 100% by mass, preferably 5 to 25% by mass, more preferably 8 to 20% by mass, and particularly preferably 10 to 18% by mass. When the total amount is less than 5% by mass, the impact resistance is inferior, whereas when it exceeds 30% by mass, the heat resistance is lowered.

  The mass ratio [a1]: [a2] of the ethylene / α-olefin rubber polymer [a1] and the diene rubber polymer [a2] in the component [A] is usually 90-15: 10 to 85, preferably 80 to 20:20 to 80, more preferably 75 to 25:25 to 75, and particularly preferably 75 to 50:25 to 50. By setting the mass ratio of each rubbery polymer within this range, the squeaking noise reduction effect, impact resistance and heat resistance are sufficient.

  As described above, the thermoplastic resin composition [X] of the present invention comprising the component [A] and the component [B] and, if necessary, further the component [C], is optionally filled with a filler, a nucleating agent, Various additives such as a lubricant, a heat stabilizer, an antioxidant, an ultraviolet absorber, a flame retardant, an anti-aging agent, a plasticizer, an antibacterial agent, and a colorant can be contained within a range that does not impair the purpose of the present invention. .

  Furthermore, the thermoplastic resin composition [X] of the present invention can be used for other resins such as polyethylene, polypropylene, polybutylene terephthalate, polyethylene terephthalate, polycarbonate, polyphenylene sulfide, polyamide, etc., if necessary. It can contain in the range which is not impaired.

  In the thermoplastic resin composition [X] of the present invention, each component is mixed in a predetermined blending ratio with a tumbler mixer, a Henschel mixer, etc., and then a single screw extruder, twin screw extruder, Banbury mixer, kneader, roll, feeder. It can be manufactured by melt-kneading under suitable conditions using a mixer such as a ruder. A preferred kneader is a twin screw 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 more preferable to supply the fibrous thing among fillers from the middle of an extruder with a side feeder in order to prevent the cutting | disconnection in kneading | mixing. The melt kneading temperature is usually 200 to 300 ° C, preferably 220 to 280 ° C.

4). Thermoplastic resin [Y]:
The thermoplastic resin composition of the present invention [X] is a molded article by molding, the fitting of the automobile interior parts and the like are assembled and molded articles of the thermoplastic resin (Y) which is another molded article material for later It is considered a product. There is no limitation on the method for producing the molded article of the present invention from the thermoplastic resin composition [X] and the thermoplastic resin [Y], and injection molding, injection compression molding, gas assist molding, press molding, calendar molding, It can be produced by a known method such as T-die extrusion, profile extrusion, or film molding.

The thermoplastic resin [Y] of the present invention is selected from the following groups Y1 to Y4.
Y1: Polycarbonate / rubber reinforced styrene resin alloy with HDT of 85 ° C. or higher,
Y2: Styrenic resin having an HDT of 85 ° C. or higher (excluding Y1 above),
Y3: Polyolefin resin with HDT of 85 ° C. or higher, and Y4: Methacrylic resin with HDT of 85 ° C. or higher.
These may be used alone or in combination of two or more as required.

4-1. Polycarbonate / rubber reinforced styrene resin alloy [Y1] (hereinafter also referred to as “component [Y1]”) having an HDT of 85 ° C. or higher:
In the present invention, the polycarbonate / rubber reinforced styrene resin [Y1] is not particularly limited as long as the HDT is 85 ° C. or higher. The polycarbonate (Y1a) and the rubber reinforced styrene resin (Y1b) shown below are usually 10/90 to 90 / 10 parts by mass, preferably 30/70 to 70/30 parts by mass, and more preferably 40/60 to 60/40 parts by mass. When the compounding amount of the component [Y1a] is less than 10 parts by mass, heat resistance may be insufficient. On the other hand, when the compounding amount of the component [Y1a] exceeds 90 parts by mass, moldability and impact resistance are increased. May be insufficient.

  The polycarbonate resin [Y1a] is not particularly limited, and may be an aromatic polycarbonate or an aliphatic polycarbonate. Moreover, you may use combining an aromatic polycarbonate and an aliphatic polycarbonate. The polycarbonate resin may have a terminal modified with an R—CO— group or an R′—O—CO— group (R and R ′ each represents an organic group).

  In the present invention, an aromatic polycarbonate is preferable, and those obtained by a reaction between a dihydroxyaryl compound and phosgene (phosgene method), those obtained by a transesterification reaction between a dihydroxyaryl compound and diphenyl carbonate (transesterification method), etc. Can be mentioned.

Here, as a dihydroxyaryl compound used as a raw material of the aromatic polycarbonate, bis (4-hydroxyphenyl) methane, 1,1′-bis (4-hydroxyphenyl) ethane, 2,2′-bis (4-hydroxyphenyl) ) Propane (hereinafter also referred to as “bisphenol A”), 2,2′-bis (4-hydroxyphenyl) butane, 2,2′-bis (4-hydroxyphenyl) octane, 2,2′-bis (4 -Hydroxyphenyl) phenylmethane, 2,2'-bis (4-hydroxy-3-methylphenyl) propane, 2,2'-bis (4-hydroxy-3-tert-butylphenyl) propane, 2,2'- Bis (4-hydroxy-3-bromophenyl) propane, 2,2′-bis (4-hydroxy-3,5-dichlorophenyl) propane, 1,1′-bis (4-hydroxyphenyl) cyclopentane, 1,1′-bis (4-hydroxyphenyl) cyclohexane, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dimethyldiphenyl ether, 4,4 ′ -Dihydroxyphenyl sulfide, 4,4'-dihydroxyphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethylphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxyphenyl sulfoxide, 4, Examples include 4′-dihydroxy-3,3′-dimethyldiphenyl sulfoxide, 4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfone, hydroquinone, resorcin and the like. Of these, bisphenol A is preferred. Moreover, these can be used individually or in combination of 2 or more types.
A typical aromatic polycarbonate is obtained by reaction of bisphenol A and phosgene.
The aromatic polycarbonate and the aliphatic polycarbonate can be used alone or in combination of two or more.

The viscosity average molecular weight of the polycarbonate resin [Y1a] is preferably 8,000 to 50,000, more preferably 12,000 to 30,000, and further preferably 15,000 to 26,000. This viscosity average molecular weight can be measured by a known method. If the viscosity average molecular weight is too small, the impact resistance of the molded product tends to be inferior. On the other hand, if the viscosity average molecular weight is too large, the moldability of the composition tends to be inferior. Two or more kinds of polycarbonate resins having different viscosity average molecular weights within the above range can also be used.
Moreover, the specific gravity at 20 ° C. of the polycarbonate resin is usually 1.18 to 1.22 g / cm ³ .

  The rubber-reinforced styrene-based resin [Y1b] is obtained by polymerizing a vinyl-based monomer essentially containing an aromatic vinyl compound in the presence of a rubbery polymer. For example, a styrene-based resin [Y2 described later] ] Can be used. Among rubber-reinforced styrene resins, it is preferable from the viewpoint of impact resistance to use an ABS resin that uses polybutadiene as the rubbery polymer.

  The content of the rubbery polymer in the polycarbonate / rubber-reinforced styrene resin [Y1] is usually 5 to 30% by mass, preferably 5 to 25% by mass, more preferably 100% by mass of the [Y1] component. Is 8 to 18% by mass. If the blending amount of the rubbery polymer is less than 5% by mass, the resulting molded article may have insufficient impact resistance. On the other hand, if the blending amount of the rubbery polymer exceeds 30% by mass, May be insufficient.

  There are no restrictions on the mixing order and state of the polycarbonate [Y1a] and the rubber-reinforced styrene resin [Y1b], and simultaneous mixing in the form of powder, pellets, etc., mixing the remaining components after premixing specific components A method is illustrated. In the melt mixing, a Banbury mixer, a roll, an extruder, or the like can be used.

  The polycarbonate / rubber reinforced styrene resin [Y1] is within the range of not impairing the effects of the present invention, and other thermoplastic resins, further antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents, lubricants. Dyes, pigments, plasticizers, flame retardants, mold release agents, glass fibers, metal fibers, carbon fibers, metal flakes and other known additives, reinforcing materials, fillers, and the like can be added.

4-2. Styrenic resin having an HDT of 85 ° C. or higher [Y2] (excluding the above [Y1]) (hereinafter also referred to as “component [Y2]”):
In the present invention, the styrene resin [Y2] is not particularly limited as long as the HDT is 85 ° C. or higher, and is an aromatic vinyl compound or aromatic vinyl in the presence or absence of the rubbery polymer (a1 ′). A polymer obtained by polymerizing a compound and at least one vinyl monomer (a2 ′) selected from monomers such as vinyl cyanide compounds, alkyl (meth) acrylates and maleimide compounds Or a copolymer (a1 ′) polymerized (a2 ′) in the presence (rubber-reinforced styrene resin), (a1 ′) polymerized (a2 ′) in the absence (co) Polymers and mixtures thereof are included in the [Y2] component of the present invention. In addition, the ratio of the repeating unit derived from the aromatic vinyl compound in the component (a2 ′) is usually 95 to 40% by mass, preferably 90 to 60% by mass.

  Examples of the rubbery polymer (a1 ′) include polybutadiene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, butadiene- (meth) acrylic acid ester copolymer, styrene-butadiene-styrene block copolymer, styrene. -Butadiene block copolymers, styrene-isoprene-styrene block copolymers, styrene-isoprene block copolymers, and hydrogenated products of these diene polymer parts (thickening ratio of diene parts of 30% or more) , Ethylene-propylene- (non-conjugated diene) copolymer, ethylene-butene- (non-conjugated diene) copolymer, urethane rubber, acrylic rubber, silicone rubber, silicone-acrylic IPN rubber, and the like. Or a combination of two or more.

Among these, polybutadiene, butadiene-styrene copolymer, styrene-butadiene-styrene block copolymer, and hydrogenated product of the butadiene portion of the block copolymer (diene portion hydrogenation rate of 30% or more), ethylene-propylene -(Non-conjugated diene) copolymers, acrylic rubbers and silicone rubbers are preferred.
The styrene-based resin [Y2] of the present invention is preferably a rubber-reinforced styrene-based resin containing a rubbery polymer from the viewpoint of impact resistance. In this case, the amount of the rubbery polymer (a1 ′) is usually 5 to 80. % By mass, preferably 5 to 50% by mass, more preferably 8 to 40% by mass, and particularly preferably 10 to 35% by mass.

  The vinyl monomer (a2 ′) used in the styrene resin [Y2] of the present invention is the vinyl monomer used in the production of the rubber-reinforced vinyl resin [A] and the (co) polymer [B]. The same monomers (b1) to (b3) can be used.

  Preferred combinations of the vinyl monomers (a2 ′) include styrene / acrylonitrile, α-methylstyrene / acrylonitrile, styrene / methyl methacrylate, styrene / methyl methacrylate / acrylonitrile, styrene / phenylmaleimide, styrene / anhydrous malein. Acid, styrene / acrylonitrile / 2-hydroxyethyl methacrylate, styrene / acrylonitrile / methacrylic acid, styrene / acrylonitrile / glycidyl methacrylate, and a preferred use ratio when styrene and acrylonitrile are essential components is a repeating unit derived from styrene / acrylonitrile It is the range of 60-90 / 10-40 mass% in the ratio of the repeating unit derived from.

  The styrenic resin [Y2] of the present invention can be polymerized by known polymerization methods such as emulsion polymerization, bulk polymerization, solution polymerization, suspension polymerization, and polymerization methods combining these.

Specific examples of the styrene resin not reinforced with rubber include polystyrene, AS resin, MS resin, MAS resin and the like. These weight average molecular weights are usually 20,000 or more, preferably 30,000 or more, more preferably 50,000 or more, and usually 1,000,000 or less, preferably 500,000 or less, more preferably 300. , 000 or less.
Specific examples of the rubber-reinforced styrene resin include HIPS resin, ABS resin, AES resin, MBS resin, ASA resin and the like.
The styrenic resin [Y2] in the present invention may be composed of a styrene resin that is not reinforced with rubber, a styrene resin that is reinforced with rubber, or a mixture thereof. Good.

  When the styrene resin [Y2] of the present invention contains a rubber-reinforced styrene resin, the average particle size of the rubbery polymer dispersed in the resin is in the range of 50 to 3000 nm. It is preferable from the surface appearance, More preferably, it is 100-2000 nm, Most preferably, it is 150-800 nm.

  The graft ratio of the rubber-reinforced styrene resin obtained by copolymerizing a vinyl monomer in the presence of a rubbery polymer is preferably 20 to 200% by mass, more preferably 30 to 150% by mass, particularly preferably. It is 40-120 mass%.

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 rubber-reinforced styrenic resin in 20 ml of acetone (acetonitrile when the rubbery polymer is an acrylic rubber) and shakes for 2 hours with a shaker at 25 ° C. After that, the mass (g) of insoluble matter obtained by centrifuging for 60 minutes with a centrifuge (rotation speed: 23,000 rpm) under a temperature condition of 5 ° C. to separate the insoluble matter and the soluble matter. Yes, T is the mass (g) of the rubbery polymer contained in 1 gram of rubber-reinforced styrene resin. The mass of the rubbery polymer can be obtained by a method of calculating from a polymerization prescription and a polymerization conversion rate, a method of obtaining from an infrared absorption spectrum (IR), and the like.

  Further, the intrinsic viscosity [η] (measured in methyl ethyl ketone at 30 ° C.) of the acetone-soluble component of the styrene resin [Y2] is usually 0.1 to 1.5 dl / g, preferably 0.2. -1.0 dl / g. When the intrinsic viscosity [η] is within the above range, the physical property balance between molding processability and impact resistance is excellent.

The intrinsic viscosity [η] was measured by the following method. First, the acetone-soluble component of the styrene resin [Y2] was dissolved in methyl ethyl ketone to prepare five samples having different concentrations. The intrinsic viscosity [η] was determined from the results of measuring the reduced viscosity of each concentration at 30 ° C. using an Ubbelohde viscosity tube. The unit is dl / g.
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 styrenic resin [Y2] is within the range of not impairing the effects of the present invention, and other thermoplastic resins, further antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents, lubricants, dyes, pigments Further, known additives such as plasticizers, flame retardants, mold release agents, glass fibers, metal fibers, carbon fibers, metal flakes, reinforcing materials, fillers, and the like can be added.

4-3. Polyolefin resin [Y3] having an HDT of 85 ° C. or higher (hereinafter also referred to as “component [Y3]”):
In the present invention, the polyolefin resin [Y3] is not particularly limited as long as the HDT is 85 ° C. or higher, and is typically at least one selected from the group consisting of ethylene and an α-olefin having 3 to 10 carbon atoms. It is a polymer containing olefins as constituent monomer units. As this olefin resin, those showing crystallinity at room temperature by X-ray diffraction are preferred, more preferably the crystallinity is 20% or more, and the melting point is preferably 40 ° C. or more. The olefin resin preferably has sufficient strength for use at room temperature and sufficient moldability for injection molding, for example.

  Examples of olefins that are constituent monomer units of the component [Y3] include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 4-methyl-1- Examples include pentene and 3-methyl-1-hexene, and ethylene, propylene, 1-butene, 3-methyl-1-butene, and 4-methyl-1-pentene are preferable. In addition, non-conjugated dienes such as 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene, 1,9-decadiene and the like are used as other single quantities. It can be used as a body component.

  As the component [Y3], ionomers, ethylene / vinyl acetate copolymers, ethylene / vinyl alcohol copolymers, cyclic olefin copolymers, chlorinated polyethylene, brominated polyethylene, and the like can also be used.

  The component [Y3] used in the present invention may be a homopolymer or a copolymer, and the copolymer may be either a random copolymer or a block copolymer. Of these, propylene homopolymer is particularly preferred.

  For example, the polypropylene resin as the component [Y3] preferably has a melt flow rate (MFR) measured under the conditions of 230 ° C. and 2.16 kg of 0.01 to 500 g / 10 minutes, more preferably 0.05 to 100 g / 10 min.

  The polyolefin-based resin [Y3] is not limited to the effects of the present invention, and other thermoplastic resins, further antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents, lubricants, dyes, pigments Further, known additives such as plasticizers, flame retardants, mold release agents, glass fibers, metal fibers, carbon fibers, metal flakes, reinforcing materials, fillers, and the like can be added.

  The polyolefin resin [Y3] used in the present invention may contain an inorganic filler as necessary. By blending the inorganic filler, the hardness and rigidity of the polyolefin resin may be increased, and the squeaking noise reduction effect may be improved. Examples of the inorganic filler used in the present invention include inorganic compound powders such as talc, calcium carbonate, mica, silica, and titania, and fibrous fillers such as metals, ceramics, glass beads, and glass fibers.

  Examples of the fibrous filler include organic fibers such as glass fibers, carbon fibers, and aramid fibers, inorganic fibers such as ceramic whiskers, and metal fibers. In the present invention, glass fibers are preferably used from the viewpoint of improving hardness and rigidity at high temperatures.

  Examples of the glass composition used for the glass fiber include silicate glass, borosilicate glass, and phosphate glass. Examples of the glass include E glass, C glass, A glass, S glass, M glass, AR glass, and L glass, and E glass and C glass are preferable. An appropriate sizing agent may be used for the glass fiber used in the present invention. Examples of the sizing agent include a surface treatment agent, a film forming agent, a lubricant, a surfactant, and an antistatic agent. Examples of the surface treatment agent include amine-based, silane-based, and epoxy-based coupling agents. The glass fiber used in the present invention may be a long fiber type using roving or a chopped strand.

The average length of the glass fiber before mixing with the polyolefin resin is preferably 1 to 10 mm, more preferably 2 to 6 mm, and the average diameter is preferably 5 to 100 μm, particularly preferably 8 to 20 μm.
Furthermore, the residual average fiber length of the glass fibers dispersed in the molded product obtained by molding the polyolefin resin is preferably 150 to 1000 μm, more preferably 200 to 800 μm, and further preferably 250 to 700 μm. When the residual average fiber length is in the above range, it is more preferable from the viewpoints of hardness and rigidity at high temperatures.
The residual average fiber length is measured by cutting out a part of the molded product. Specifically, the cut molded product is heated to 800 ° C. to decompose the resin component, and then the fiber length of the remaining glass fiber is measured by image analysis.

  The compounding quantity of the inorganic filler with respect to 100 mass parts of polyolefin resin is 1-50 mass parts normally, Preferably it is 5-45 mass parts.

[Y4]: Methacrylic resin having HDT of 85 ° C. or higher (hereinafter also referred to as “component [Y4]”):
In the present invention, the methacrylic resin [Y4] is not particularly limited as long as the HDT is 85 ° C. or higher. The methacrylic resin is a resin whose main raw material is a methacrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms. For example, the content of the compound unit derived from the methacrylic acid alkyl ester in the methacrylic resin is Usually, the resin is 50 to 100% by mass, preferably 60 to 100% by mass, more preferably 70 to 100% by mass, and particularly preferably 80 to 100% by mass.

  The methacrylic resin [Y4] is, for example, a homopolymer of a methacrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms, or a copolymer of the methacrylic acid alkyl ester and another monomer. Good. Examples of the alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms include methyl methacrylate, ethyl methacrylate, butyl methacrylate and the like, and these can be used alone or in combination of two or more. . As said alkyl methacrylate, it is preferable to use methyl methacrylate.

  Examples of monomers copolymerizable with the above methacrylic acid alkyl ester include acrylic acid alkyl esters; styrene and o-methyl styrene, p-methyl styrene, 2,4-dimethyl styrene, ethyl styrene, pt-butyl styrene. Alkyl-substituted styrenes such as, and aromatic vinyl compounds such as α-methylstyrene and α-alkyl-substituted styrenes such as α-methyl-p-methylstyrene; vinyl cyanides such as acrylonitrile and methacrylonitrile; N- Maleimides such as phenylmaleimide and N-cyclohexylmaleimide; unsaturated carboxylic acid anhydrides such as maleic anhydride; unsaturated acids such as acrylic acid, methacrylic acid and maleic acid. These monomers copolymerizable with methacrylic acid alkyl esters can be used alone or in combination of two or more.

  Of these monomers copolymerizable with methyl methacrylate, acrylic acid alkyl esters are particularly preferred because of their excellent thermal decomposition resistance, and methacrylic resins obtained by copolymerizing alkyl acrylates are It is preferable in terms of high fluidity during molding. The amount of alkyl acrylates used when methyl acrylate is copolymerized with methyl methacrylate is preferably 0.1% by weight or more from the viewpoint of thermal decomposition resistance, and 15% from the viewpoint of heat resistance. % Or less is preferable. The amount of alkyl acrylates used in this case is more preferably 0.2 wt% or more and 14 wt% or less, and particularly preferably 1 wt% or more and 12 wt% or less. Among these alkyl acrylates, especially methyl acrylate and ethyl acrylate are most preferable because they have a remarkable improvement effect even when only a small amount is copolymerized with methyl methacrylate. The said monomer copolymerizable with methyl methacrylate can also be used individually or in combination of 2 or more types.

  The methacrylic resin has a weight average molecular weight of usually 30,000 to 300,000, preferably 50,000 to 200,000. The weight average molecular weight is desirably 30,000 or more from the viewpoint of the strength of the molded product, and desirably 300,000 or less from the viewpoint of molding processability and fluidity. In the present invention, isotactic polymethacrylate and syndiotactic polymethacrylate can be used simultaneously.

  The methacrylic resin [Y4] is not limited to the effects of the present invention, and other thermoplastic resins, as well as antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents, lubricants, dyes and pigments. Further, known additives such as plasticizers, flame retardants, mold release agents, glass fibers, metal fibers, carbon fibers, metal flakes, reinforcing materials, fillers, and the like can be added.

According to the present invention, a fitting product formed by assembling the molded product of the thermoplastic resin composition [X] and the molded product of the thermoplastic resin [Y] is in contact with each other and squeezes generated by rubbing. It can be greatly reduced. As such a fitting parts, door trim, door lining, pillar garnish, console, door pockets, a ventilator, ducts, air conditioning, meter visor, instrument panel upper garnish, instrument panel lower garnish, A / T indicator, on-off switches (the slide portion , 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.), cup holder, switch box And steering wheel horn pad. Among them, it can be suitably used as an automobile ventilator, and can be particularly suitably used as a plate-like blade, a valve shutter, etc. of an automobile ventilator and an automobile air conditioner. Thus, it is suitable for a component having a fitting portion with another member.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated more concretely, this invention is not restrict | limited at all to the following Example, unless the summary is exceeded. In the examples, parts and% are based on mass unless otherwise specified.

(1) Evaluation method:
The measuring methods of various evaluation items in the following examples and comparative examples are shown below.

(1-1) Itching sound evaluation I (friction speed dependence of friction coefficient):
Thermoplastics listed in Table 1 using an electric injection molding machine “ELECT NEX30” (model name) manufactured by Nissei Plastic Industrial Co., Ltd. under conditions of a molding temperature of 240 ° C., a mold temperature of 50 ° C., and an injection speed of 30 mm / s. A cylindrical test piece having an inner diameter of 20 mm, an outer diameter of 24.8 mm, and a height of 15 mm made of the resin composition [X] and the thermoplastic resin [Y] is injection-molded, and then the test piece is subjected to a gear oven at 80 ° C. For 400 hours. Next, using an abrasion friction tester “EFM-III-EN” (trade name) manufactured by Orientec Co., Ltd., set a test piece made of the thermoplastic resin [Y] shown in Table 1 as a contact partner on the rotating side. Then, a test piece made of the thermoplastic resin composition [X] shown in Table 1 is set on the fixed side, and the friction strength is set under the conditions of a load of 3 kg, a rotational speed (friction speed) of 50, 100 mm / s, and 150 mm / s. Measurement was made to determine the slope of the friction coefficient with respect to the friction speed.

(1-2) Itching sound evaluation II (practical evaluation):
Using an injection molding machine “J-100E” (model name) manufactured by Nippon Steel Co., Ltd., an ISO dumbbell test piece made of the thermoplastic resin composition [X] shown in Table 1 was injection molded and then tested. The piece was left in a gear oven at 80 ° C. for 400 hours. Next, five ISO dumbbell test pieces made of the thermoplastic resin composition [X] shown in Table 1 and an ISO dumbbell made of a thermoplastic resin [Y] and left in a gear oven at 80 ° C. for 400 hours. Five test pieces were alternately stacked, and the both ends were twisted by hand to evaluate the state of generation of squeaking noise. Evaluation was performed 5 times, and determination was performed based on the following evaluation criteria.
Evaluation of squeaking noise reduction effect:
○: In all five evaluations, the occurrence of itching was slight.
(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.

(1-3) Molding Appearance Evaluation Using an electric injection molding machine “Erject NEX30” (model name) manufactured by Nissei Plastic Industry Co., Ltd., comprising a thermoplastic resin composition [X] described in Table 1, having a diameter of 80 mm, Five disk-shaped test pieces each having a thickness of 2 mm were injection molded. The test piece was provided with a φ1 mm × 1 mm gate at the center of the disk, the molding temperature was 240 ° C., the mold temperature was 50 ° C., and the injection speed was 30 mm / s. The obtained five test pieces were observed and judged based on the following evaluation criteria.
○: No jetting occurred in all five test pieces.
Δ: Among the five test pieces, jetting occurred, but the size was 10 mm or less.
X: Jetting occurred in 5 test pieces, and the size thereof exceeded 10 mm.

(1-3) Drop weight impact strength:
Using an electric injection molding machine “Erject NEX30” (model name) manufactured by Nissei Plastic Industry Co., Ltd., a flat plate type of 80 mm × 55 mm × 2.4 mm made of the thermoplastic resin composition [X] shown in Table 1 Test specimens were injection molded. The test piece was provided with a side gate of 4 mm × 1 mm at the center of one side of 55 mm, the resin temperature during molding was 240 ° C., the mold temperature was 50 ° C., and the injection speed was 30 mm / s. Next, using the Shimadzu hydro-shot / high-speed puncture impact tester “HITS-P10” (model name) manufactured by Shimadzu Corporation, the test piece was punched under the following conditions to measure the fracture energy (J).
Measurement temperature: 23 ° C
Punching speed: 6.7mm / s
Punching test jig striker tip: φ12.7mm
Die diameter of specimen holder: 43 mm

(2-1) Component [A]
A1-1: AES-1
A 20-liter stainless steel autoclave equipped with a ribbon-type stirrer blade, an auxiliary agent continuous addition device, a thermometer, etc., was used as an ethylene / α-olefin rubber polymer [a1] as an ethylene / propylene copolymer (ethylene / propylene copolymer). Propylene = 78/22 (%), Mooney viscosity (ML _{1 + 4} , 100 ° C.) 20) 22 parts, styrene 55 parts, acrylonitrile 23 parts, t-dodecyl mercaptan 0.5 part, toluene 110 parts, internal temperature Was heated to 75 ° C., and the contents of the autoclave were stirred for 1 hour to obtain a uniform solution. Thereafter, 0.45 part of t-butylperoxyisopropyl monocarbonate was added, the internal temperature was further raised, and after reaching 100 ° C., the polymerization reaction was carried out at a stirring speed of 100 rpm while maintaining this temperature. went. From 4 hours after the start of the polymerization reaction, the internal temperature was raised to 120 ° C., and the reaction was further continued for 2 hours while maintaining this temperature to complete the polymerization reaction. Thereafter, the internal temperature was cooled to 100 ° C., and 0.2 part of octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenol) -propionate was added, and then the reaction mixture was extracted from the autoclave, Unreacted substances and the solvent were distilled off by distillation, and the volatile matter was substantially degassed using a 40 mmφ vented extruder (cylinder temperature 220 ° C., vacuum degree 760 mmHg), and pelletized. The resulting ethylene / α-olefin rubber-reinforced vinyl resin had a graft rate of 70% and an intrinsic viscosity [η] of acetone-soluble content of 0.47 dl / g.

A2-1: ABS-1
In a polymerizer with a stirrer, 280 parts of water and diene rubber polymer [a2], 60 parts of polybutadiene latex having a weight average particle diameter of 0.26 μm and a gel fraction of 90% (in terms of solid content), sodium formaldehyde sulfoxylate 0.3 parts, 0.0025 parts of ferrous sulfate and 0.01 parts of disodium ethylenediaminetetraacetate were added, and after deoxidation, the mixture was heated to 60 ° C. with stirring in a nitrogen stream, and then 10 parts of acrylonitrile and 30 parts of styrene. Part, t-dodecyl mercaptan 0.2 part, and a monomer mixture consisting of cumene hydroperoxide 0.3 part were continuously added dropwise at 60 ° C. over 5 hours. After completion of the dropwise addition, the polymerization temperature was set to 65 ° C. and stirring was continued for 1 hour, and then the polymerization was terminated to obtain a latex of a graft copolymer. The polymerization conversion rate was 98%. Thereafter, 0.2 part of 2,2′-methylene-bis (4-ethylene-6-tert-butylphenol) is added to the obtained latex, and calcium chloride is added to coagulate, washing, filtering and drying steps. After that, a powdery resin composition was obtained. The graft ratio of the obtained resin composition was 40%, and the intrinsic viscosity [η] of the acetone-soluble component was 0.38 dl / g.

A1-2: AES-2
Ethylene / propylene / dicyclopentadiene copolymer as an ethylene / α-olefin rubbery polymer [a1] in a 20 liter stainless steel autoclave equipped with a ribbon stirrer blade, auxiliary additive device, thermometer, etc. (Ethylene / propylene / dicyclopentadiene = 63/32/5 (%), Mooney viscosity (ML _{1 + 4} , 100 ° C.) 33) 30 parts, styrene 45 parts, acrylonitrile 25 parts, t-dodecyl mercaptan 0.5 part Then, 140 parts of toluene was charged, the internal temperature was raised to 75 ° C., and the contents of the autoclave were stirred for 1 hour to obtain a uniform solution. Thereafter, 0.45 part of t-butylperoxyisopropyl monocarbonate was added, the internal temperature was further raised, and after reaching 100 ° C., the polymerization reaction was carried out at a stirring speed of 100 rpm while maintaining this temperature. went. From 4 hours after the start of the polymerization reaction, the internal temperature was raised to 120 ° C., and the reaction was further continued for 2 hours while maintaining this temperature to complete the polymerization reaction. Thereafter, the internal temperature was cooled to 100 ° C., and 0.2 part of octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenol) -propionate was added, and then the reaction mixture was extracted from the autoclave, Unreacted substances and the solvent were distilled off by distillation, and the volatile matter was substantially degassed using a 40 mmφ vented extruder (cylinder temperature 220 ° C., vacuum degree 760 mmHg), and pelletized. The resulting ethylene / α-olefin rubber-reinforced vinyl resin had a graft rate of 60% and an intrinsic viscosity [η] of acetone-soluble content of 0.45 dl / g.

B-1: AS-1
In a polymerization vessel equipped with a stirrer, 250 parts of water and 1.0 part of sodium palmitate were charged, and after deoxygenation, the mixture was heated to 70 ° C. with stirring in a nitrogen stream. Further, 0.4 parts of sodium formaldehyde sulfoxylate, 0.0025 part of ferrous sulfate and 0.01 part of disodium ethylenediaminetetraacetate were added, and then 70 parts of α-methylstyrene, 25 parts of acrylonitrile, 5 parts of styrene, t- A monomer mixture composed of 0.5 parts of dodecyl mercaptan and 0.2 parts of cumene hydroperoxide was continuously added dropwise at a polymerization temperature of 70 ° C. over 7 hours. After completion of the dropping, the polymerization temperature was set to 75 ° C., and stirring was continued for 1 hour to complete the polymerization, thereby obtaining a copolymer latex. The polymerization conversion rate was 99%. Thereafter, the obtained latex was coagulated by adding calcium chloride, and a powdery copolymer was obtained through washing, filtration and drying steps. The intrinsic viscosity [η] of the acetone-soluble component of the obtained copolymer was 0.40 dl / g.

(2-2) Component [C] (silicone oil):
C-1: Methylphenyl silicone oil; KF54 (trade name: manufactured by Shin-Etsu Silicone Co., Ltd.), kinematic viscosity at 25 ° C. was 400 cSt.

C-2: amino-modified silicone oil; TSF4700 (trade name: manufactured by Momentive Performance Materials Japan), kinematic viscosity at 25 ° C. was 50 cSt.

C-3: alkyl aralkyl-modified silicone oil; XF42-334 (trade name: manufactured by Momentive Performance Materials Japan), kinematic viscosity at 25 ° C. was 1300 cSt.

(2-3) Additive:
D-1: Ethylene bis-stearic acid amide; Kao wax EB-P (trade name: manufactured by Kao Corporation)
D-2: 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) -s-triazine-2,4,6- (1H, 3H, 5H) trione; Adekastab AO- 20 (Product name: Made by ADEKA Corporation)
D-3: Bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite; ADK STAB PEP-24G (trade name: manufactured by ADEKA Corporation)

(2-4) Thermoplastic resin [Y]
Y1: Techno Polymer Co., Ltd. PC / ABS CK43 (HDT 95 ° C)
Y2: Technopolymer Co., Ltd. Heat-resistant ABS E7301 (HDT95 ° C)
Y3: Prime polymer Prime polypro (short fiber GFPP) V-7000 (HDT 150 ° C)
Y4: Mitsubishi Rayon Co., Ltd. PMMA Acrypet VH001 (HDT100 ℃)
Y5: Technopolymer ABS170 (HDT 76 ° C)

Examples 1 to 13 and Comparative Examples 1 to 5
After mixing the above components [A] to [D] with a Henschel mixer at the blending ratio shown in Table 1, they are kneaded with a twin-screw extruder (manufactured by Nippon Steel, TEX44, barrel setting temperature 250 ° C.), and thermoplastic. The resin composition [X] was pelletized. Each test piece for evaluation was shape | molded with the obtained pellet. The HDT of the thermoplastic resin composition [X] is 93 ° C. for the compositions of Examples 1 to 8 and 13, 90 ° C. for the compositions of Examples 9 to 12, and 91 for the compositions of Comparative Examples 1 to 5. ° C.
On the other hand, the thermoplastic resin [Y] was pelletized in the same manner, and each test piece for evaluation was molded from the obtained pellet. And it evaluated by the said method using the obtained test piece. The above evaluation results are shown in Table 1.

As apparent from Table 1, the molded product of the thermoplastic resin composition [X] of the present invention represented by Examples 1 to 13 and the molded product of the thermoplastic resins [Y1] to [Y4] are assembled. The fitting product can provide a molded product in which the squeaking noise targeted by the present invention is reduced, and the impact resistance and the molded appearance are provided in a well-balanced manner.
On the other hand, Comparative Examples 1 to 4 are examples in which the rubber-reinforced vinyl resin [A1] obtained by polymerizing the ethylene / α-olefin rubber polymer [a1] was not used. Inferior. Comparative Example 5 is an example in which the resin [Y5] other than [Y1] to [Y4] of the present invention was used as the thermoplastic resin [Y]. The test piece of [Y5] was left in the gear oven (80 ° C., 400 hours), the measurement of the friction strength became unstable, and the stagnation sound evaluation could not be performed.

In the thermoplastic resin composition [X] of the present invention, the squeaking noise generated when the members rub against each other is remarkably reduced, and the squeaking noise reduction effect is maintained without being deteriorated even when placed at a high temperature for a long time. Furthermore, it is possible to provide a molded product having excellent impact resistance and molded appearance. In addition, a fitting product composed of the molded product of the present invention and a molded product of thermoplastic resin [Y] can be suitably used for automotive interior parts such as automotive ventilators and automotive air conditioners. It can be suitably used for a part having a portion.

M Object V Drive speed μs Static friction coefficient μl Sawtooth waveform lower end Δμ μs-μl

Claims (9)

A molded article of the following thermoplastic resin composition [X] and a molded article of the thermoplastic resin [Y] selected from the following groups Y1 to Y4, and molded of the thermoplastic resin composition [X] Product and a molded product of the thermoplastic resin [Y] are assembled:
Thermoplastic resin composition [X]:
Rubber reinforced vinyl resin [A1] obtained by polymerizing vinyl monomer [b1] containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of ethylene / α-olefin rubber polymer [a1] And a rubber-reinforced vinyl resin [A2] obtained by polymerizing a vinyl monomer [b2] containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of a diene rubber polymer [a2] And a thermoplastic resin composition comprising a (co) polymer [B] of a vinyl monomer [b3] containing an aromatic vinyl compound and a vinyl cyanide compound An object [X],
The total amount of the ethylene / α-olefin rubbery polymer [a1] and the diene rubbery polymer [a2] is 5 to 30% by mass with respect to 100% by mass of the entire thermoplastic resin composition [X]. Yes,
The mass ratio [a1]: [a2] of the ethylene / α-olefin rubbery polymer [a1] and the diene rubbery polymer [a2] is 90 to 34:10 to 66, Thermoplastic resin composition with reduced squeaking noise.
Molded product of thermoplastic resin [Y]:
A molded product selected from the following Y1 to Y4.
Y1: Polycarbonate / rubber reinforced styrene resin alloy with HDT of 85 ° C. or higher,
Y2: Styrenic resin having an HDT of 85 ° C. or higher (excluding Y1 above),
Y3: polyolefin resin having an HDT of 85 ° C. or higher, and
Y4: Methacrylic resin having an HDT of 85 ° C. or higher. The fitting according to claim 1, wherein HDT is 85 ° C or higher. The fitting according to claim 1 or 2, wherein the ethylene / α-olefin rubbery polymer [a1] has an ethylene: α-olefin mass ratio of 5 to 95:95 to 5. The fitting according to any one of claims 1 to 3, wherein the ethylene / α-olefin rubbery polymer [a1] is an ethylene / propylene copolymer. The thermoplastic resin composition [X] is 100 parts by mass, and a silicone oil [C] having a kinematic viscosity at 25 ° C. of 10 to 100,000 cSt is blended in an amount of 0.1 to 8 parts by mass. The fitting product according to any one of the items . The fitting according to claim 5, wherein the silicone oil [C] is methylphenyl silicone oil . The fitting product according to any one of claims 1 to 6, which is an automobile interior part. The fitting product according to claim 7 , wherein the automobile interior part is an automobile ventilator. 7. Symbol mounting of the fitting parts automotive interior component is an air conditioner for an automobile.

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