JP6530836B2 - 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 stagnant noise generated by contact with other members and rubbing is significantly reduced.

ABS resin is excellent in mechanical strength and moldability and is used in a wide range of fields such as automobiles, home appliances and OAs, but heat resistance and impact resistance are insufficient and its application is limited. On the other hand, polycarbonate (PC) resin is excellent in heat resistance and impact resistance, and is used in a wide range of fields such as automobiles, home appliances and precision machinery, but its moldability and impact resistance at low temperatures are insufficient. Is limited.
As a method of compensating for these drawbacks, it is known to blend an ABS resin and a polycarbonate resin. When this method is used, the heat resistance and impact resistance of the ABS resin are improved, and the moldability of the polycarbonate resin and the impact resistance at low temperatures are also improved. As a result, the moldability, impact resistance and mechanical strength In addition, a resin blend with excellent heat resistance is obtained, and it has become possible to be used in a wide range of fields such as automotive interior parts that are required to have passenger safety at the time of a collision.

  However, when a molded product made of PC / ABS resin in which ABS resin and polycarbonate resin are blended is used for automobile interior parts, PC / ABS resin automobile interior parts are said to be each other or part due to vibration during traveling of the automobile. Makes contact with other members such as ABS resin, acrylic resin, polyvinyl chloride, chloroprene rubber, polyurethane, natural rubber, polyester or polyethylene lining sheet, foam, etc. Sometimes. In addition, when used for desk drawers and applications around doors, PC / ABS parts contact metal members such as SUS, aluminum and brass parts, and other members such as ABS resin, resulting in noise ) May occur. These noises are a major cause of impairing the comfort and quietness of the automobile room, the office, and the house interior, and there is a strong demand for reduction of the noise.

Since the above PC / ABS resin and PC resin are amorphous resins, they have a high coefficient of friction as compared with crystalline resins such as polyethylene, polypropylene and polyacetal, and switch parts of instrument panels in automobiles and office desks When used in a part that comes into contact with other members by fitting etc., such as slide parts, etc., the stick-slip phenomenon as shown in FIG. Occurs. The stick-slip phenomenon occurs when two objects rub against each other, and as shown by the model in FIG. 2A, when the spring-connected object M is placed on a driving base moving at a driving speed V The object M first moves rightward as shown in FIG. 2 (b) together with a platform which moves at the driving speed V by the action of the static friction force. Then, when the force to be returned by the spring becomes equal to this static friction force, the object M slides in the direction opposite to the driving speed V. At this time, the object M is subjected to a dynamic friction force, so the slip stops at the point of FIG. 2 (c) where the force of the spring and this dynamic friction force become equal, that is, the object M adheres to the drive stand. It moves in the same direction as the driving speed V (FIG. 2 (d)). This is called a stick-slip phenomenon, and as shown in FIG. 1, it is said that when the difference Δμ between the static friction coefficient μs and the μl at the lower end of the sawtooth waveform is large, a stagnant noise is easily generated. The dynamic friction coefficient is an intermediate value between μs and μl.
These noises are a major cause of impairing the comfort and quietness of the automobile room, the office, and the house interior, and there is a strong demand for reduction of the noise.

  On the other hand, it is known that the stick-slip phenomenon appears notably when the friction velocity dependency of the friction coefficient obtained by the Amonton-Coulomb law takes a negative value (see Non-Patent Document 1). Therefore, it is possible to suppress the occurrence of the stick-slip phenomenon and reduce the generation of stagnant noise by making the friction velocity dependency of the friction coefficient close to zero or to have a positive value of zero or more.

  Then, in order to prevent the stagnation sound of these contact parts, the method of applying Teflon (registered trademark) coating on the member surface, the method of attaching a Teflon (registered trademark) tape, the method of attaching a non-woven fabric, the method of applying silicone oil, etc. However, the process of mounting and coating is very complicated and time-consuming, and there is a problem that the effect is not sustained when placed for a long time under high temperature.

  Also, as a method of modifying the material itself of the contact parts used for automobile interior parts and indoor mechanical parts, a method of blending silicone oil with ABS resin, a method of blending an epoxy resin containing olefin copolymer with ABS resin, etc. Proposed. For example, a technique of blending an organosilicon compound in a resin consisting of a polycarbonate resin and an ABS resin (see Patent Document 1) and a technique of blending a flame retardant, a flame retardant aid and a silicone oil in ABS resin (see Patent Document 2) Also, the technology of blending silicone oil into ABS resin, MBS resin and HIPS (high impact polystyrene) resin (see Patent Document 3), and the technology of blending alkane sulfonate-based surfactant in ABS resin (Patent Document 4) (See also) further mix modified polyorganosiloxane containing at least one reactive group selected from epoxy group, carboxyl group and acid anhydride group into ABS resin to increase water repellency and water in bathroom and toilet The technique (refer patent document 5) used for a turning part is disclosed.

  However, the reduction effect of stagnation noise by these methods is not sufficient, and even if it shows some stagnation noise prevention effect immediately after molding, the persistence of the effect is poor, especially when it is left under high temperature for a long time There was a problem that the effect was greatly reduced. Furthermore, in recent years, in order to secure the safety of the occupant in the event of a collision, not only the impact resistance but also the brittle fracture which may cause the fragments of the broken molded article to be scattered is required in the vehicle interior application. Came to be

Japanese Patent Publication No. 63-56267 Patent No. 2798396 gazette Patent No. 2688619 gazette Patent 2659467 gazette Japanese Patent Application Laid-Open No. 10-316833

Surface science Vol. 24, No. 6, PP 328-333, 2003

  In view of such circumstances, the present invention significantly reduces the generation of stagnation noise generated when the members rub against each other, and the stagnant noise reduction effect is maintained without reduction even when the product is placed under high temperature for a long time. Is a thermoplastic resin composition excellent in moldability, impact resistance, mechanical strength and heat resistance, which can be used in a wide range of fields such as automobile interior parts which are required to have passenger safety at the time of a collision The purpose is to provide goods.

MEANS TO SOLVE THE PROBLEM As a result of conducting earnest research in order to solve the said subject, the present inventors graft-polymerized the vinyl-type monomer to the specific ethylene and alpha-olefin type rubbery polymer to polycarbonate resin, and rubber modified vinyl-type resin By blending a specific amount of it, the generation of stagnation noise generated when the members rub against each other is significantly reduced, and the stagnant noise reduction effect is maintained without reduction even when placed under high temperature for a long time, and further , Thermoplastic resin compositions and molded articles excellent in moldability, impact resistance, mechanical strength and heat resistance that can be used in a wide range of fields such as automobile interior parts that require safety for occupants in the event of a collision It was found that was obtained. In addition, it has also been found that by blending a specific amount of a specific silicone oil and / or a polyolefin wax with the above-mentioned thermoplastic resin composition, it is further excellent in the reduction effect of stagnant noise.
The present invention has been completed based on such findings.

According to the present invention, the following thermoplastic resin composition and molded article are provided. That is ,
1 . A thermoplastic resin comprising 20 to 65 parts by mass of a rubber-reinforced vinyl resin [A] and 35 to 80 parts by mass of a polycarbonate resin [B] (however, 100 parts by mass of the total of [A] and [B]) Resin composition [X], which is
Ethylene / α-olefin consisting of 60 to 95% by mass of ethylene and 40 to 5% by mass of α-olefin (wherein the total of ethylene and α-olefin is 100% by mass) of the rubber-reinforced vinyl resin [A] In the presence of a rubber-reinforced vinyl resin [A1] obtained by polymerizing a vinyl monomer [c1] in the presence of a rubber-based polymer [a1] and a diene rubber polymer [a2] A rubber-reinforced vinyl-based resin [A2] obtained by polymerizing a vinyl-based monomer [c2], and the ethylene / α-olefin-based rubber-like polymer [a1] and the diene-based rubber The thermoplastic resin composition in which the total amount of polymer [a2] is 5-30 mass% which is 100 mass% of thermoplastic resin composition [X], and which has reduced stagnant noise.
2 . The 1 rubber-reinforced vinyl-based resin (A) is, which comprises further vinyl monomer [c3] The (co) polymer (C). The thermoplastic resin composition as described in-.
3 . The 1 10 to 85: the weight ratio of the ethylene · alpha-olefin rubbery polymer as [a1] diene-based rubbery polymer and [a2] [a1]: [a2] is 90 to 15. To 2 . The thermoplastic resin composition as described in-.
4 . In 100 parts by mass of the thermoplastic resin composition [X], 0.1 to 8 parts by mass of silicone oil [D] and / or 0.1 to 8 parts by mass of polyolefin wax [E] are further contained. Above 1 . To 3 . The thermoplastic resin composition according to any one of the above.
5 . Silicone oil (D) is at least one selected from the group consisting of methylphenyl silicone oil, alkyl-aralkyl-modified silicone oil and amino-modified silicone oil above 4. The thermoplastic resin composition as described in-.
6 . Above 1 . To 5 . The molded article which reduced the lingling sound formed by shape | molding the thermoplastic resin composition in any one of these.
7 . The above 6 which is a contact component which contacts and rubs with other members. Articles described in.

  According to the present invention, when a rubber-reinforced vinyl resin obtained by graft polymerizing a vinyl monomer with a specific ethylene / α-olefin rubber polymer and a polycarbonate resin are blended in a specific amount, the members rub against each other It is possible to significantly reduce the generation of stagnant noise, and to maintain the stagnant noise reduction effect without lowering even when the product is placed under high temperature for a long time, and further, for automobile interior parts where safety of occupants in a collision is required. And thermoplastic resin compositions and molded articles excellent in moldability, impact resistance, mechanical strength and heat resistance that can be used in a wide range of fields such as

FIG. 1 is an explanatory view of the stick-slip phenomenon. FIGS. 2 (a), (b), (c) and (d) are model diagrams of stick-slip. FIG. 3 is a schematic view showing a method of examining the generation of a stagnant sound.

Hereinafter, the present invention will be described in detail.
The thermoplastic resin composition in the present invention comprises 20 to 65 parts by mass of a rubber-reinforced vinyl resin [A] and 35 to 80 parts by mass of a polycarbonate resin [B] (however, 100 in total of [A] and [B]). A thermoplastic resin composition [X] which comprises (parts by mass),
Rubber-reinforced vinyl-based resin [A1] obtained by polymerizing vinyl-based monomer [c1] in the presence of ethylene / α-olefin rubber-based polymer [a1] And a rubber-reinforced vinyl-based resin [A2] obtained by polymerizing a vinyl-based monomer [c2] in the presence of a diene-based rubbery polymer [a2],
The total amount of the ethylene / α-olefin rubbery polymer [a1] and the diene rubbery polymer [a2] is 5 to 30% by mass, based on 100% by mass of the thermoplastic resin composition [X]. It is characterized by

  In the present specification, “(co) polymerization” means homopolymerization and copolymerization, “(meth) acrylic” means acrylic and / or methacryl, and “(meth) acrylate” Means acrylate and / or methacrylate.

1. Rubber-reinforced vinyl resin [A] (hereinafter, also referred to as “component [A]” hereinafter):
The component [A] used in the present invention is a rubber-reinforced vinyl resin [A1] obtained by polymerizing a vinyl monomer [c1] in the presence of an ethylene / α-olefin rubbery polymer [a1]. A mixture with a rubber-reinforced vinyl resin [A2] obtained by polymerizing a vinyl monomer [c2] alone and, if necessary, in the presence of a diene rubber polymer [a2], and / or Alternatively, it is a rubber-reinforced vinyl resin comprising a mixture of a vinyl monomer [c3] with a (co) polymer [C]. The (co) polymer [C] is obtained by polymerizing the vinyl monomer [c3] in the absence of a rubbery polymer.

1-1. Ethylene / α-olefin rubber polymer [a1] (hereinafter also referred to as “component [a1]):
The ethylene / α-olefin rubber polymer [a1] used in the present invention may have a Tm (melting point) or may not have a Tm. For example, an ethylene / α-olefin copolymer And ethylene / α-olefin / nonconjugated diene copolymers. Here, Tm is a value obtained by measuring the endothermic change at a constant temperature rising rate of 20 ° C. per minute using DSC (differential scanning calorimeter) and reading the peak temperature of the obtained endothermic pattern, the details , JIS K 712 1-1987. In the measurement of DSC, those which do not show the peak of endothermic change clearly are those having substantially no crystallinity in the rubbery polymer and judged to have no Tm, and the above-mentioned Tm is not less than 0 ° C. Is not included in the rubbery polymer. Therefore, the thing without Tm is inferior to the reduction effect of itching sound, when it leaves it under high temperature for a long time excessively.
Further, the glass transition temperature (Tg) of the rubbery polymer is preferably -20 ° C or less, more preferably -30 ° C or less, and particularly preferably -40 ° C or less. When the glass transition temperature exceeds -20 ° C, the impact resistance may be insufficient. In addition, the said glass transition temperature can be calculated | required based on JISK7121-1987 using DSC (differential scanning calorimeter) similarly to measurement of Tm (melting | fusing point).

As an alpha olefin which constitutes the above-mentioned ingredient [a1], C3-C20 alpha olefin is mentioned, for example, 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 combination of two or more. The carbon number of the α-olefin is preferably 3 to 20, more preferably 3 to 12, and further preferably 3 to 8. When the carbon number is more than 20, the copolymerizability may be reduced, and the surface appearance of the molded article may not be sufficient. The mass ratio of ethylene: α-olefin is usually 5 to 95:95 to 5, preferably 50 to 95:50 to 5, and more preferably 60 to 95:40 to 5.
When the mass ratio of the α-olefin exceeds 95, the impact resistance of the resulting rubber-reinforced vinyl-based resin becomes insufficient, which is not preferable. Moreover, even if it is less than 5, since the rubber elasticity of the rubbery polymer [a1] is not sufficient, the impact resistance of the resin composition is not sufficient.

  Nonconjugated dienes include alkenyl norbornenes, cyclic dienes and aliphatic dienes, preferably 5-ethylidene-2-norbornene and dicyclopentadiene. These nonconjugated dienes can be used alone or in combination of two or more. The ratio of the nonconjugated diene to the total amount of the rubbery polymer is usually 0 to 20% by mass, preferably 0 to 10% by mass, and more preferably 0 to 5% by mass. When the proportion of the nonconjugated diene exceeds 20% by mass, the melting point (Tm) of the rubber-like polymer [a1] may decrease or the melting point may disappear, and the reduction effect of the stagnant sound may be insufficient.

  The Mooney viscosity (ML1 + 4, 100 ° C .; in accordance with JIS K6300) of the component [a1] is usually 5 to 80, preferably 10 to 65, and more preferably 10 to 45. When the Mooney viscosity exceeds 80, the fluidity of the resulting rubber-reinforced vinyl resin may be insufficient, and when the Mooney viscosity is less than 5, the impact resistance of the resulting molded article may be insufficient. There is.

  The ethylene / α-olefin rubbery polymer [a1] is preferably an ethylene / α-olefin copolymer not containing a non-conjugated diene component from the viewpoint of reducing the stagnant sound, and among these, ethylene / propylene copolymer Combined, ethylene / 1-butene copolymer, ethylene / 1-octene copolymer are more preferable, and ethylene / propylene copolymer is particularly preferable.

  Further, a polymer obtained by hydrogenating a block (co) polymer obtained by using a conjugated diene compound such as butadiene and isoprene in this ethylene / α-olefin rubbery polymer [a1] 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-based rubbery polymer [a2] (hereinafter referred to as "component a2"):
Examples of diene-based rubbery polymers [a2] include homopolymers such as polybutadiene and polyisoprene; styrene-butadiene copolymer, styrene-butadiene-styrene copolymer, acrylonitrile-styrene-butadiene copolymer, acrylonitrile-butadiene Butadiene-based copolymers such as copolymers; styrene-isoprene copolymers, styrene-isoprene-styrene copolymers, isoprene-based copolymers such as acrylonitrile-styrene-isoprene copolymers, and the like. These may be random copolymers or block copolymers. Moreover, these can be used individually or in combination of 2 or more types. The diene rubbery polymer [a2] may be a crosslinked polymer or an uncrosslinked polymer.

1-3. Vinyl-based monomer [c1] to [c3]:
The vinyl monomers [c1], [c2] and [c3] are not particularly limited as long as they are polymerizable compounds having unsaturated bonds.
The vinyl monomers [c1], [c2] and [c3] 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 one or more functional groups such as an oxazoline group may be used in combination. The vinyl monomers [c1] and [c2] used to form the rubber-reinforced vinyl resins [A1] and [A2] may be identical to or different from each other.
The vinyl monomer [c3] used to form the (co) polymer [C] may be the same as or different from the vinyl monomers [c1] and / or [c2]. May be

  As the aromatic vinyl compound, any compound having at least one vinyl bond and at least one aromatic ring can be used without particular limitation. Examples thereof include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, vinyltoluene, β-methylstyrene, ethylstyrene, p-tert-butylstyrene, vinylxylene, vinylnaphthalene, monochlorostyrene, dichloro Styrene, monobromostyrene, dibromostyrene, fluorostyrene and the like can be mentioned. These can be used alone or in combination of two or more. Among these, styrene and α-methylstyrene are preferred.

  Examples of the above-mentioned vinyl cyanide compound include acrylonitrile and methacrylonitrile. These can be used alone or in combination of two or more. Among these, acrylonitrile is preferable.

  As the (meth) acrylic acid ester, 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, methacryl Methacrylic acid esters such as octadecyl acid, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate and the like can be mentioned. These can be used alone or in combination of two or more. Among these, methyl methacrylate is preferred.

Examples of the maleimide compound include maleimide, N-methyl maleimide, N-butyl maleimide, N-cyclohexyl maleimide, N-phenyl maleimide and the like. These can be used alone or in combination of two or more. Moreover, among these, N-cyclohexyl maleimide and N-phenyl maleimide are preferable.
In addition, as a method of introduce | transducing the monomer unit which consists of this maleimide compound into a polymer, there exists a method of copolymerizing a maleic anhydride previously, and imidating after that.

  Among the above functional group-containing vinyl monomers, examples of unsaturated compounds having a carboxyl group include acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, cinnamic acid and the like. . 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, citraconic anhydride and the like. 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 And -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 the unsaturated compound 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, acrylamine, methacrylamine, N- Methyl acryl amine etc. are mentioned. These can be used alone or in combination of two or more.
As the unsaturated compound having an amide group, acrylamide, N-methyl acrylamide, methacrylamide, N-methyl methacrylamide and the like can be mentioned. These can be used alone or in combination of two or more.

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

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

  The type and amount of use of the vinyl monomers [c1], [c2] and [c3] are selected according to the purpose, use, etc., but the total amount of the aromatic vinyl compound and the cyanidated vinyl compound is The amount is usually 30 to 100% by mass, preferably 50 to 100% by mass, and more preferably 70 to 100% by mass, based on 100% by mass of the total amount of the vinyl-based monomer. The content of the other copolymerizable vinyl-based monomer is usually 0 to 70% by mass, preferably 0 to 50% by mass, and more preferably 0 to 30 based on 100% by mass of the entire vinyl-based monomer. It is mass%. The content of the functional group-containing vinyl-based monomer is usually 0 to 40% by mass, preferably 0 to 30% by mass, and more preferably 0 to 20% by mass, based on 100% by mass of the total amount of the vinyl-based monomer. %. In addition, 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 above-mentioned 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 form of its content is not particularly limited.
In the above-mentioned rubber-reinforced vinyl resin [A], a graft copolymer in which a (co) polymer of a vinyl monomer is usually grafted on a rubbery polymer and not grafted on a rubbery polymer Included are (co) polymers of vinyl monomers. However, this graft copolymer may contain a rubbery polymer in which the (co) polymer of the vinyl monomer is not grafted.
Moreover, the content aspect in the case of using said ethylene * alpha-olefin rubber polymer [a1] and diene rubber polymer [a2] is illustrated below.
(1) When both the ethylene / α-olefin rubbery polymer [a1] and the diene rubbery polymer [a2] are contained as a graft copolymer.
(2) When any one of the ethylene / α-olefin rubbery polymer [a1] and the diene rubbery polymer [a2] is contained as a graft copolymer.
(3) In the case where both the ethylene / α-olefin rubbery polymer [a1] and the diene rubbery polymer [a2] are contained as an ungrafted rubbery polymer.
Among these, (1) is particularly preferable.

The rubber-reinforced vinyl-based resin [A] of the above aspect (1) is exemplified below.
[I] A rubber-reinforced vinyl resin [A1] obtained by polymerizing a vinyl monomer [c1] 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 [c2] in the presence of the diene rubber polymer [a2]. .
[Ii] A mixture comprising the above mixture [i] and a (co) polymer [C] of the vinyl monomer [c3] (hereinafter also referred to as “(co) polymer [C]”).
[Iii] obtained by polymerizing a vinyl monomer [c1] or [c2] 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 [C].
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, methods for producing the above-described 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-based monomer may be charged at one time and reacted, or may be reacted in divided or continuous addition. In addition, the rubbery polymer may be reacted in its entirety or in part during the polymerization with the vinyl monomer.
The amount of the rubbery polymer used is usually 5 to 80% by mass, preferably 10 to 70% by mass, based on 100% by mass of the total of the rubbery polymer and the vinyl monomer.

The method for producing the rubber-reinforced vinyl resin [A1] is preferably solution polymerization or bulk polymerization, more preferably solution polymerization, and the method for producing the rubber-reinforced vinyl resin [A2] is emulsion polymerization, suspension polymerization Emulsion polymerization, solution polymerization, suspension polymerization and bulk polymerization are preferred as the method for producing the rubber-reinforced vinyl resin [A3], and these methods may be combined.
When the 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. When the rubber polymer is not in the form of a latex but in the form of a solid, it can be used as a latex by re-emulsification.

As a polymerization initiator, a combination of an organic peroxide such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramenthane hydroperoxide, and a reducing agent typified by a sugar-containing pyrophosphate formulation, a sulfoxylate formulation, etc. Redox type polymerization initiators; persulfates such as potassium persulfate; benzoyl peroxide (BPO), lauroyl peroxide, peroxides such as tert-butyl peroxy laurate, tert-butyl peroxy monocarbonate, etc. Azo polymerization initiators such as 2'-azobis (isobutyronitrile) and the like can be mentioned. 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, relative to the total amount of the vinyl monomer [c1] or [c2].
The polymerization initiator is usually added all at once or continuously to the reaction system.

  Chain transfer agents include mercaptans such as octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, n-hexyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, tert-tetradecyl mercaptan; terpinolenes, α -A dimer of methylstyrene, tetraethylthiuram sulfide, acrolein, methacrolein, allyl alcohol, 2-ethylhexyl thioglycol 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 [c1] or [c2].

  As an emulsifier, anionic surfactant and nonionic surfactant are mentioned. Examples of anionic surfactants include sulfuric acid esters of higher alcohols; alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate; aliphatic sulfonates such as sodium lauryl sulfate; rosin acid salts and phosphates. Further, examples of the nonionic surfactant include alkyl ester type compounds of polyethylene glycol, alkyl ether type compounds and the like. These can be used alone or in combination of two or more. The amount of the emulsifier used is usually 0.3 to 5% by mass with respect to the total amount of the vinyl monomer [c1] or [c2].

  The emulsion polymerization can be carried out under known conditions depending on the type and amount of the vinyl monomer [c1] or [c2], polymerization initiator, etc. to be used. The latex obtained by the above-mentioned emulsion polymerization is usually coagulated with a coagulant to make a polymer component into a powder, which is then purified by washing with water and drying. As the coagulant, 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 are used. These can be used alone or in combination of two or more. In addition, depending on the required performance, after coagulation, an alkali component or an acid component may be added and subjected to neutralization treatment, followed by washing.

When the above-mentioned rubber-reinforced vinyl resins [A1], [A2] and [A3] are produced by solution polymerization, a solvent, a polymerization initiator, a chain transfer agent, etc. are usually used.
As the solvent, known inert polymerization solvents used in radical polymerization, for example, aromatic hydrocarbons such as ethylbenzene and toluene; ketones such as methyl ethyl ketone and acetone; halogenated hydrocarbons such as dichloromethane 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 peroxides, dialkyl peroxides, diacyl peroxides, peroxy esters, and hydroperoxides. These can be used alone or in combination of two or more.
As a chain transfer agent, mercaptans, terpinolenes, the dimer of alpha-methylstyrene, etc. are mentioned. 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 [c1] or [c2], polymerization initiator, etc. to be used. The polymerization temperature is usually in the range of 80 to 140 ° C. In addition, in the case of solution polymerization, it can also be manufactured 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, etc. used in these methods are not particularly limited, but the same compounds as exemplified in the solution polymerization can be used.

1-5. Physical Properties of Rubber-Reinforced Vinyl-Based Resin [A]:
The graft ratio of each of the rubber-reinforced vinyl resins [A1], [A2] and [A3] obtained as described above is usually 10 to 150% by mass, preferably 20 to 120% by mass, particularly preferably Is 20 to 80% by mass. If the grafting ratio is less than 10% by mass, the interface strength between the graft copolymer and the (co) polymer of the vinyl monomer [c1] or [c2] is poor, so the impact resistance may not be sufficient. . On the other hand, if it exceeds 150% by mass, the layer consisting of the (co) polymer of the vinyl monomer [c1] or [c2] on the surface of the rubbery polymer will be thick, and grafting to the inside of the rubbery polymer As a layer made of the above (co) polymer develops, the rubber elasticity may be reduced, and as a result, the impact resistance may be reduced.

  The graft ratio can be determined by the following equation.

  Graft ratio (mass%) = {(S−T) / T} × 100

  In the above formula, S is charged with 1 gram of rubber-reinforced vinyl resin in 20 ml of acetone (acetonitrile when the rubber polymer is acrylic rubber), and shaken for 2 hours by a shaker under a temperature condition of 25 ° C. Then, under the temperature condition of 5 ° C, centrifuge for 60 minutes in a centrifuge (rotational speed: 23,000 rpm), separate the insoluble matter and the soluble matter, and use the mass (g) of the insoluble matter obtained. T is the mass (g) of the rubbery polymer contained in 1 gram of the rubber-reinforced vinyl resin. The mass of the rubbery polymer can be obtained by the method of calculating from the polymerization formulation and the polymerization conversion rate, the method of determining by infrared absorption spectrum (IR), or the like.

  The intrinsic viscosity [.eta.] (Measured at 30.degree. C. in methyl ethyl ketone) of the acetone-soluble component of the rubber-reinforced vinyl resins [A1], [A2] and [A3] is usually 0.1 to 1 in all cases. 0.5 dl / g, preferably 0.2 to 1.0 dl / g. When the intrinsic viscosity [η] is in the above-mentioned range, it is excellent in balance of physical properties of molding processability and impact resistance.

In addition, the measurement of the said intrinsic viscosity [eta] was performed by the following method. First, acetone-soluble components of the above-mentioned rubber-reinforced vinyl resins [A1], [A2] and [A3] were dissolved in methyl ethyl ketone to make five different concentrations. The limiting viscosity [η] was determined from the result of measuring the reduced viscosity at each concentration at 30 ° C. using a Ubbelohde viscosity tube. The unit is dl / g.
The above-mentioned intrinsic viscosity can be adjusted by appropriately selecting the type and amount of chain transfer agent used at the time of production, the type and amount of polymerization initiator, and the polymerization temperature.

  As described above, the rubber-reinforced vinyl-based resin [A] according to the present invention is formed using the rubber-reinforced vinyl-based resin [A1] or a mixture of [A1] and [A2] separately prepared. Obtained by polymerizing the vinyl monomer [c1] or [c2] in the presence of the ethylene / α-olefin rubber polymer [a1] and the diene rubber polymer [a2] A rubber-reinforced vinyl resin [A3] may be used. Therefore, when using a plurality of rubber-reinforced vinyl resins such as the former, a mixture of each resin obtained in each manufacturing step may be used, but as another method, for example, each resin by emulsion polymerization The respective latexes can be obtained by mixing the latexes and then coagulating.

2. Polycarbonate resin [B] (hereinafter, also referred to as "component [B]"):
The polycarbonate resin [B] used in the present invention is not particularly limited, but is preferably an aromatic polycarbonate resin. As the above-mentioned aromatic polycarbonate resin, those obtained by transesterification (ester exchange reaction) of an aromatic dihydroxy compound and a carbonic diester by melting, those obtained by the interfacial polycondensation method using phosgene, pyridine and phosgene What was obtained by the pyridine method which used the reaction product of, etc. can be used.

  As the aromatic dihydroxy compound, any compound having two hydroxyl groups in the molecule may be used, such as hydroquinone, dihydroxybenzene such as resorcinol, 4,4′-biphenol, 2,2-bis (4-hydroxyphenyl) propane ( Hereinafter, referred to as “bisphenol A”), 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl-3-methylphenyl) propane, 2,2 -Bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) methane, 1,1-bis p-hydroxyphenyl) ethane, 2,2-bis (p-hydroxyphenyl) butane, 2,2-bis ( -Hydroxyphenyl) pentane, 1,1-bis (p-hydroxyphenyl) cyclohexane, 1,1-bis (p-hydroxyphenyl) -4-isopropylcyclohexane, 1,1-bis (p-hydroxyphenyl) -3, 3,5-trimethylcyclohexane, 1,1-bis (p-hydroxyphenyl) -1-phenylethane, 9,9-bis (p-hydroxyphenyl) fluorene, 9,9-bis (p-hydroxy-3-methyl) Phenyl) fluorene, 4,4 '-(p-phenylenediisopropylidene) diphenol, 4,4'-(m-phenylenediisopropylidene) diphenol, bis (p-hydroxyphenyl) oxide, bis (p-hydroxy) Phenyl) ketone, bis (p-hydroxyphenyl) ether, bis (p-hydroxy) Phenyl) ester, bis (p-hydroxyphenyl) sulfide, bis (p-hydroxy-3-methylphenyl) sulfide, bis (p-hydroxyphenyl) sulfone, bis (3,5-dibromo-4-hydroxyphenyl) sulfone, Bis (p-hydroxyphenyl) sulfoxide and the like can be mentioned. These can be used alone or in combination of two or more.

  Among the above aromatic dihydroxy compounds, compounds having a hydrocarbon group between two benzene rings are preferred. In this compound, the hydrocarbon group may be a halogen-substituted hydrocarbon group. Further, the benzene ring may be one in which a hydrogen atom contained in the benzene ring is substituted by a halogen atom. Therefore, as the above compounds, bisphenol A, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl-3-methylphenyl) propane, 2,2 -Bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) methane, 1,1-bis p-hydroxyphenyl) ethane, 2, 2-bis (p- hydroxyphenyl) butane etc. are mentioned. Among these, bisphenol A is particularly preferred.

  Dimethyl carbonate, diethyl carbonate, di-tert- butyl carbonate, diphenyl carbonate, ditolyl carbonate etc. are mentioned as a carbonic diester used in order to obtain an aromatic polycarbonate by transesterification. These can be used alone or in combination of two or more.

  The viscosity average molecular weight of the polycarbonate resin (A) is preferably 15,000 to 40,000, more preferably 17,000 to 30,000, and particularly preferably 18,000 to 28,000. As the viscosity average molecular weight is higher, the impact resistance is higher, but the flowability is not sufficient and the moldability tends to be inferior. If the viscosity average molecular weight as a whole falls within the above range, two or more polycarbonate resins having different viscosity average molecular weights may be mixed and used.

3. (Co) polymer [C] (hereinafter, also referred to as “component [C]”):
3-1. Method of producing (co) polymer [C]:
The (co) polymer [C] polymerizes the vinyl monomer [c3] in the absence of a rubbery polymer by a known method such as solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization, etc. Can be manufactured by The polymerization may be thermal polymerization without using a polymerization initiator, or catalytic polymerization using a polymerization initiator.

3-2. Physical Properties of (Co) polymer [C]:
The intrinsic viscosity [η] (measured in methyl ethyl ketone at 30 ° C.) of the polymer [C] is usually 0.1 to 1.5 dl / g, preferably 0.2 to 1.0 dl / g. If the intrinsic viscosity [η] is in the above range, the physical properties balance between moldability and impact resistance is excellent.

In addition, the measurement of the said intrinsic viscosity [eta] was performed by the following method. First, the above (co) polymer [C] was dissolved in methyl ethyl ketone to make five different concentrations. The limiting viscosity [η] was determined from the result of measuring the reduced viscosity at each concentration at 30 ° C. using a Ubbelohde viscosity tube. The unit is dl / g.
The above-mentioned intrinsic viscosity can be adjusted by appropriately selecting the type and amount of chain transfer agent used at the time of production, the type and amount of polymerization initiator, and the polymerization temperature.

4. Silicone oil [D] (hereinafter, also referred to as “component [D]”):
As the silicone oil as the component [D] used in the present invention, any known silicone oils having a polyorganosiloxane structure can be used. The silicone oil [D] may be unmodified silicone oil such as dimethyl silicone oil, methyl phenyl silicone oil, methyl hydrogen silicone oil, etc., or a part of side chains in the polyorganosiloxane structure and / or polyorgano. It may be a modified silicone oil in which various organic groups are introduced into one end portion of the siloxane structure or both end portions of the polyorganosiloxane structure. As the above-mentioned modified silicone oil, alkyl modified silicone oil, alkyl / aralkyl modified silicone oil, polyether modified silicone oil, fluorine modified silicone oil, higher alkoxy modified silicone oil, higher fatty acid modified silicone oil, methylstyryl modified silicone oil, methyl chlorine Phenyl silicone oil, methylhydrogen silicone oil, amino modified silicone oil, epoxy modified silicone oil, carboxyl modified silicone oil, acrylic modified silicone oil, methacrylic modified silicone oil, mercapto modified silicone oil, phenol modified silicone oil, carbinol modified silicone Oil etc. can be used. Among these, methylphenyl silicone oil, alkyl / aralkyl modified silicone oil and amino modified silicone oil are preferable. These can be used alone or in combination of two or more.
When the silicone oil [D] used in the present invention is a methylphenyl silicone oil, an alkyl / aralkyl modified silicone oil and an amino modified silicone oil, the occurrence of itching noise is significantly reduced and it has been kept for a long time under high temperature Even in the case, the thermoplastic resin composition and the molded article having excellent impact resistance and the molded appearance can be obtained without reducing the stagnant sound reduction effect.
In addition, when the silicone oil [D] used in the present invention is a methylphenyl silicone oil, the generation of itching is significantly reduced, and when it is left under high temperature for a long time, maintenance of the itching reduction effect It is even better.

  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 part of the side chain of silicone oil.

  The amino-modified silicone oil used in the present invention is obtained by introducing an amino group 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 silicone oil [D] 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, particularly preferably 20. ~ 30,000 cSt. When the kinematic viscosity at 25 ° C. of the silicone oil [D] is less than 10 cSt, the reduction effect of the stagnation noise tends to be insufficient, while when the kinematic viscosity exceeds 100,000 cSt, the thermoplastic resin composition [X] The dispersibility of the silicone oil [D] in this case is deteriorated, so that the impact resistance and the noise reduction effect are not stably exhibited, and the extrusion processability at the time of melt-kneading tends to be lowered.

  The kinematic viscosity of the silicone oil was measured with a Ubbelohde viscometer according to ASTM D445-46T (which may be JIS 8803).

5. Polyolefin wax [E] (hereinafter, also referred to as “component [E]”):
The polyolefin wax as the component [E] used in the present invention is a relatively low molecular weight one having a number average molecular weight of usually 100 to 10,000 among homopolymers and copolymers of olefins. Is preferred. Specifically, polyethylene wax, polypropylene wax, olefin copolymer wax (for example, ethylene copolymer wax) and the like can be mentioned, and partial oxides of these or mixtures thereof are also included. The structure of the polyolefin wax may be a linear structure or a branched structure. These can be used alone or in combination of two or more.
As the above-mentioned olefin copolymer, for example, two or more of olefins such as ethylene, propylene, 1-butene, 1-hexene, 1-decene, 4-methyl-1-butene, 4-methyl-1-pentene and the like are used Copolymers, monomers which can be copolymerized with these olefins, for example, unsaturated carboxylic acids and their acid anhydrides [(meth) acrylic acid, maleic anhydride etc.], (meth) acrylic acid esters [ Examples thereof include copolymers with polymerizable monomers such as methyl (meth) acrylate and (meth) acrylic acid alkyl ester such as ethyl (meth) acrylate. In addition, these copolymers include random copolymers, block copolymers or graft copolymers.

The preferable number average molecular weight of the said polyolefin type wax is 1,000-6,000, More preferably, it is 1,200-5,500. When the number average molecular weight is in this range, the releasability is particularly excellent.
Moreover, the preferable viscosity (140 degreeC) of the said polyolefin type wax is 100-10,000 cps, More preferably, it is 100-5,000 cps. When the viscosity is in this range, the releasability is particularly excellent.

6. Thermoplastic resin composition [X]:
The thermoplastic resin composition [X] in the present invention is obtained by mixing the above component [A], the above component [B], and, if desired, the above components [C], [D] and [E] at a predetermined blending ratio And obtained by melt-kneading.

  The amount of the component [A] and the component [B] used in the present invention is 20 to 65 parts by mass, and 35 to 80 parts by mass based on 100 parts by mass of the total of the component [A] and the component [B]. Parts, preferably 25 to 65 parts by mass, and 35 to 75 parts by mass, more preferably 35 to 65 parts by mass, and 35 to 65 parts by mass, particularly preferably 45 to 65 parts by mass and 35 to 65 parts by mass 55 parts by mass. When the use amount of the component [A] is less than 20 parts by mass and the use amount of the component [B] exceeds 80 parts by mass, the effect of reducing the stagnant sound and the formability are inferior. On the other hand, when the amount of the component [A] used exceeds 65 parts by mass and the amount of the component [B] used is less than 35 parts by mass, the fracture mode becomes brittle and the impact strength is also inferior.

  The content of the ethylene / α-olefin rubbery polymer [a1] in the component [A] is 5 to 30% by mass, preferably 100% by mass of the thermoplastic resin composition [X]. It is 5 to 25% by mass, particularly preferably 5 to 20% by mass. If this total amount is less than 5% by mass, the effect of reducing stagnant noise and moldability are inferior, while if it exceeds 30% by mass, the heat resistance is lowered.

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

  Furthermore, the said component [A] can mix | blend the (co) polymer [C] of vinyl-type monomer [c3] as needed. The compounding amount of the component [C] is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, based on 100% by mass of the total amount of the component [A].

  The compounding amount of the silicone oil [D] relative to 100 parts by mass of the thermoplastic resin composition [X] is usually 0.1 to 8 parts by mass, preferably 0.2 to 6 parts by mass, more preferably 0.5 to 0.5 The amount is 5 parts by mass, particularly preferably 2.5 to 3.5 parts by mass. If the compounding amount of the component [D] is less than 0.1 parts by mass, there may be a case where the reduction effect of the stagnation noise can not be sufficiently obtained. On the other hand, when the compounding quantity of the said component [D] exceeds 8 mass parts, the external appearance and impact resistance of a molded article may become inadequate, and melt mixing may become difficult.

  The compounding amount of the polyethylene wax [E] is usually 0.1 to 8 parts by mass, preferably 0.2 to 6 parts by mass, more preferably 0.5 to 6 parts by mass with respect to 100 parts by mass of the thermoplastic resin composition [X]. The amount is 5 parts by mass, particularly preferably 2.0 to 5.0 parts by mass. If the compounding amount of the component [E] is less than 0.1 parts by mass, there may be a case where the reduction effect of the stagnation noise can not be sufficiently obtained. On the other hand, when the compounding quantity of the said component [E] exceeds 8 mass parts, the external appearance and impact resistance of a molded article may become inadequate, and melt mixing may become difficult.

  As described above, the thermoplastic resin composition [X] in the present invention may, if necessary, be a filler, a nucleating agent, a lubricant, a heat stabilizer, an antioxidant, an ultraviolet absorber, a flame retardant, an antiaging agent, a plastic Various additives, such as an agent, an antibacterial agent, and a coloring agent, can be contained in the range which does not impair the object of the present invention.

  Furthermore, the thermoplastic resin composition [X] of the present invention does not impair the object of the present invention, if necessary, other resins such as polyethylene, polypropylene, polybutylene terephthalate, polyethylene terephthalate, polyphenylene sulfide, polyamide and the like. It can be contained in the range.

  The thermoplastic resin composition [X] of the present invention is a single screw extruder, a twin screw extruder, a Banbury mixer, a kneader, a roll, a feeder after mixing each component with a tumbler mixer, a Henschel mixer or the like at a predetermined blending ratio. It can be produced by melt-kneading under appropriate conditions using a mixer such as a ruder. The preferred kneader is a twin screw extruder. Furthermore, when the respective components are kneaded, the respective components may be kneaded at once or may be compounded in multiple stages, divided and kneaded. In addition, after knead | mixing with a Banbury mixer, a kneader etc., it can also be pelletized with an extruder. Further, it is preferable to supply fibrous material among the fillers from the middle of the extruder by a side feeder in order to prevent cutting during kneading. The melt-kneading temperature is usually 200 to 300 ° C, preferably 220 to 280 ° C.

7. Molding:
The molded article of the present invention is obtained by molding the above-mentioned thermoplastic resin composition. There is no restriction in the method of producing the molded article of the present invention from the thermoplastic resin composition, and injection molding, injection compression molding, gas assist molding, press molding, calendar molding, T-die extrusion molding, profile extrusion molding, film It can manufacture by well-known methods, such as shaping | molding.

The molded article of the present invention is suitable as a contact part to be in contact with, joined to, and fitted with other members, and the other members to which the contact parts contact are not particularly limited. For example, the thermoplastic resin composition of the present invention The thermoplastic resin containing [X], a thermosetting resin, rubber, an organic material, an inorganic material, a metal material, etc. are mentioned.
As a thermoplastic resin, for example, polyvinyl chloride, polyethylene, polypropylene, AS resin, ABS resin, ABS resin, AES resin, ASA resin, PMMA, polystyrene, high impact polystyrene, EVA, polyamide (PA), polyethylene terephthalate, polybutylene terephthalate And polycarbonate (PC), polylactic acid, PC / ABS, PC / AES, PA / ABS, PA / AES and the like. These can be used alone or in combination of two or more.
As a thermosetting resin, a phenol resin, an epoxy resin, a urea resin, a melamine resin, unsaturated polyester resin etc. are mentioned, for example. These can be used alone or in combination of two or more.
Examples of the rubber include chloroprene rubber, polybutadiene rubber, ethylene / propylene rubber, various synthetic rubbers such as SEBS, SBS, SIS, and natural rubber. These can be used alone or in combination of two or more.
As the organic material, for example, insulation board, MDF (medium quality fiber board), hard board, particle board, lumbar core, LVL (single board laminate material), OSB (oriented board), PSL (pararam), WB (wafer (wafer) Board), hard fiber board, soft fiber board, lumbar core plywood, board core plywood, special core-plywood, veneer core-veneer board, laminated sheet / plate of paper impregnated with tap resin, (fine) small pieces of crushed paper, etc. -A board obtained by mixing an adhesive in a linear body and heating and compressing, various woods and the like can be mentioned. These can be used alone or in combination of two or more.
Examples of the inorganic material include calcium silicate board, flexible board, homocement board, gypsum board, sheathed gypsum board, reinforced gypsum board, gypsum lath board, decorative gypsum board, composite gypsum board, various ceramics, glass and the like. These can be used alone or in combination of two or more.
Furthermore, as a metal material, iron, aluminum, copper, various alloys, etc. are mentioned. These can be used alone or in combination of two or more.

The parts for contact of the present invention can be suitably used for parts for automobile interiors, places for office work, parts for home interiors, etc. having places where they contact, join, or fit with other members.
The parts for automobile interiors of the present invention can significantly reduce the stagnant noise generated by contacting and rubbing with other members. Furthermore, due to the ductile fracture, the safety at the time of collision is excellent. Such car interior parts include door trim, door lining, pillar garnish, console, door pocket, ventilator, duct, air conditioner, meter visor, instrument panel upper garnish, instrument panel lower garnish, A / T indicator, on-off switches (sliding parts, Slide plate), grill front defroster, grill side defroster, lid cluster, cover instroir, masks (mask switch, mask radio etc), glove box, pockets (pocket deck, pocket card etc), steering wheel horn pad, switch Parts, exterior parts for car navigation, etc. can be mentioned. Among them, it can be particularly suitably used as an automotive ventilator, a plate-like blade of an automotive air conditioner, a valve shutter, a louver, a switch component, an exterior component for car navigation, and the like.

  The parts for office equipment of the present invention can significantly reduce the stagnant noise generated by contacting and rubbing with other members. Furthermore, due to the ductile fracture, the safety such as collision is excellent. Such contact parts for office equipment can be suitably used for desk lock parts, desk drawers, and the like.

  The housing interior part of the present invention can significantly reduce the stagnant noise generated by contacting and rubbing with other members. Furthermore, due to the ductile fracture, the safety such as collision is excellent. Such parts for housing interiors can be particularly suitably used as shelf doors, chair dampers, table folding leg movable parts, door opening and closing dampers, sliding door rails, curtain rails and the like.

  EXAMPLES Hereinafter, the present invention will be more specifically described by way of examples. However, the present invention is not limited at all by the following examples as long as the gist of the present invention is not 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) Damping Sound Evaluation I (Practical Evaluation):
Using an injection molding machine “J-100E” (type name) manufactured by Japan Steel Works, Ltd., an ISO dumbbell test piece made of the thermoplastic resin composition described in Table 1 is injection molded, and then the test piece is 80 It was left in the gear oven for 200 hours. Next, five ISO dumbbell test pieces consisting of the thermoplastic resin composition described in Table 1 above, and PC / ABS "CK 43" (trade name) manufactured by Techno Polymer Co., Ltd. as other parts to be contacted, Similarly, five ISO dumbbell test pieces left to stand in an 80 ° C. gear oven for 200 hours were alternately laminated, and both ends were twisted by hand to evaluate the generation of a stagnant sound. Evaluation was performed 5 times, and determination was performed based on the following evaluation criteria.
Evaluation of the noise reduction effect:
○: The generation of stagnation sound was slight in all five evaluations.
Δ: The occurrence of itching sound was prominent in the five evaluations.
X: In all 5 evaluations, generation | occurrence | production of itching sound was remarkable.
A similar evaluation was also conducted with the standing time in the gear oven as 400 hours.

(1-2) Damping sound evaluation II (frictional velocity dependency of friction coefficient):
Thermoplastic described in Table 1 under the conditions of a molding temperature of 240 ° C., a mold temperature of 50 ° C., and an injection speed of 30 mm / s using an electric injection molding machine “Elject NEX 30” (type name) manufactured by Nisshin Plastic Industry Co., Ltd. Injection of a cylindrical test piece with an inner diameter of 20 mm, an outer diameter of 24.8 mm, and a height of 15 mm consisting of a resin composition and PC / ABS “CK43” (trade name) manufactured by Technopolymer Co., Ltd. After molding, both specimens were left in an 80 ° C. gear oven for 400 hours. Next, using a wear friction tester “EFM-III-EN” (trade name) manufactured by ORIENTEC Co., Ltd., a test piece consisting of CK43 as a contact partner is set on the rotating side, and the fixing side is described in Table 1. A test piece made of a thermoplastic resin composition was set, and the frictional strength was measured under the conditions of a load of 3 kg and a rotational speed (frictional speed) of 50, 100 and 150 mm / sec to determine the slope of the coefficient of friction with respect to the frictional speed.

(1-3) Deflection temperature under load Using the thermoplastic resin composition described in Table 1, a test piece of 80 mm in length, 10 mm in width, 4 mm in thickness was prepared by an injection molding machine J100E (manufactured by Japan Steel Works, Ltd.) did. The molding conditions were a molding temperature of 250 ° C. and a mold temperature of 60 ° C. Evaluation was based on ISO75, and measured by Flat-wise method, load 1.82MPa.
The evaluation results show that the higher the deflection temperature under load, the better the heat resistance.

(1-4) Melt Mass Flow Rate Using the thermoplastic resin composition described in Table 1 and using pellets produced by a twin-screw extruder (manufactured by Japan Steel Works TEX44), ISO 1133 (temperature 240 ° C., load 98 N) The melt mass flow rate (MFR) was measured in the same manner. The unit is g / 10 minutes.

(1-5) Drop weight impact strength:
An 80 mm × 55 mm × 2.4 mm flat-plate test piece made of the thermoplastic resin composition described in Table 1 is manufactured using an electric injection molding machine “Elject NEX 30” (type name) manufactured by Nisshin Plastic Industry Co., Ltd. It was injection molded. The test piece was equipped with a 4 mm × 1 mm side gate at the center of one side of 55 mm, the resin temperature at molding was 240 ° C., and the mold temperature was 50 ° C. Next, using the Shimadzu hydro-shot high-speed puncture impact tester "HITS-P10" (type name) manufactured by Shimadzu Corporation, the test piece was punched out under the conditions shown below to measure the breaking energy (J).
Measurement temperature: 23 ° C
Punching speed: 6.7 mm / s
Striker tip of punching test jig: φ12.7 mm
Die diameter of specimen holder: 43 mm

(1-6) Failure mode:
The cracks around the punching part of the evaluation plate after the drop weight impact strength test of the evaluation method (1-5) are observed, and the ductility fracture when the crack length from the end of the punching part is within 5 mm, in the case of exceeding 5 mm Was evaluated as brittle fracture.
If the molded article or the part for contact causes a brittle fracture at the time of a collision, there is a possibility that the safety of the occupant can not be sufficiently secured, for example, fragments are scattered around, and the ductile fracture is preferable.

(2-1) Component [A]
A1-1: AES-1
A 20 l stainless steel autoclave equipped with a ribbon stirrer blade, auxiliary additive continuous addition device, thermometer, etc., as an ethylene / α-olefin rubber polymer [a1], an ethylene / propylene copolymer (ethylene / propylene copolymer Propylene = 78/22 (%), Mooney viscosity (ML 1 + 4, 100 ° C) 20, melting point (Tm) 40 ° C, glass transition temperature (Tg)-50 ° C 22 parts, styrene 55 parts, acrylonitrile 23 parts, tert 0.5 parts of dodecyl mercaptan and 110 parts of toluene were charged, the internal temperature was raised to 75 ° C., and the contents of the autoclave were stirred for 1 hour to make a homogeneous solution. Thereafter, 0.45 parts of tert-butylperoxyisopropyl monocarbonate is added, the internal temperature is further raised, and after reaching 100 ° C., while maintaining this temperature, the polymerization reaction is carried out at a stirring rotational speed of 100 rpm. went. Four hours after initiation of the polymerization reaction, the internal temperature was raised to 120 ° C., and the reaction was carried out for 2 hours while maintaining this temperature to complete the polymerization reaction. Thereafter, the internal temperature is cooled to 100 ° C., 0.2 parts of octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenol) -propionate is added, and the reaction mixture is withdrawn from the autoclave, The unreacted material and the solvent were distilled off by distillation, and the volatile matter was substantially degassed using a 40 mm diameter vented extruder (cylinder temperature 220 ° C., degree of vacuum 760 mmHg) and pelletized. The graft ratio of the obtained ethylene / α-olefin rubber polymer reinforced vinyl resin was 70%, and the intrinsic viscosity [η] of acetone soluble matter was 0.47 dl / g.

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

A3: AES-2
A 20 l stainless steel autoclave equipped with a ribbon stirrer blade, auxiliary additive continuous addition device, thermometer, etc., an ethylene / propylene / dicyclopentadiene copolymer as an ethylene / α-olefin rubber polymer [a1] (Ethylene / propylene / dicyclopentadiene = 63/32/5 (%), Mooney viscosity (ML 1 + 4, 100 ° C) 33, no melting point (Tm), glass transition temperature (Tg)-52 ° C) 30 parts, styrene 45 25 parts of acrylonitrile, 0.5 parts of tert-dodecyl mercaptan, and 140 parts of toluene were 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 parts of tert-butylperoxyisopropyl monocarbonate is added, the internal temperature is further raised, and after reaching 100 ° C., while maintaining this temperature, the polymerization reaction is carried out at a stirring rotational speed of 100 rpm. went. Four hours after initiation of the polymerization reaction, the internal temperature was raised to 120 ° C., and the reaction was carried out for 2 hours while maintaining this temperature to complete the polymerization reaction. Thereafter, the internal temperature is cooled to 100 ° C., 0.2 parts of octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenol) -propionate is added, and the reaction mixture is withdrawn from the autoclave, The unreacted material and the solvent were distilled off by distillation, and the volatile matter was substantially degassed using a 40 mm diameter vented extruder (cylinder temperature 220 ° C., degree of vacuum 760 mmHg) and pelletized. The graft ratio of the obtained ethylene / α-olefin rubber polymer reinforced vinyl resin was 60%, and the intrinsic viscosity [η] of acetone soluble matter was 0.45 dl / g.

A1-2: AES-3
A polyolefin elastomer “ENGAGE 8100” (trade name, ethylene / 1-octene = 76/24 (%), manufactured by DuPont Dow Elastomers, ethylene / α-olefin rubber polymer [a1], Mooney viscosity (ML1 + 4, A rubber-reinforced vinyl resin was obtained in the same manner as in AES-1, except that the temperature was 121 ° C., the melting point (Tm) was 60 ° C., and the glass transition temperature (Tg) was −56 ° C. [a1]. The graft ratio of the obtained rubber-reinforced vinyl-based resin was 60%, and the intrinsic viscosity [η] of acetone-soluble matter was 0.41 dl / g.

(2-2) Component [B] (polycarbonate resin):
B-1: Novarex 7022PJ (manufactured by Mitsubishi Engineering Plastics Co., Ltd.), and the viscosity average molecular weight (Mv) was 22,000.

B-2: Novarex 7022 PJ-LH1 (manufactured by Mitsubishi Engineering Plastics Co., Ltd.), viscosity average molecular weight (Mv) was 18,500.

(2-3) Component [C] AS:
In a polymerization vessel equipped with a stirrer, 250 parts of water and 1.0 part of sodium palmitate were charged, and after deoxygenation, they were heated to 70 ° C. while being stirred in a nitrogen stream. Further, 0.4 parts of sodium formaldehyde sulfoxylate, 0.0025 parts of ferrous sulfate, 0.01 parts of disodium ethylenediaminetetraacetate are charged, and 70 parts of α-methylstyrene, 25 parts of acrylonitrile, 5 parts of styrene, tert- A monomer mixture consisting of 0.5 part of dodecyl mercaptan and 0.2 parts of cumene hydroperoxide was dropped continuously at a polymerization temperature of 70 ° C. for 7 hours. After completion of the dropwise addition, the polymerization temperature was raised to 75 ° C., and stirring was continued for 1 hour to complete the polymerization, to obtain a copolymer latex. The polymerization conversion was 99%. Thereafter, the obtained latex was coagulated by adding calcium chloride, and after washing, filtration and drying steps, a powdery copolymer was obtained. The intrinsic viscosity [η] of the acetone soluble matter of the obtained copolymer was 0.40 dl / g.

(2-4) Component [D] (silicone oil):
D-1: Methyl phenyl silicone oil; KF54 (manufactured by Shin-Etsu Silicone Co., Ltd.), the kinematic viscosity at 25 ° C. was 400 cSt.

D-2: Amino-modified silicone oil; TSF 4700 (manufactured by Momentive Performance Materials Japan), kinematic viscosity at 25 ° C. was 50 cSt.

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

(2-5) Component [E] (polyolefin wax):
E-1: Sun wax 171-P (manufactured by Sanyo Chemical Industries, Ltd.), polyethylene wax, and the number average molecular weight (Mn) was 1,500.

E-2: Sun wax 161-P (manufactured by Sanyo Chemical Industries, Ltd.), polyethylene wax, and the number average molecular weight (Mn) was 5,000.

(2-6) Component [F] (Additive):
F-1: ethylene bisstearic acid amide; Kao wax EB-P (manufactured by Kao Corporation)

F-2: 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -s-triazine-2,4,6- (1H, 3H, 5H) trione; Adekastab AO- 20 (made by ADEKA Corporation)

F-3: bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite; adecastab PEP-24G (manufactured by ADEKA Co., Ltd.)

Examples 1-19, Comparative Examples 1-5, Example 20
A thermoplastic composition consisting of the above components [A] to [F] is mixed with a Henschel mixer at the compounding ratio described in Table 1 and Table 2, and then a twin-screw extruder (made by Nippon Steel Co., Ltd., TEX44α, barrel set temperature) It melt-kneaded at 250 degreeC, and pelletized. Each specimen for evaluation was shape | molded as above-mentioned with the obtained pellet. And it evaluated by said method using the obtained test piece. The evaluation results are shown in Table 1.

As is clear from Table 1, the thermoplastic resin compositions of the present invention represented by Examples 1 to 19 reduce the stagnant noise targeted by the present invention, and further, the heat resistance, impact resistance, resin flowability It is possible to provide a molded article having a well-balanced failure mode.
On the other hand, as shown in Table 2, Comparative Example 1 is an example which does not contain the specific ethylene / α-olefin rubber polymer [a1] of the present invention, and is inferior in the effect of reducing the stagnant noise. Comparative Example 2 is an example in which the blending amount of the polycarbonate resin [B] is insufficient, and since it is brittle fracture, the safety is inferior. Comparative Example 3 is an example in which the compounding amount of the polycarbonate resin [B] is excessive, and the reduction effect of the stagnant noise is significantly reduced and the fluidity of the molten resin is insufficient, so the moldability is also inferior. The comparative example 4 is an example which does not contain polycarbonate resin [B], and since heat resistance is low and it becomes a brittle fracture, it is inferior to safety. Comparative Example 5 is an example in which the compounding amount of the rubber-reinforced vinyl resin [A] is excessive and the compounding amount of the polycarbonate resin [B] is too small, and the heat resistance and the impact resistance are low and the brittle fracture is caused. Less secure.
Example 20 is an example using AES with an ethylene / α-olefin rubber polymer [a1] different from that used in Examples 1 to 19 of the present invention as a base rubber, but it reduces stagnant sound It is excellent in the effect (practice evaluation: 200 hours), and can further provide a molded article having heat resistance, impact resistance, resin flowability, and fracture mode in a well-balanced manner.

Example 21
As shown in FIG. 3, the contact component A is made of the thermoplastic resin composition of Example 2 and includes a T-shaped component including the bottom 1 and the rising portion 2, and another contact component B is a technopolymer. A PC / ABS “CK43” (trade name) manufactured in Japan, and a sandwiching part consisting of a bottom 3 and two rising portions 4 4 for tightly holding the rising portion 2 is manufactured. After leaving in a gear oven for 200 hours, assemble the T-shaped rising part 2 between the two rising parts 4 of the clamping part and slide it as shown by the arrow. The presence or absence of generation of a sorrow sound was examined. As a result, no generation of itching was observed.

Comparative Examples 6 and 7
Except that the thermoplastic resin composition of the T-shaped part was changed to the thermoplastic resin composition of Comparative Examples 1 and 3 as the contact part A, the presence or absence of generation of stagnant noise was examined in the same manner as in Example 21. The As a result, the generation of a stagnation sound was recognized in each case.

  As is apparent from the above, the thermoplastic resin composition and the molded article of the present invention are in contact with parts such as automobile interior parts, office equipment, housing interior parts, etc. which have places where they contact, join, and fit with other members. It turns out that it is suitable for parts.

  In the thermoplastic resin composition of the present invention, the stagnation noise generated when the members rub against each other is significantly reduced, and the stagnant noise reduction effect is maintained without reduction even when the product is placed under high temperature for a long time, and further It can provide molded products excellent in impact resistance, and is suitable for parts for contact such as parts for automobile interiors, office equipment, parts for home interiors, etc. that have places where they contact, join, or fit with other members. It can be used.

M Object V Driving speed μs Static friction coefficient μl Sawtooth lower end Δμ μs-μl
A Contact parts B Other contact parts 1 Bottom 2 Rising portion 3 Bottom 4 Rising portion

Claims (7)

A member for contacting, bonding or mating, and a member comprising at least one resin composition selected from the group consisting of polypropylene, ABS resin, PMMA, polycarbonate (PC), and PC / ABS Thermoplastic resin composition [X], which is
20 to 65 parts by mass of a rubber-reinforced vinyl resin [A] and 35 to 80 parts by mass of a polycarbonate resin [B] (provided that the total of [A] and [B] is 100 parts by mass),
Ethylene / α-olefin consisting of 60 to 95% by mass of ethylene and 40 to 5% by mass of α-olefin (wherein the total of ethylene and α-olefin is 100% by mass) of the rubber-reinforced vinyl resin [A] In the presence of a rubber-reinforced vinyl resin [A1] obtained by polymerizing a vinyl monomer [c1] in the presence of a rubber-based polymer [a1] and a diene rubber polymer [a2] A rubber-reinforced vinyl-based resin [A2] obtained by polymerizing a vinyl-based monomer [c2], and the ethylene / α-olefin-based rubber-like polymer [a1] and the diene-based rubber The thermoplastic resin composition whose total amount of polymer [a2] is 5-30 mass% as thermoplastic resin composition [X] 100 mass%. The thermoplastic resin composition according to claim 1 , wherein the rubber-reinforced vinyl resin [A] further contains a (co) polymer [C] of a vinyl monomer [c3]. Ethylene · alpha-olefin-based rubbery polymer [a1] and the mass ratio of the diene-based rubbery polymer [a2] [a1]: [a2] is 90 to 15: a is in claim 1 or 2 10-85 Thermoplastic resin composition as described. In 100 parts by mass of the thermoplastic resin composition [X], 0.1 to 8 parts by mass of silicone oil [D] and / or 0.1 to 8 parts by mass of polyolefin wax [E] are further contained. The thermoplastic resin composition according to any one of claims 1 to 3 . The thermoplastic resin composition according to claim 4 , wherein the silicone oil [D] is at least one selected from the group consisting of methylphenyl silicone oil, alkyl / aralkyl modified silicone oil and amino modified silicone oil. A member made of at least one resin composition selected from the group consisting of polypropylene, ABS resin, PMMA, polycarbonate (PC), and PC / ABS, and a contact component for contacting, bonding or fitting, ,
An article for contact comprising the thermoplastic resin composition according to any one of claims 1 to 5 . The contact part according to claim 6 , which is used in an application in which the other member is rubbed by the contact, joining or fitting.

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