WO2013031946A1 - 軋み音低減用熱可塑性樹脂組成物及び軋み音低減構造体 - Google Patents

軋み音低減用熱可塑性樹脂組成物及び軋み音低減構造体 Download PDF

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WO2013031946A1
WO2013031946A1 PCT/JP2012/072155 JP2012072155W WO2013031946A1 WO 2013031946 A1 WO2013031946 A1 WO 2013031946A1 JP 2012072155 W JP2012072155 W JP 2012072155W WO 2013031946 A1 WO2013031946 A1 WO 2013031946A1
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Prior art keywords
resin composition
thermoplastic resin
mass
squeaking noise
ethylene
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English (en)
French (fr)
Japanese (ja)
Inventor
望月勇
江川和也
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Techno UMG Co Ltd
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Techno Polymer Co Ltd
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Priority to US14/241,219 priority Critical patent/US9353249B2/en
Priority to EP12828558.2A priority patent/EP2752454B1/en
Publication of WO2013031946A1 publication Critical patent/WO2013031946A1/ja
Anticipated expiration legal-status Critical
Priority to US15/140,518 priority patent/US9777147B2/en
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • C08F255/04—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms on to ethylene-propylene copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L19/00—Compositions of rubbers not provided for in groups C08L7/00 - C08L17/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/12—Copolymers of styrene with unsaturated nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/18—Homopolymers or copolymers of nitriles
    • C08L33/20—Homopolymers or copolymers of acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/006—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to block copolymers containing at least one sequence of polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
    • B60R13/00—Elements for body-finishing, identifying, or decorating; Arrangements or adaptations for advertising purposes
    • B60R13/02—Internal Trim mouldings ; Internal Ledges; Wall liners for passenger compartments; Roof liners

Definitions

  • the present invention relates to a thermoplastic resin composition that reduces the occurrence of squeaking noise and a structure that reduces the squeaking noise made of the composition, and more specifically, stagnation that occurs when at least two parts come into contact with each other and rub against each other.
  • the present invention relates to a thermoplastic resin composition capable of greatly reducing sound and a squeaking noise reducing structure comprising the composition.
  • Styrenic resin typified by ABS resin is widely used in automobiles, home appliances, office automation equipment, etc. due to its excellent moldability, mechanical properties, chemical resistance, and secondary processability.
  • parts made of styrenic resin typified by ABS resin are members made of other resins such as polyethylene and polyvinyl chloride, and other members such as lining sheets and foams such as chloroprene rubber, natural rubber, polyester, and polyethylene. If it is used for a part that comes into contact with and rubs, a squeaking noise may be generated.
  • a vehicle ventilator made of ABS resin is equipped with a valve shutter that uses chloroprene rubber foam or the like as a sealing material to adjust the air volume, and seals when the valve shutter is rotated to adjust the air volume. The material and the case of the ventilator may rub against each other and a squeaking noise may occur.
  • styrene resins such as 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.
  • the stick-slip phenomenon occurs due to a large friction coefficient, and an abnormal sound (stagnation sound) may occur.
  • the stick-slip phenomenon occurs when two objects rub against each other.
  • the object M 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. As shown in FIG. 1, it is said that if the difference ⁇ between the static friction coefficient ⁇ s at the upper end of the sawtooth waveform and the friction coefficient ⁇ l at the lower end of the sawtooth waveform is large, itching is likely to occur. .
  • the dynamic friction coefficient is an intermediate value between ⁇ s and ⁇ l.
  • Non-Patent Document 1 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.
  • Patent Document 1 a technique for blending an organosilicon compound with a PC / ABS resin
  • Patent Document 2 a technique for blending a flame retardant, a flame retardant aid, and silicone oil with an ABS resin
  • Patent Document 2 a technique for blending silicone oil into a modified polystyrene resin
  • Patent Document 4 a technology for blending an alkali (earth) metal salt of alkane sulfonic acid into an ABS resin
  • Patent Document 5 A technique for blending a modified polyorganosiloxane containing at least one reactive group selected from an epoxy group, a carboxyl group and an acid anhydride group (see Patent Document 5) is disclosed.
  • 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. Furthermore, when using parts made of styrenic resin represented by ABS resin in combination, even if these methods are used, the effect of reducing the squeaking noise cannot be sufficiently obtained, and the use range is limited. was there.
  • the present invention has the effect of reducing the squeaking noise even when the styrenic resin member is used for a portion that rubs against each other, and the squeaking noise is remarkably reduced and the squeaking noise is reduced even when left at a high temperature for a long time.
  • the resin composition capable of providing a structure including a styrenic resin part that is maintained without deterioration and further has excellent impact resistance and molded appearance, and a squeaking noise reducing structure comprising the composition The purpose is to provide.
  • silicone oil is blended in the resin composition for the purpose of improving the slidability of the molded product, and when melt-kneading or devolatilizing a rubber-reinforced vinyl resin with an extruder, It may be added for the purpose of preventing deterioration of the rubber-reinforced vinyl-based resin due to a rise in the resin temperature due to shear force in the extruder. In the step of polymerizing the rubbery polymer, silicone oil may be added for the same purpose as described above. As a result of intensive studies to solve the above problems, the present inventors have determined that the silicon content contained in the thermoplastic resin composition [X] containing a specific rubber-reinforced vinyl resin is within a specific range.
  • the present invention was completed by discovering that the resin composition was maintained without being used, and further excellent in impact resistance and molding appearance.
  • thermoplastic resin composition containing rubber-reinforced vinyl resin [A] obtained by polymerizing vinyl monomer [b1] in the presence of ethylene / ⁇ -olefin rubbery polymer [a1] having a Tm (melting point) of 0 ° C. or higher.
  • a thermoplastic resin composition [X] comprising: The thermoplastic resin for reducing squeaking noise, wherein the silicon content in the thermoplastic resin composition [X] is 0.15% by mass or less with respect to 100% by mass of the thermoplastic resin composition [X]. Resin composition. 2. 2.
  • thermoplastic resin composition for sound reduction 3.
  • a rubber-reinforced vinyl resin [A] is obtained by polymerizing a vinyl monomer [b1] in the presence of an ethylene / ⁇ -olefin rubber polymer [a1] having a Tm (melting point) of 0 ° C. or higher.
  • the ethylene / ⁇ -olefin rubbery polymer [a1] is composed of 5 to 95% by mass of ethylene and 95 to 5% by mass of ⁇ -olefin (however, the total of ethylene and ⁇ -olefin is 100% by mass).
  • the graft ratio of the rubber-reinforced vinyl resin [A] is 10 to 150% by mass, and the intrinsic viscosity [ ⁇ ] (30 ° C. in methyl ethyl ketone) of the acetone-soluble component is 0.1 to 1.5 dl / g.
  • thermoplastic resin composition for reducing stagnation noise according to any one of 1 to 4 above, wherein: 6). Any one of 1 to 5 above, wherein the intrinsic viscosity [ ⁇ ] (in methyl ethyl ketone, 30 ° C.) of the acetone-soluble component of the thermoplastic resin composition [X] is 0.1 to 1.5 dl / g.
  • the thermoplastic resin composition for reducing squeaking noise as described in 1. 7). 7.
  • thermoplastic resin composition for reducing squeaking noise as described in 1. 9. Any one of 1 to 7 above, wherein the silicon content in the thermoplastic resin composition [X] is 0.07% by mass or less with respect to 100% by mass of the thermoplastic resin composition [X]. The thermoplastic resin composition for reducing squeaking noise as described in 1. 10. Any one of 1 to 7 above, wherein the silicon content in the thermoplastic resin composition [X] is 0.03% by mass or less with respect to 100% by mass of the thermoplastic resin composition [X]. The thermoplastic resin composition for reducing squeaking noise as described in 1. 11.
  • the contact part is an automobile interior part, a switch part, an office equipment part, a home appliance part, a desk lock part, a house interior part, or an indoor door opening / closing damper part.
  • the stagnation sound reducing structure according to any one of the above.
  • a meter visor for automobile interior comprising a contact component comprising the thermoplastic resin composition [X] according to any one of claims 1 to 10.
  • a center panel for automobile interior comprising a contact part made of the thermoplastic resin composition [X] according to any one of claims 1 to 10.
  • a console box for automobile interior comprising a contact part made of the thermoplastic resin composition [X] according to any one of claims 1 to 10.
  • a switch bezel for automobile interior comprising a contact part made of the thermoplastic resin composition [X] according to any one of claims 1 to 10.
  • a part including the part consisting of the component [X] by making the silicon content of the thermoplastic resin composition [X] containing the specific rubber-reinforced vinyl resin into a specific range. Even if they are rubbed together, the generation of squeaking noise is remarkably reduced, and even when placed at high temperatures for a long time, the squeaking noise reduction effect is maintained without deterioration, and also excellent in impact resistance and molded appearance It is possible to obtain a stagnation sound reduction structure.
  • FIG. 1 is an explanatory diagram of the stick-slip phenomenon.
  • FIGS. 2A, 2B, 2C, and 2D are stick-slip model diagrams.
  • thermoplastic resin composition for reducing squeaking noise in the present invention is obtained by polymerizing a vinyl monomer [b1] in the presence of an ethylene / ⁇ -olefin rubber polymer [a1] having a Tm (melting point) of 0 ° C. or higher.
  • (co) polymerization means homopolymerization and copolymerization
  • (meth) acryl means acryl and / or methacryl
  • (meth) acrylate Means acrylate and / or methacrylate.
  • Rubber reinforced vinyl resin [A] (hereinafter also referred to as “component [A]”):
  • the component [A] used in the present invention is obtained by polymerizing a vinyl monomer [b1] in the presence of an ethylene / ⁇ -olefin rubber polymer [a1] having a Tm (melting point) of 0 ° C. or more.
  • the rubber-reinforced vinyl resin made of a mixture of the rubber-reinforced vinyl resin [A1] alone and / or the vinyl monomer [b2] with the (co) polymer [B].
  • the (co) polymer [B] is obtained by polymerizing the vinyl monomer [b2] in the absence of a rubbery polymer.
  • Ethylene / ⁇ -olefin rubbery polymer [a1] (hereinafter also referred to as “component [a1]”):
  • the ethylene / ⁇ -olefin rubbery polymer [a1] used in the present invention is not particularly limited except that Tm (melting point) is 0 ° C. or higher.
  • Tm is a value obtained by measuring endothermic changes at a constant temperature increase rate of 20 ° C. per minute using a DSC (differential scanning calorimeter), and reading the peak temperature of the obtained endothermic pattern. , JIS K7121-1987.
  • the Tm is preferably 0 to 120 ° C., more preferably 10 to 100 ° C., and particularly preferably 20 to 80 ° C.
  • the rubber is crystallized around room temperature where parts are often used. Since it does not have the property, it is inferior in the effect of reducing itchiness.
  • those that do not clearly show the endothermic change peak are those that have substantially no crystallinity in the rubbery polymer and are judged to have no Tm, and the above Tm is 0 ° C. or higher. It is not included in the rubbery polymer. Those in which Tm does not exist are inferior in the effect of reducing itchiness.
  • the rubbery polymer having a melting point (Tm) means that the rubbery polymer has a crystalline part. If a crystalline part is present in the rubbery polymer, it is considered that the generation of the squeaking noise is suppressed in order to suppress the occurrence of the slip stick phenomenon.
  • the glass transition temperature (Tg) of the rubbery polymer is preferably ⁇ 20 ° C. or lower, more preferably ⁇ 30 ° C. or lower, and particularly preferably ⁇ 40 ° C. or lower. If the glass transition temperature exceeds ⁇ 20 ° C., impact resistance may be insufficient.
  • the glass transition temperature can be determined according to JIS K7121-1987 using a DSC (differential scanning calorimeter) in the same manner as the measurement of Tm (melting point).
  • Examples of the ⁇ -olefin constituting the component [a1] include ⁇ -olefins having 3 to 20 carbon atoms. Specific examples include propylene, 1-butene, 1-pentene, 1-hexene, 4- Examples thereof include methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene, 1-eicosene and the like. These ⁇ -olefins can be used alone or in admixture of two or more.
  • the carbon number of the ⁇ -olefin is preferably 3 to 20, more preferably 3 to 12, and still more preferably 3 to 8.
  • the mass ratio of ethylene: ⁇ -olefin is usually 5 to 95:95 to 5, preferably 50 to 95:50 to 5, more preferably 60 to 95:40 to 5, particularly preferably 70 to 90:30 to 10. It is.
  • the ⁇ -olefin weight ratio exceeds 95, the resulting rubber-reinforced vinyl resin is not preferable because the impact resistance is insufficient. If it is less than 5, the rubber elasticity of the rubber polymer [a1] is not sufficient, and the impact resistance of the resin composition is not sufficient.
  • the Mooney viscosity (ML1 + 4, 100 ° C .; conforming to JIS K6300) of component [a1] is usually 5 to 80, preferably 10 to 65, more preferably 10 to 45.
  • the Mooney viscosity exceeds 80, the fluidity of the resulting rubber-reinforced vinyl resin may be insufficient.
  • the Mooney viscosity is less than 5, the resulting molded article may have insufficient impact resistance. There is.
  • the ethylene / ⁇ -olefin rubbery polymer [a1] is usually an ethylene / ⁇ -olefin copolymer that does not contain a non-conjugated diene component from the viewpoint of reducing squeaking noise.
  • the non-conjugated diene component include 5-ethylidene-2-norbornene and dicyclopentadiene.
  • the blending amount is preferably 3% by mass or less based on 100% by mass of ethylene and ⁇ -olefin.
  • the component [a1] is more preferably an ethylene / propylene copolymer, an ethylene / 1-butene copolymer, or an ethylene / 1-octene copolymer, and particularly preferably an ethylene / propylene copolymer.
  • Vinyl monomers [b1] and [b2] are not particularly limited as long as both are polymerizable compounds having an unsaturated bond.
  • the vinyl monomers [b1] and [b2] usually contain an aromatic vinyl compound and a vinyl cyanide compound.
  • 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 copolymerizable functional group-containing vinyl monomer having at least one functional group such as an oxazoline group may be used in combination.
  • the vinyl monomer [b2] used for forming the (co) polymer [B] may be the same as or different from the vinyl monomer [b1].
  • 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, ⁇ -methylstyrene, o-methylstyrene, p-methylstyrene, vinyltoluene, ⁇ -methylstyrene, ethylstyrene, p-tert-butylstyrene, vinylxylene, vinylnaphthalene, 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 ⁇ -methylstyrene are preferred.
  • vinyl cyanide compound examples 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.
  • maleimide compound examples include maleimide, N-methylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide and the like. These can be used alone or in combination of two or more. Of these, N-cyclohexylmaleimide and N-phenylmaleimide are preferable.
  • 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.
  • 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.
  • 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.
  • 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 types and amounts of the vinyl monomers [b1] and [b2] are selected according to the purpose, application, etc., but the total amount of the aromatic vinyl compound and the vinyl cyanide compound is the vinyl monomer. It is usually 30 to 100% by mass, preferably 50 to 100% by mass, and more preferably 70 to 100% by mass with respect to 100% by mass of the total 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 vinyl monomers. %.
  • the use ratio of aromatic vinyl compound and vinyl cyanide compound is usually 40 to 85% by mass / 15 to 60% by mass when the total of these is 100% by mass. It is preferably 45 to 85% by mass / 15 to 55% by mass, particularly preferably 60 to 85% by mass / 15 to 40% by mass.
  • the rubber-reinforced vinyl resin [A] is a polymer component containing an ethylene / ⁇ -olefin rubbery polymer [a1], but the containing form is not particularly limited.
  • (Co) polymers of vinyl monomers are included.
  • this graft copolymer may contain a rubbery polymer to which a (co) polymer of a vinyl monomer is not grafted.
  • the content of the ethylene / ⁇ -olefin rubbery polymer [a1] is exemplified below. (1) When the ethylene / ⁇ -olefin rubbery polymer [a1] is contained as a graft copolymer. (2) The case where the ethylene / ⁇ -olefin rubber polymer [a1] is 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] A rubber-reinforced vinyl resin [A1] obtained by polymerizing a vinyl monomer [b1] in the presence of the ethylene / ⁇ -olefin rubber polymer [a1].
  • [Ii] A mixture comprising the above [i] and a (co) polymer [B] of the vinyl monomer [b2] (hereinafter also referred to as “(co) polymer [B]”).
  • [ii] is particularly preferable because the amount of the ethylene / ⁇ -olefin rubber polymer [a1] in the rubber-reinforced vinyl resin [A] can be freely adjusted.
  • the rubber-reinforced vinyl resin [A] may be a combination of the above [i] and [ii].
  • the manufacturing method of said rubber reinforced vinyl resin [A1] is demonstrated.
  • the polymerization method include known polymerization methods such as emulsion polymerization, solution polymerization, suspension polymerization, and bulk polymerization.
  • the vinyl monomers may be charged all at once, or may be reacted by dividing or continuously adding them.
  • the rubbery polymer may be added or reacted in the whole 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, when the total of the rubbery polymer and the vinyl monomer is 100% by mass.
  • the method for producing the rubber-reinforced vinyl resin [A1] is preferably solution polymerization and bulk polymerization, more preferably solution polymerization, and a combination of these methods.
  • a polymerization initiator When the above rubber-reinforced vinyl resin [A1] is 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.
  • a 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, tert-butyl peroxylaurate, tert-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 vinyl monomer [b1].
  • the polymerization initiator is usually added all at once or continuously to the reaction system.
  • chain transfer agents examples 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, ⁇ -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 vinyl monomer [b1].
  • the emulsifier examples include anionic surfactants and nonionic surfactants.
  • anionic surfactant examples include sulfates of higher alcohols; alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate; aliphatic sulfonates such as sodium lauryl sulfate; rosinates and phosphates.
  • 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 amount of the emulsifier is usually 0.3 to 5% by mass with respect to the vinyl monomer [b1].
  • Emulsion polymerization can be performed under known conditions depending on the type and amount of the vinyl monomer [b1] and the polymerization initiator used.
  • 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.
  • 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.
  • a solvent 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, etc. can be used. These can be used alone or in combination of two or more.
  • polymerization initiator examples 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.
  • chain transfer agents include mercaptans, terpinolenes, ⁇ -methylstyrene dimers, and the like. These can be used alone or in combination of two or more.
  • Solution polymerization can be performed under known conditions according to the type of vinyl monomer [b1], polymerization initiator, and the like to be used.
  • the polymerization temperature is usually in the range of 80 to 140 ° C.
  • it can also manufacture without using a polymerization initiator in the case of solution polymerization.
  • polymerization initiator, chain transfer agent and the like used in these methods are not particularly limited, but the same compounds as those exemplified in emulsion polymerization and solution polymerization can be used.
  • the graft ratio of the rubber-reinforced vinyl resin [A1] obtained as described above is usually 10 to 150% by mass, preferably 20 to 120% by mass, particularly preferably 30 to 70% by mass. If the graft ratio is less than 10% by mass, the density of the (co) polymer of the vinyl monomer [b1] graft-polymerized on the surface of the rubbery polymer is decreased, or the graft chain length is shortened. The impact resistance may not be sufficient.
  • the layer made of the (co) polymer of the vinyl monomer [b1] on the surface of the rubbery polymer becomes thick, and the above (copolymer) grafted inside the rubbery polymer. ) Since the polymer layer develops, the rubber elasticity decreases, and as a result, the impact resistance may decrease.
  • the graft ratio can be obtained by the following formula.
  • S is a mixture of 1 g of rubber-reinforced vinyl resin in 20 ml of acetone, shaken with a shaker for 2 hours under a temperature condition of 25 ° C., and then centrifuged under a temperature condition of 5 ° C.
  • This is the mass (g) of insoluble matter obtained by centrifuging for 60 minutes at (rotation speed: 23,000 rpm) and separating insoluble matter and soluble matter
  • T is contained in 1 gram of rubber-reinforced vinyl resin. It is the mass (g) of the rubbery polymer.
  • 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.
  • the intrinsic viscosity [ ⁇ ] (measured in methyl ethyl ketone at 30 ° C.) of the acetone-soluble component of the rubber-reinforced vinyl resin [A1] is usually 0.1 to 1.5 dl / g, preferably 0. .2 to 0.8 dl / g.
  • the intrinsic viscosity [ ⁇ ] is within the above range, the physical property balance between molding processability and impact resistance is excellent.
  • the intrinsic viscosity [ ⁇ ] was measured by the following method. First, acetone (acetonitrile in the case where the rubber polymer is an acrylic rubber) of the rubber-reinforced vinyl resin [A1] was dissolved in methyl ethyl ketone to prepare five samples having different concentrations. The intrinsic viscosity [ ⁇ ] 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.
  • (Co) polymer [B] (hereinafter also referred to as “component [B]”): 2-1.
  • Production method of (co) polymer [B] The (co) polymer [B] polymerizes the vinyl monomer [b2] by a known method such as solution polymerization, bulk polymerization, emulsion polymerization or suspension polymerization in the absence of a rubbery polymer. Can be manufactured.
  • the polymerization may be thermal polymerization without using a polymerization initiator, or may be catalytic polymerization using a polymerization initiator.
  • the intrinsic viscosity [ ⁇ ] (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 [ ⁇ ] is within the above range, the physical property balance between molding processability and impact resistance is excellent.
  • the intrinsic viscosity [ ⁇ ] 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 [ ⁇ ] 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.
  • Silicone oil [C] (hereinafter also referred to as “component [C]”):
  • the silicone oil as the component [C] used in the present invention is mainly used when a rubber-reinforced vinyl resin is melt-kneaded or devolatilized by an extruder and the resin temperature rises due to shear force in the extruder.
  • a known resin can be used as long as it has a polyorganosiloxane structure and is added to prevent deterioration of the reinforced vinyl resin.
  • 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.
  • the modified silicone oil include 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, and methylchlorine.
  • Phenyl silicone oil methyl hydrogen 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. can be used. These can be used alone or in combination of two or more.
  • the amount of the silicone oil [C] used is such that the silicon content in the thermoplastic resin composition [X] is 0.15% by mass or less, preferably 0.1% with respect to 100% by mass of the thermoplastic resin composition. It is not more than mass%, more preferably not more than 0.07 mass%, still more preferably not more than 0.03% by mass.
  • the silicon content in the thermoplastic resin composition [X] exceeds 0.15% by mass, a squeaking noise is generated when the same materials are used in combination, and a silver streak is generated near the gate, resulting in a molded appearance. Damaged.
  • the silicon content in the thermoplastic resin composition [X] was measured with a fluorescent X-ray analyzer MagiX PRO manufactured by PANalytal.
  • Thermoplastic resin composition [X] is obtained by mixing the above component [A] and, if desired, the above component [B] at a predetermined blending ratio, and melt-kneading.
  • the amount of component [B] is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, based on 100% by mass of the total of component [A] and component [B].
  • the intrinsic viscosity [ ⁇ ] (measured in methyl ethyl ketone at 30 ° C.) of the acetone-soluble component of the thermoplastic resin composition [X] is usually 0.1 to 1.5 dl / g, preferably 0. .3 to 0.7 dl / g.
  • the intrinsic viscosity [ ⁇ ] is within the above range, the physical property balance between molding processability and impact resistance is excellent.
  • the intrinsic viscosity [ ⁇ ] was measured by the following method. First, the acetone-soluble portion of the thermoplastic resin composition [X] (acetonitrile when the rubbery polymer is an acrylic rubber) was dissolved in methyl ethyl ketone to prepare five samples having different concentrations. The intrinsic viscosity [ ⁇ ] 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 content of the ethylene / ⁇ -olefin-based rubbery polymer [a1] in the component [A] is 5 to 30% by mass with respect to 100% by mass of the thermoplastic resin composition [X], preferably 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 squeaking noise and moldability are inferior, while if it exceeds 30% by mass, the heat resistance decreases.
  • thermoplastic resin composition [X] can be used as necessary with a filler, a nucleating agent, a lubricant, a heat stabilizer, an antioxidant, an ultraviolet absorber, a flame retardant, an antiaging agent, a plasticizer.
  • Various additives such as an agent, an antibacterial agent, and a coloring agent can be contained within a range that does not impair the object of the present invention.
  • thermoplastic resin composition [X] of the present invention may be prepared by using other resins such as polyethylene, polypropylene, polybutylene terephthalate, polyethylene terephthalate, polyphenylene sulfide, and polyamide as necessary. It can be contained in a range.
  • each component is mixed at a predetermined blending ratio using 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.
  • each component may be kneaded in a lump or may be kneaded in multiple stages.
  • the melt kneading temperature is usually 200 to 300 ° C, preferably 220 to 280 ° C.
  • thermoplastic resin composition [X] of the present invention has the same heat resistance in the stick-slip test measured by the method described in the examples below using a stick and slip measuring device SSP-02 manufactured by ZIEGLER.
  • the abnormal noise risk measured using the contact parts made of the plastic resin composition [X] is 1 mm / second and 10 mm / second at each load of 5N and 40N.
  • the abnormal sound level is preferably 5 or less, and more preferably 3 or less. According to the German Automobile Manufacturers Association standard (VDA203-260), if the abnormal noise level is 3 or less, it is acceptable.
  • the abnormal noise risk value measured using contact parts made of the same thermoplastic resin composition [X] uses an ethylene / ⁇ -olefin rubber polymer with a Tm (melting point) of 0 ° C. or less, and is thermoplastic. It can adjust by making silicon content in resin composition [X] into a predetermined quantity.
  • the structure in the present invention is assembled by contacting at least two contact parts.
  • the structure of the present invention includes a contact part obtained by molding the thermoplastic resin composition [X].
  • two or more contact parts are the thermoplastic resin composition [X]. It consists of a molded body.
  • thermoplastic resins including the thermoplastic resin composition [X] of the present invention
  • thermosetting resins and the like.
  • the contact part made of the thermoplastic resin composition [X] is particularly effective when at least two contact parts are made of the thermoplastic resin composition [X] of the present invention. It is more effective when all the parts are made of the thermoplastic resin composition [X] of the present invention.
  • thermoplastic resin examples include polyvinyl chloride, polyethylene, polypropylene, AS resin, ABS resin, AES resin, ASA resin, PMMA, polystyrene, high impact polystyrene, EVA, polyamide (PA), polyethylene terephthalate, and polybutylene terephthalate. , 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.
  • thermosetting resin examples include phenol resin, epoxy resin, urea resin, melamine resin, and unsaturated polyester resin. 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, and SIS, and natural rubber. These can be used alone or in combination of two or more.
  • Examples of the organic material include insulation board, MDF (medium fiber board), hard board, particle board, lumbar core, LVL (single board laminate), OSB (orientation board), PSL (pararam), WB (wafer). Board), hard fiberboard, soft fiberboard, lumbar core plywood, board core plywood, special core-plywood, veneer core-plywood, laminated sheet / board of paper impregnated with tap resin, small pieces of crushed (old) paper, etc.
  • -Boards obtained by mixing a linear body with an adhesive and heating and compressing, various kinds of wood, and the like. These can be used alone or in combination of two or more.
  • the inorganic material include calcium silicate board, flexible board, homocement board, gypsum board, sizing gypsum board, reinforced gypsum board, gypsum lath board, decorative gypsum board, composite gypsum board, various ceramics, and glass. These can be used alone or in combination of two or more.
  • iron, aluminum, copper, various alloys, etc. are mentioned as a metal material. These can be used alone or in combination of two or more.
  • the contact parts in the present invention can be suitably used for various structures in parts for automobile interiors, office equipment, parts for home interiors, parts for home appliances, and the like having parts to be contacted, joined and fitted to each other. .
  • automobile interior parts it is possible to significantly reduce the squeaking noise that occurs when parts come into contact with each other and rub against each other, for example, due to vibration during vehicle travel. Furthermore, it is excellent in safety at the time of collision by performing ductile fracture.
  • Such automotive interior parts include door trim, door lining, pillar garnish, console, console box, center panel, door pocket, ventilator, duct, air conditioner, instrument visor, instrument panel upper garnish, instrument panel upper garnish, A / T indicator, On / off switches (slide part, slide plate), switch bezel, grill front defroster, grill side defroster, lid cluster, cover intro, masks (mask switch, mask radio, etc.), glove box, pockets (pocket deck, pocket) Card), steering wheel horn pad, switch parts, car navigation exterior parts, and the like.
  • it can be particularly suitably used as a ventilator for automobiles, plate blades for air conditioners for automobiles, valve shutters, louvers, switch parts, car navigation exterior parts, and the like.
  • Office equipment parts can greatly reduce the squeaking noise that occurs when they come into contact with other parts and rub against each other by, for example, vibration during operation of the equipment and opening and closing of the desk drawer. Furthermore, it is excellent in safety, such as a collision, by performing ductile fracture.
  • Such contact parts for office equipment can be suitably used for exterior parts, interior parts, parts around switches, parts of movable parts, desk lock parts, desk drawers, and the like.
  • Residential interior parts can greatly reduce the squeaking noise caused by contact and rubbing with other parts, for example, by opening and closing doors and sliding doors. Furthermore, it is excellent in safety, such as a collision, by performing ductile fracture.
  • Such home interior parts can be suitably used as shelf doors, chair dampers, table folding leg movable parts, door opening / closing dampers, sliding door rails, curtain rails, and the like.
  • Household appliance parts can significantly reduce the squeaking noise that occurs when they come into contact with other parts and rub against each other, for example, due to vibration during device operation.
  • Such home appliance parts can be suitably used for exterior parts such as cases and housings, interior parts, parts around switches, parts of movable parts, and the like.
  • Evaluation method The measurement method of silicon content and the measurement / evaluation method of various evaluation items in the following Examples and Comparative Examples are shown below.
  • thermoplastic resin composition shown in Table 1 was injection molded at a cylinder temperature of 250 ° C., an injection pressure of 50 MPa, and a mold temperature of 60 ° C. using an EC40 injection molding machine manufactured by Toshiba Machine.
  • An injection-molded plate having a length of 25 mm, a width of 50 mm, and a thickness of 2 mm was used as a test piece, and the amount of silicon in a range of 25 mm in diameter at the center of the test piece was measured with a fluorescent X-ray analyzer MagiX PRO manufactured by PANalytal. The results are shown in Table 1.
  • thermoplastic resin composition of the contact parts 1 and 2 listed in Table 2 was injection molded at a cylinder temperature of 250 ° C., an injection pressure of 50 MPa, and a mold temperature of 60 ° C. using an IS-170FA injection molding machine manufactured by Toshiba Machine.
  • a test piece having a length of 60 mm, a width of 100 mm, a thickness of 4 mm and a length of 50 mm, a width of 25 mm, and a thickness of 4 mm was cut out from an injection-molded plate of 150 mm, width 100 mm, and thickness 4 mm with a disc saw, and finished with sandpaper of # 100 After chamfering the part, fine burrs were removed with a cutter knife, and two large and small plates were used as test pieces for the contact parts 1 and 2. Two test pieces of the contact parts 1 and 2 are aged in an oven adjusted to 80 ° C. ⁇ 5 ° C. for 300 hours, cooled at 25 ° C.
  • thermoplastic resin composition of the contact part 1 listed in Table 2 was injection molded at a cylinder temperature of 250 ° C., an injection pressure of 50 MPa, and a mold temperature of 60 ° C. with a Toshiba Machine IS-170FA injection molding machine.
  • a test piece with a length of 60 mm, a width of 100 mm, and a thickness of 4 mm was cut out from a 100 mm, 4 mm thick injection molded plate with a disc saw, and the edges were chamfered with sandpaper of # 100, and then a fine burr was removed with a cutter knife. This was removed and used as a test piece of the contact part 1.
  • Polycarbonate resin S-300 (trade name) manufactured by Mitsubishi Engineering Plastics Co., Ltd.
  • thermoplastic resin composition for the contact part 2 is used as a thermoplastic resin composition for the contact part 2 using a Toshiba Machine IS-170FA injection molding machine with a cylinder temperature of 270 ° C., an injection pressure of 50 MPa, and a mold temperature.
  • a test piece of length 50 mm, width 25 mm, thickness 4 mm was cut out from an injection-molded plate 150 mm long, 100 mm wide, 4 mm thick, which was injection-molded at 60 ° C., and edged with a sandpaper of count # 100. After chamfering, fine burrs were removed with a cutter knife and used as a test piece for the contact part 2.
  • Two test pieces of the contact parts 1 and 2 are aged in an oven adjusted to 80 ° C. ⁇ 5 ° C.
  • thermoplastic resin composition of the contact part 1 listed in Table 2 was injection molded at a cylinder temperature of 250 ° C., an injection pressure of 50 MPa, and a mold temperature of 60 ° C. with a Toshiba Machine IS-170FA injection molding machine.
  • a test piece with a length of 60 mm, a width of 100 mm, and a thickness of 4 mm was cut out from a 100 mm, 4 mm thick injection molded plate with a disc saw, and the edges were chamfered with sandpaper of # 100, and then a fine burr was removed with a cutter knife. This was removed and used as a test piece of the contact part 1.
  • test piece made of SUS304 having a length of 50 mm, a width of 25 mm, and a thickness of 4 mm was chamfered with a sandpaper of # 100 and used as a test piece for the contact component 2.
  • Two test pieces of the contact parts 1 and 2 are aged in an oven adjusted to 80 ° C. ⁇ 5 ° C. for 300 hours, cooled at 25 ° C.
  • thermoplastic resin composition of the contact part 1 listed in Table 2 was injection molded at a cylinder temperature of 250 ° C., an injection pressure of 50 MPa, and a mold temperature of 60 ° C. with a Toshiba Machine IS-170FA injection molding machine.
  • a test piece with a length of 60 mm, a width of 100 mm, and a thickness of 4 mm was cut out from a 100 mm, 4 mm thick injection molded plate with a disc saw, and the edges were chamfered with sandpaper of # 100, and then a fine burr was removed with a cutter knife. This was removed and used as a test piece of the contact part 1.
  • a glass test piece having a length of 50 mm, a width of 25 mm, and a thickness of 4 mm was chamfered with sandpaper of count # 100 and used as a test piece for the contact part 2.
  • Two test pieces of the contact parts 1 and 2 are aged in an oven adjusted to 80 ° C. ⁇ 5 ° C. for 300 hours, cooled at 25 ° C.
  • thermoplastic resin composition of Table 1 was injection molded with an EC40 injection molding machine manufactured by Toshiba Machine at a cylinder temperature of 250 ° C., an injection pressure of 80 MPa, a mold temperature of 60 ° C., and a 1 mm diameter center pin gate mold with a diameter of 80 mm.
  • Five disk-shaped molded articles each having a thickness of 2 mm were collected. The obtained five test pieces were visually observed, and the molded appearance was judged according to the following evaluation criteria. The results are shown in Table 1.
  • ⁇ Silver streaks did not occur in the vicinity of the gates in all five test pieces.
  • X Five test pieces contained silver streaks near the gate.
  • Table 2 shows the appearance of the molded structure. The appearance of the entire structure including the contact parts 1 and 2 was judged and evaluated in two stages: ⁇ : good and x: bad.
  • AES-1 A 20 liter stainless steel autoclave equipped with a ribbon stirrer blade, an auxiliary agent continuous addition device, a thermometer, etc., was used as an ethylene / ⁇ -olefin rubbery polymer [a1] as an ethylene / propylene copolymer (ethylene / propylene).
  • Propylene 78/22 (%), Mooney viscosity (ML1 + 4, 100 ° C) 20, melting point (Tm) 40 ° C, glass transition temperature (Tg) -50 ° C 22 parts, styrene 55 parts, acrylonitrile 23 parts , 0.5 parts of t-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 obtain a homogeneous solution.
  • the internal temperature was cooled to 100 ° C., and 0.2 parts of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenol) -propionate, dimethyl silicone oil; KF-96-100 cSt (trade name) : Shin-Etsu Silicone Co., Ltd.) 0.02 part was added, the reaction mixture was extracted from the autoclave, unreacted substances and solvent were distilled off by steam distillation, and an extruder with a 40 mm ⁇ vent (cylinder temperature 220 ° C., degree of vacuum) 760 mmHg) was used to substantially degas the volatiles and pelletize.
  • the resulting ethylene / ⁇ -olefin rubber-reinforced vinyl resin had a graft ratio of 70% and an intrinsic viscosity [ ⁇ ] of acetone-soluble component of 0.47 dl / g.
  • Propylene / dicyclopentadiene copolymer ethylene / propy
  • the internal temperature was cooled to 100 ° C., and 0.2 parts of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenol) -propionate, dimethyl silicone oil; KF-96-100 cSt (trade name) : Shin-Etsu Silicone Co., Ltd.) 0.02 part was added, the reaction mixture was extracted from the autoclave, unreacted substances and solvent were distilled off by steam distillation, and a 40 mm ⁇ vented extruder (cylinder temperature 220 ° C., vacuum) 760 mmHg), the volatile matter was substantially degassed and pelletized.
  • the resulting ethylene / ⁇ -olefin rubber-reinforced vinyl resin had a graft rate of 60% and an intrinsic viscosity [ ⁇ ] of acetone-soluble component of 0.45 dl / g.
  • A-3 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 ⁇ m 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.
  • a monomer mixture consisting of 0.2 parts of t-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 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 [ ⁇ ] of the acetone-soluble component was 0.38 dl / g.
  • B-1 AS-1 A synthesis apparatus in which two jacketed polymerization reactors equipped with ribbon blades were connected was used. After purging nitrogen gas into each reactor, the first reactor was charged with a mixture of 75 parts of styrene, 25 parts of acrylonitrile and 20 parts of toluene, and 0.15 part of tert-dodecyl mercaptan as a molecular weight regulator. was dissolved in 5 parts of toluene and a solution in which 0.1 part of dicumyl peroxide as a polymerization initiator was dissolved in 5 parts of toluene, and polymerization was carried out at 110 ° C.
  • the average residence time of the supplied monomers and the like was 2 hours, and the polymerization conversion after 2 hours was 56%.
  • the obtained polymer solution was continuously taken out by a pump provided outside the first reactor and supplied to the second reactor.
  • the amount continuously taken out is the same as the amount supplied to the first reactor.
  • polymerization was performed at 130 ° C. for 2 hours, and the polymerization conversion after 2 hours was 74%.
  • the polymer solution was recovered from the second reactor, and this was introduced into an extruder with a biaxial three-stage vent. Then, the unreacted monomer and toluene (polymerization solvent) were directly devolatilized to recover the styrene / acrylonitrile copolymer.
  • This styrene / acrylonitrile copolymer was used as Component [B-1].
  • the intrinsic viscosity [ ⁇ ] of this component [B-1] (in methyl ethyl ketone, 30 ° C.) was 0.60 dl / g.
  • 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
  • ADK STAB 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
  • Examples 4 to 12 and Comparative Examples 5 to 9 Using the resin compositions obtained in Examples 1 to 3 and Comparative Examples 1 to 4, contact parts 1 and 2 were prepared by the above-described method, and these were combined as shown in Table 2 to form a structure. Evaluation of stagnation noise, molding appearance and recyclability were evaluated by the above methods. Furthermore, as the contact component 2, those made of polycarbonate (Y3), metal (stainless steel) (Y4), and glass (Y5) were used, and the structures combined with these and the contact component 1 were similarly evaluated. . The evaluation results are shown in Table 2.
  • the structures using the resin compositions X1 to X3 of the present invention represented by Examples 4 to 6 as the contact parts 1 and 2 have an evaluation of squeaking noise and a molded appearance. It is good. Moreover, since the structure using each of these resin compositions X1, X2, and X3 does not require separation for each resin composition, the recyclability is good.
  • the structure of Example 7 is an example in which the resin compositions X1 and X3 are combined. Although the evaluation of the squeaking sound is excellent, the recyclability is inferior.
  • Example 8 is an example in which the resin composition X1 and the resin composition X5 having too much silicon content are combined, and although the evaluation of the squeaking noise is excellent, the molding appearance and the recyclability are inferior.
  • the structures of Examples 10 to 12 are examples in which the resin composition X1 and a different material are combined, and although the evaluation of the squeaking sound is excellent, the resin composition and the different material are required to be separated and the recyclability is inferior. Yes.
  • the structure of Comparative Example 5 is a rubber-reinforced vinyl resin [A-2] using an ethylene / ⁇ -olefin rubber polymer [a1] having no melting point (Tm) as the contact parts 1 and 2.
  • Comparative Example 6 is an example in which resin compositions X5 and X5 having too much silicon content are combined as the contact parts 1 and 2, and the evaluation of the squeaking noise and the molded appearance are inferior.
  • the structure of Comparative Example 7 is a rubber-reinforced vinyl resin [A-3] using a polybutadiene rubber polymer instead of the ethylene / ⁇ -olefin rubber polymer [a1] as the contact parts 1 and 2. ], And the evaluation of the squeaking sound is inferior.
  • Comparative Example 8 is a rubber-reinforced vinyl resin [A-3] using a polybutadiene rubber polymer instead of the ethylene / ⁇ -olefin rubber polymer [a1] as the contact parts 1 and 2. ], which is a combination of resin compositions Y2 and Y2 containing succinic acid, and the evaluation of the squeaking noise and the molded appearance are inferior.
  • the structure of Comparative Example 9 is an example in which resin components Y1 and Y2 containing a rubber-reinforced vinyl resin [A-3] using a polybutadiene rubber polymer are combined as the contact parts 1 and 2. The evaluation of stagnation noise and the molded appearance are inferior, and the recyclability is inferior because the resin compositions Y1 and Y2 need to be separated.
  • thermoplastic resin composition of the present invention has an excellent squeaking noise reduction effect for a wide range of materials regardless of the material of the contact component to be assembled, contact between components, It can be seen that the present invention is suitable for automobile interior parts, office equipment, house interior parts, home appliance parts, and the like having parts to be joined and fitted.
  • thermoplastic resin composition for reducing squeaking noise significantly reduces the squeaking noise that occurs when two or more parts rub against each other, and reduces the squeaking noise reducing effect even when left at high temperatures for a long time. It is possible to provide a structure made of a contact component that is maintained without any impact, and further has excellent impact resistance. It can be suitably used for home interior parts, home appliance parts, and the like.

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PCT/JP2012/072155 2011-09-02 2012-08-31 軋み音低減用熱可塑性樹脂組成物及び軋み音低減構造体 Ceased WO2013031946A1 (ja)

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US15/140,518 US9777147B2 (en) 2011-09-02 2016-04-28 Thermoplastic resin composition for reduction of squeaking noises and structure of reduced squeaking noises

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