JP6193453B2 - Thermoplastic resin composition for reducing squeaking noise, contact parts and structure - Google Patents

Description

  The present invention relates to a thermoplastic resin composition that reduces the occurrence of squeaking noise, a contact part made of the composition, and a structure including the contact part, and more specifically, at least two parts are in contact with each other and rub against each other. The present invention relates to a thermoplastic resin composition capable of greatly reducing the squeaking noise generated by the above, a contact part made of the composition, and a structure including the contact part.

  Styrenic resins typified by ABS resins are widely used in automobiles, home appliances, OA equipment and the like due to their excellent moldability, mechanical properties, chemical resistance, and secondary processability.

  However, 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. For example, 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.

  Further, it is known that a squeaking noise is generated when parts made of styrene resin are rubbed together. For this reason, for example, in applications where parts that are in contact with each other due to vibration, rotation, and the like are rubbed together, there is a high risk of squeaking noise, so it is avoided to use parts made of styrenic resin in combination. .

Since 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. When fitting with a member made of other resin such as a button, a stick-slip phenomenon as shown in FIG. 1 occurs due to a large friction coefficient, and abnormal noise (stagnation sound) is often generated. Are known. The stick-slip phenomenon occurs when two objects rub against each other. When the object M connected by a spring is placed on a driving table that moves at a driving speed V as shown in the model of FIG. The object M first moves to the right as shown in FIG. 2 (b) together with the table moving at the driving speed V by the action of the static friction force. When the force to be restored by the spring becomes equal to the static friction force, the object M starts to slide in the direction opposite to the driving speed V. At this time, the object M receives a dynamic frictional force, so that the sliding stops at the time of FIG. 2C when the dynamic force of the spring becomes equal to the dynamic frictional force, that is, adheres to the drive base. It moves in the same direction as the driving speed V (FIG. 2 (d)). This is called a stick-slip phenomenon. As shown in FIG. 1, it is said that if the difference Δμ between the static friction coefficient μs at the upper end of the sawtooth waveform and the friction coefficient μl at the lower end of the sawtooth waveform is large, itching is likely to occur. . The dynamic friction coefficient is an intermediate value between μs and μl.
When these squeaking noises are used, for example, in automobile interiors, they are a major cause of impairing comfort and quietness when riding, and there is a strong demand for reduction of squeaking noises.

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

  In order to prevent such squeaking noise, a method of applying a Teflon (registered trademark) coating to a member surface, a method of mounting a Teflon (registered trademark) tape, a method of applying silicone oil, etc. have been performed. Such a process is not only complicated and time-consuming, but also has a problem that the effect is not sustained when placed at a high temperature for a long time.

  In addition, as a method for modifying the material itself in order to reduce the squeaking noise, a method of blending silicone oil into the ABS resin, a method of blending an epoxy-containing olefin copolymer into the ABS resin, and the like have been proposed. For example, a technique for blending an organosilicon compound with a PC / ABS resin (see Patent Document 1), a technique for blending a flame retardant, a flame retardant aid, and silicone oil with an ABS resin (see Patent Document 2), and rubber A technology for blending silicone oil into a modified polystyrene resin (see Patent Document 3), a technology for blending an alkali (earth) metal salt of alkane sulfonic acid into an ABS resin (see Patent Document 4), and further to an ABS resin. 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.

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

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

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

  In view of such circumstances, the present invention significantly reduces the generation of squeaking noise even when the styrene-based members are rubbed against each other, and reduces squeaking noise even when left at high temperatures for a long time. A resin composition capable of providing a structure including a part made of a styrene resin that is maintained without deterioration of the effect and excellent in impact resistance and molding appearance, a contact part comprising the composition, and An object is to provide a structure including the contact component.

  As a result of diligent research to solve the above problems, the present inventors polymerized a vinyl monomer [b1] in the presence of a specific ethylene / α-olefin rubber polymer [a1]. A thermoplastic resin composition [X] containing the resulting rubber-reinforced vinyl resin [A], wherein the free rubber content in the thermoplastic resin composition [X] is within a specific range, thereby allowing a styrene resin The generation of squeaking noise is remarkably reduced even when the parts made of each other are rubbed together, and even when left at high temperatures for a long time, the squeaking noise reduction effect is maintained without deteriorating. Furthermore, impact resistance and molding It has been found that the appearance is excellent, and the present invention has been completed.

According to the present invention, the following thermoplastic resin composition for reducing squeaking noise, a contact part comprising the composition, and a structure including the contact part are provided.
1. Rubber-reinforced vinyl resin [A] obtained by polymerizing vinyl monomer [b1] containing aromatic vinyl compound and vinyl cyanide compound in the presence of ethylene / α-olefin rubber polymer [a1] A thermoplastic resin composition [X] comprising
The content of the ethylene / α-olefin rubber polymer [a1] is 5 to 30% by mass with respect to 100% by mass of the thermoplastic resin composition [X],
The crystallinity of the ethylene / α-olefin rubbery polymer [a1] is 1 to 20%,
The ethylene / α-olefin rubbery polymer [a1] has a tensile strength (T _S ) of 0.5 to 7 MPa, an elongation at break (E _B ) of 500% or more, and a hardness (type A durometer) of 40 to 40. 85, Mooney viscosity (ML _{1 + 4} , ₁₀₀ ° C.) is 5 to 60,
The free rubber content of the ethylene / α-olefin rubber polymer [a1] in which the vinyl monomer [b1] in the thermoplastic resin composition [X] is not polymerized is 1 to 30% by mass. A thermoplastic resin composition for reducing squeaking noise, which is characterized in that it exists.
2. 2. The thermoplastic resin composition for reducing squeaking noise according to the above 1, wherein the ethylene / α-olefin rubbery polymer [a1] has a Tm (melting point) of 0 ° C. or higher.
3. The content of the ethylene / α-olefin-based rubbery polymer [a1] is 5 to 20% by mass with respect to 100% by mass of the thermoplastic resin composition [X]. Thermoplastic resin composition for reducing squeaking noise.
4). 4. The thermoplastic resin composition for reducing squeaking noise according to any one of 1 to 3 above, wherein the graft ratio of the rubber-reinforced vinyl resin [A] is 30 to 70% by mass.
5. 5. The thermoplastic resin composition for reducing squeaking noise according to any one of 1 to 4 above, wherein the free rubber content in the thermoplastic resin composition [X] is 2 to 20% by mass.
6). A thermoplastic resin composition [X] polymerizes a vinyl monomer [b1] containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of an ethylene / α-olefin rubber polymer [a1]. It comprises a rubber-reinforced vinyl resin [A1] obtained and a (co) polymer [B] of a vinyl monomer [b2] containing an aromatic vinyl compound and a vinyl cyanide compound. The thermoplastic resin composition for reducing stagnation noise according to any one of 1 to 5 above.
7). 7. The thermoplastic resin composition for reducing squeaking noise according to any one of 1 to 6 above, wherein the ethylene / α-olefin rubbery polymer [a1] is an ethylene / propylene copolymer.
8). The ethylene / α-olefin rubbery polymer [a1] is composed of 5 to 95% by mass of ethylene and 95 to 5% by mass of α-olefin (however, the total of ethylene and α-olefin is 100% by mass). The thermoplastic resin composition for reducing stagnation noise according to any one of 1 to 7 above.
9. The above 6 characterized in that the rubber-reinforced vinyl resin [A1] is 10 to 90% by mass and the (co) polymer [B] is 10 to 90% by mass (however, the total of both is 100% by mass). The thermoplastic resin composition for reducing squeaking noises as described.
10. A contact component comprising the thermoplastic resin composition [X] according to any one of 1 to 9 above.
11. 11. The contact part as described in 10 above, wherein an abnormal noise risk value of the contact part measured under the following conditions is 10 or less.
〔Measurement condition〕
From an injection-molded plate 150mm long, 100mm wide, 4mm thick, injection-molded at a cylinder temperature of 250 ° C, an injection pressure of 50MPa, and a mold temperature of 60 ° C using a Toshiba Machine IS170FA injection molding machine. Cut out a large and small test piece of 4mm in length, 50mm in length, 25mm in width and 4mm in thickness with a disc saw, chamfer the end with sandpaper of count # 100, and remove fine burrs with a cutter knife. Prepare the plate as a test piece for the contact part. The two large and small test pieces are held in an oven adjusted to 80 ° C. ± 5 ° C. for 400 hours, cooled at 25 ° C. for 24 hours, and then fixed to a stick slip tester SSP-002 manufactured by ZIEGLER, with a load of 40 N and a speed. The abnormal noise risk value is measured by rubbing three times under the conditions of 10 mm / second and an amplitude of 20 mm, and the highest value is defined as the abnormal noise risk value.
12 A structure including at least two contact parts, wherein the at least two contact parts include the contact parts described in 10 or 11 above.
13. A squeaking noise reducing structure characterized in that all of the contact parts are made of the contact parts described in 10 or 11 above.
14 14. The squeaking noise reducing structure according to 12 or 13 above, wherein the structure is an automobile part, a part for office equipment, a part for housing, or a part for home appliance.

  According to the present invention, the rubber-reinforced vinyl resin [A] obtained by polymerizing the vinyl monomer [b1] in the presence of the specific ethylene / α-olefin rubber polymer [a1] is contained. The ethylene resin and the α-olefin rubber polymer [a1] have a crystallinity, tensile strength, elongation at break, hardness and Mooney viscosity within a specific range. In addition, by setting the free rubber content in the thermoplastic resin composition [X] within a specific range, even if the parts made of styrene resin are rubbed together, the generation of squeaking noise is significantly reduced, and A contact component and a structure including the contact component, which are maintained without deterioration in the squeaking noise reduction effect even when placed at a high temperature for a long time, and further excellent in impact resistance and molded appearance, are obtained. Is possible.

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

Hereinafter, the present invention will be described in detail.
The thermoplastic resin composition for reducing squeaking noise in the present invention has a tensile strength (T _S ) of 0.5 to 7 MPa, an elongation at break (E _B ) of 500% or more, and a hardness (type A durometer) of 40 to 85. A rubber obtained by polymerizing a vinyl monomer [b1] in the presence of an ethylene / α-olefin rubber polymer [a1] having a Mooney viscosity (ML _{1 + 4} , ₁₀₀ ° C.) of 5 to 60 A thermoplastic resin composition [X] containing a reinforced vinyl resin [A], wherein the free rubber content in the thermoplastic resin composition [X] is 1 to 30% by mass. And

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

1. Rubber reinforced vinyl resin [A] (hereinafter also referred to as “component [A]”):
The component [A] used in the present invention has a tensile strength (T _S ) of 0.5 to 7 MPa, a tensile elongation (E _B ) of 500% or more, a hardness (type A durometer) of 40 to 85, a Mooney viscosity ( A rubber-reinforced vinyl resin obtained by polymerizing a vinyl monomer [b1] in the presence of an ethylene / α-olefin rubber polymer [a1] having an ML _{1 + 4} of ₁₀₀ ° C. of 5 to 60 [A1] A rubber-reinforced vinyl resin composed of a single or a mixture of the rubber-reinforced vinyl resin [A1] and a (co) polymer [B] of the vinyl monomer [b2]. The (co) polymer [B] is obtained by polymerizing the vinyl monomer [b2] in the absence of a rubbery polymer.

1-1. Ethylene / α-olefin rubbery polymer [a1] (hereinafter also referred to as “component [a1]”):
The ethylene / α-olefin rubbery polymer [a1] used in the present invention has a tensile strength (T _S ) of 0.5 to 7 MPa, a tensile elongation (E _B ) of 500% or more, and a hardness (type A durometer). ) Is 40 to 85, and the Mooney viscosity (ML _{1 + 4} , ₁₀₀ ° C.) is 5 to 60. Here, the tensile strength (T _S ) and the tensile elongation (E _B ) were measured according to JIS K6251. The hardness (type A durometer) was measured according to JIS K6253. The Mooney viscosity (ML _{1 + 4} , ₁₀₀ ° C.) was measured according to JIS K6300.
The tensile strength (T _s ) of the component [a1] is 0.5 to 7 MPa, preferably 0.5 to 5 MPa, and more preferably 0.5 to 3 MPa. When the tensile strength (T _S ) is within the above range, the effect of reducing squeaking noise is excellent.
The tensile elongation (E _B ) of the component [a1] is 500% or more, preferably 650% or more, more preferably 750% or more, and particularly preferably 800% or more. If the tensile elongation (E _B ) is less than 500%, the effect of reducing the squeaking noise is inferior. The upper limit of the tensile elongation (E _B ) of the component (a1) is usually 3,000%.
The hardness of the component [a1] (type A durometer) is 40 to 85, preferably 45 to 85, and more preferably 50 to 85. When the hardness (type A durometer) is within the above range, the effect of reducing the squeaking noise is excellent.
Furthermore, the Mooney viscosity (ML _{1 + 4} , ₁₀₀ ° C.) of the component [a1] is 5 to 60, preferably 5 to 50, more preferably 10 to 45. When the Mooney viscosity is within the above range, the effect of reducing squeaking noise and the surface appearance of the resulting molded product are excellent.

As an alpha olefin which comprises the said component [a1], a C3-C20 alpha olefin is mentioned, for example, Specifically, a propylene, 1-butene, 1-pentene, 1-hexene, 4- Examples include methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene, 1-eicosene and the like. These α-olefins can be used alone or in admixture of two or more. The carbon number of the α-olefin is preferably 3 to 20, more preferably 3 to 12, and still more preferably 3 to 8. When the number of carbon atoms exceeds 20, the copolymerizability is lowered and the surface appearance of the molded product may be insufficient. The mass ratio of ethylene: α-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 mass ratio of ethylene and α-olefin can be determined by calculating from the polymerization prescription and by measuring by ¹³ C-NMR method.
When the weight ratio of α-olefin exceeds 95, the resulting rubber-reinforced vinyl resin tends to have insufficient impact resistance, such being undesirable. If it is less than 5, rubber elasticity of the rubbery polymer [a1] is not sufficient, and the impact resistance of the resin composition tends to be insufficient, which is not preferable.

The component [a1] preferably has a Tm (melting point), and more preferably has a Tm of 0 ° C. or higher. Here, 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. If the Tm is less than 0 ° C., the effect of reducing the squeaking noise is inferior. In the DSC measurement, 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. Therefore, those without Tm are also inferior in the effect of reducing the squeaking noise.
Further, 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. In addition, the said glass transition temperature can be calculated | required based on JISK7121-1987 using DSC (differential scanning calorimeter) similarly to the measurement of Tm (melting | fusing point).

  Furthermore, the crystallinity of the component [a1] is usually 1 to 20%, preferably 1 to 15%, more preferably 3 to 15%. If the degree of crystallinity is less than 1%, the effect of reducing squeaking noise may not be sufficiently obtained. On the other hand, if the degree of crystallinity exceeds 20%, the impact resistance may be insufficient or it may be difficult to produce a rubber-reinforced vinyl resin. The crystallinity can be measured by a known X-ray diffraction method.

  The ethylene / α-olefin rubbery polymer [a1] is usually an ethylene / α-olefin copolymer that does not contain a non-conjugated diene component from the viewpoint of reducing squeaking noise. It is also possible to contain a conjugated diene component. The blending amount of the non-conjugated diene component is preferably 3% by mass or less based on 100% by mass of ethylene and α-olefin. When the amount of the non-conjugated diene component exceeds 3% by mass, the crystallinity of the rubber is lowered, and the effect of reducing the squeaking noise may not be sufficient. Moreover, the iodine value of the said component [a1] is 0-10 normally, Preferably it is 0-5, More preferably, it is 0-3. If the iodine value exceeds 10, it may be insufficient to maintain the stagnation sound reduction effect and the stagnation sound reduction effect when placed at a high temperature for a long time. 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.

Next, the ethylene-α-olefin rubbery polymer [a1] used in the present invention is, for example, a method using a Ziegler catalyst disclosed in JP-B-06-018942 and JP-B-07-103280. It can be obtained by a known method.
The α-olefin is an α-olefin having 3 to 12 carbon atoms, and specific examples include propylene, 1-butene, 4-methyl-1-pentene, 1-octene and the like. Of these, propylene and / or 1-butene is preferable, and propylene is particularly preferable. These α-olefins can be used alone or in combination of two or more.
Non-conjugated dienes include 1,4-hexadiene, 5-ethylidene-2-norbornene (ENB), dicyclopentadiene (DCP), and the like. These can be used alone or in combination of two or more.

Specifically, the ethylene-α-olefin rubbery polymer [a1] can be suitably obtained by the following production method.
That is, the catalyst component used in the production of the ethylene-α-olefin rubber polymer [a1] includes a combination of a vanadium compound and / or a titanium compound and an organometallic compound of a metal of Groups I to IV of the periodic table. A catalyst consisting of
As the vanadium compound, a trivalent to pentavalent vanadium compound soluble in an inert organic solvent is used.
The vanadium compound is preferably a vanadium halide, an oxyhalide, a chelate complex with an oxygen-containing compound, a vanadate or the like.
Specific examples of these compounds include vanadium tetrachloride, vanadium oxytrichloride, vanadium trisacetylacetonate, triethoxide vanadate, tri-n-butoxide vanadate, di-n-butoxymonochloride vanadate, vanadic acid. Examples include ethoxy dichloride, vanadium tetrachloride or a reaction product of vanadium oxytrichloride with alcohol. These can be used alone or in combination of two or more.
More preferred among these compounds are vanadium tetrachloride, vanadium oxytrichloride, and reaction products of these vanadium compounds with alcohols.
As the titanium compound, a solid or dissolved titanium trichloride catalyst, a titanium trichloride supported on magnesium chloride or a titanium tetrachloride catalyst is used, and a vanadium compound is preferable.
Examples of the organometallic compounds of the metals in Groups I to IV of the periodic table include organolithium compounds, organozinc compounds, organomagnesium compounds, and organoaluminum compounds. Of these, organoaluminum compounds are particularly preferred.
Examples of organoaluminum compounds include triethylaluminum, tri-n-propylaluminum, tri-isopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, tri-n- Decylaluminum, tri-n-dodecylaluminum, diethylmonochloroaluminum, dibutylmonochloroaluminum, di-n-hexylmonochloroaluminum, di-n-octylmonochloroaluminum, ethylaluminum sesquichloride, n-butylaluminum sesquichloride, ethylaluminum dichloride, n-butylaluminum dichloride, isobutylaluminum dichloride, n-hexylaluminum dichloride, n-octyl Such Rumi um dichloride.

These organoaluminum compounds can also be used as reactants such as alcohols and amines.
For example, methanol, ethanol, n-butanol, isobutanol, t-butanol, n-hexanol, n-octanol, 2-ethyl-hexanol, n-decanol, triethylamine, tri-n-propylamine, tri-n-butylamine, Tri-isobutylamine, tri-n-hexylamine, tri-n-octylamine, tri-2-ethylhexylamine, diethylamine, di-n-butylamine, di-isobutylamine, di-n-octylamine, di-2- Examples include ethylhexylamine, ethylamine, n-propylamine, n-butylamine, isobutylamine, 2-ethylhexylamine. The ratio of these organoaluminum compounds and reactants is 0.01 to 0.5, preferably 0.05 to 0.2 (molar ratio) with respect to the aluminum compound.
These organoaluminum compounds or reactants of organoaluminum compounds can be used in combination of two or more.

  The polymerization reaction is usually performed in an inert hydrocarbon solvent. Examples of such an inert hydrocarbon solvent include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane and dodecane; aromatic hydrocarbons such as benzene, toluene and xylene. In addition, methyl chloride, ethyl chloride, methylene chloride, ethylene chloride, or the like in which part of hydrogen constituting these hydrocarbons is substituted with a halogen atom may be used. These hydrocarbon solvents can be used alone or in admixture of two or more.

  The polymerization solvent used for the polymerization reaction is an inert hydrocarbon solvent such as n-hexane, n-heptane, n-octane, isooctane, n-decane, cyclohexane, methyl chloride, ethyl chloride, methylene chloride, ethylene chloride, etc. It is done.

  The polymerization temperature is usually −50 ° C. to 120 ° C., preferably 0 to 80 ° C. When the polymerization temperature is less than −50 ° C., a large amount of energy is required for cooling the reaction system, which is economically disadvantageous. On the other hand, when the polymerization temperature is higher than 120 ° C., the polymerization activity is lowered, and the copolymerization of the α-olefin is further lowered, so that the copolymer in the present invention cannot be obtained.

  The polymerization form in the production of the ethylene-α-olefin rubber polymer [a1] may be either slurry polymerization or homogeneous solution polymerization. The polymerization reaction operation may be either a batch type or a continuous type. As the reactor to be used, single or plural reactors are connected in series or in parallel, and each raw material olefin is introduced separately or premixed. The reaction temperature in the reaction system is maintained by an external cooling method or use of latent heat of vaporization of the solvent monomer. The pressure can be applied from a reduced pressure state (about 100 Pa) to a pressurized state (about 15 MPa).

The molecular weight of the ethylene-α-olefin-based rubbery polymer [a1] can be controlled only by appropriately selecting the catalyst composition ratio, catalyst amount, catalyst type, and polymerization temperature described above. This can be done using a molecular weight regulator.
Processes such as separation of the produced copolymer from the reaction medium and unreacted monomers, deactivation of the catalyst used, removal of catalyst residue, drying of the copolymer and granulation are well known in the industry. Can be done.

  The ethylene-α-olefin rubbery polymer [a1] used in the present invention can also be obtained by a method using a metallocene catalyst disclosed in Japanese Patent No. 3518081, for example. The metallocene catalyst can design the active site by the molecular structure of the organometallic complex, that is, the coordination structure of the complex, which has been difficult with a polymer having a very uniform molecular weight and composition, or a conventional Ziegler catalyst, Copolymer rubbery polymer of α-olefin and ethylene having a large carbon number can be produced.

1-2. Vinyl monomers [b1] and [b2]:
The 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. In addition, if necessary, other copolymerizable vinyl monomers such as (meth) acrylic acid ester and maleimide compound, carboxyl group, acid anhydride group, hydroxyl group, amino group, amide group, epoxy group A functional group-containing vinyl monomer having at least one functional group such as an oxazoline group may be used in combination.
The vinyl 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 thereof include styrene, α-methyl styrene, o-methyl styrene, p-methyl styrene, vinyl toluene, β-methyl styrene, ethyl styrene, p-tert-butyl styrene, vinyl xylene, vinyl naphthalene, monochlorostyrene, dichloromethane. Examples thereof include styrene, monobromostyrene, dibromostyrene, and fluorostyrene. These can be used alone or in combination of two or more. Of these, styrene and α-methylstyrene are preferred.

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

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

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

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

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

As unsaturated compounds having an amino group, aminoethyl acrylate, propylaminoethyl acrylate, dimethylaminomethyl acrylate, diethylaminomethyl acrylate, 2-dimethylaminoethyl acrylate, aminoethyl methacrylate, propylaminoethyl methacrylate , Dimethylaminomethyl methacrylate, diethylaminomethyl methacrylate, 2-dimethylaminoethyl methacrylate, phenylaminoethyl methacrylate, p-aminostyrene, N-vinyldiethylamine, N-acetylvinylamine, acrylicamine, methacrylamine, N- Examples include methylacrylamine. These can be used alone or in combination of two or more.
Examples of the unsaturated compound having an amide group include acrylamide, N-methylacrylamide, methacrylamide, N-methylmethacrylamide and the like. These can be used alone or in combination of two or more.

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

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

  The 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 30-100% by mass, preferably 50-100% by mass, and more preferably 70-100% 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 the vinyl monomer. %. The use ratio of the aromatic vinyl compound and the vinyl cyanide compound (aromatic vinyl compound / vinyl cyanide compound) is usually 40 to 85% by mass / 15 to 60% by mass when the total of these is 100% by mass. , Preferably 45 to 85% by mass / 15 to 55% by mass, particularly preferably 60 to 85% by mass / 15 to 40% by mass.

1-3. Method for producing the rubber-reinforced vinyl resin [A]:
The rubber-reinforced vinyl resin [A] is a polymer component containing the ethylene / α-olefin rubbery polymer [a1], but the containing form is not particularly limited.
In the rubber-reinforced vinyl resin [A], a graft copolymer in which a (co) polymer of a vinyl monomer is grafted to a rubber polymer, and a rubber polymer are not grafted. (Co) polymers of vinyl monomers are included. However, this graft copolymer may contain a rubbery polymer to which a (co) polymer of a vinyl monomer is not grafted.
Moreover, the content aspect of said ethylene * alpha-olefin type rubbery polymer [a1] is illustrated below.
(1) When the ethylene / α-olefin rubbery polymer [a1] is contained as a graft copolymer.
(2) The case where the ethylene / α-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 / α-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]”).
Among these, [ii] is particularly preferable because the amount of the ethylene / α-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].

Next, the manufacturing method of said rubber reinforced vinyl resin [A1] is demonstrated.
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 monomers may be charged all at once, or may be reacted by dividing or continuously adding them. Further, the rubbery polymer may be added or reacted in the whole or in part during the polymerization with the vinyl monomer.
In addition, the usage-amount of a rubber-like polymer is 5-80 mass% normally when the sum total of a rubber-like polymer and a vinyl-type monomer is 100 mass%, Preferably it is 10-70 mass%.

  The method for producing the rubber-reinforced vinyl resin [A1] is preferably emulsion polymerization, solution polymerization and bulk polymerization, more preferably solution polymerization, and may be a combination of these methods. When the 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.

As the polymerization initiator, a combination of an organic peroxide such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramentane hydroperoxide and a reducing agent represented by a sugar-containing pyrophosphate formulation, a sulfoxylate formulation, etc. Redox polymerization initiators by: persulfates such as potassium persulfate; peroxides such as benzoyl peroxide (BPO), lauroyl peroxide, 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 usage-amount of the said polymerization initiator is 0.05-5 mass% normally with respect to the said vinyl-type monomer [b1], Preferably it is 0.1-1 mass%.
The polymerization initiator is usually added all at once or continuously to the reaction system.

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

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

  Emulsion polymerization can be carried out under known conditions depending on the type and amount of the vinyl monomer [b1] and 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. Examples of the coagulant include inorganic salts such as calcium chloride, magnesium sulfate, magnesium chloride, and sodium chloride; inorganic acids such as sulfuric acid and hydrochloric acid; organic acids such as acetic acid, lactic acid, and citric acid. These can be used alone or in combination of two or more. Further, depending on the required performance, washing may be carried out after adding an alkali component or an acid component after solidification to neutralize it.

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

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

  Solution polymerization can be carried out under known conditions depending on the type of vinyl monomer [b1], polymerization initiator and the like 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 manufacture without using a polymerization initiator.

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

1-5. Physical properties of rubber-reinforced vinyl resin [A]:
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, and particularly preferably 30 to 70% by mass. When the graft ratio is less than 10% by mass, the interfacial strength between the graft copolymer and the (co) polymer of the vinyl monomer [b1] is inferior, and the impact resistance may not be sufficient. On the other hand, if it exceeds 150% by mass, the layer made of the (co) polymer of the vinyl monomer [b1] on the surface of the rubbery polymer becomes thick, and the above (copolymer) grafted inside the rubbery polymer. ) Since a layer made of a polymer develops, the rubber elasticity is lowered, and as a result, the impact resistance may be lowered and the appearance of the obtained molded product may be lowered.

  The graft ratio can be determined by the following formula.

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

In the above formula, 1 g of rubber-reinforced vinyl resin [A1] is added to 20 ml of acetone, shaken with a shaker for 2 hours under a temperature condition of 25 ° C., and then at a temperature condition of 5 ° C. This is the mass (g) of insoluble matter obtained by centrifuging for 60 minutes with a centrifuge (rotation speed: 23,000 rpm) and separating the insoluble matter and the soluble matter, and T is a rubber-reinforced vinyl resin [A1 ] The mass (g) of the rubbery polymer contained in 1 gram. 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 graft ratio can be adjusted by appropriately selecting the type and amount of chain transfer agent used during production, the type and amount of polymerization initiator, the polymerization temperature, and the like.

  In addition, the intrinsic viscosity [η] (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. If the intrinsic viscosity [η] is in the above range, the resulting molded article is excellent in the balance of appearance, molding processability and impact resistance, and is preferable.

The intrinsic viscosity [η] 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 [η] was determined from the results of measuring the reduced viscosity of each concentration at 30 ° C. using an Ubbelohde viscosity tube. The unit is dl / g.
The intrinsic viscosity can be adjusted by appropriately selecting the type and amount of chain transfer agent used during production, the type and amount of polymerization initiator, the polymerization temperature, and the like.

The free rubber content in the rubber-reinforced vinyl resin [A1] is preferably 1 to 30% by mass, more preferably 1 to 25% by mass, and still more preferably 2 to 20% by mass. When the free rubber content is within the above range, the squeaking noise reduction effect is excellent, which is preferable.
The free rubber content in the rubber-reinforced vinyl resin [A1] is the type and amount of the ethylene / α-olefin rubber polymer [a1] used, the component [A1] the polymerization prescription at the time of polymerization, the polymerization temperature, It can adjust by selecting suitably polymerization time, the kind of polymerization initiator, its usage-amount, etc. For example, when the amount of the polymerization initiator is reduced, a graft reaction with respect to rubber is less likely to occur, and a rubber-reinforced vinyl resin [A1] having a high free rubber content can be obtained.

2. (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.

2-2. Physical properties of (co) polymer [B]:
The intrinsic viscosity [η] (measured in methyl ethyl ketone at 30 ° C.) of the polymer [B] is usually 0.1 to 1.5 dl / g, preferably 0.2 to 1.0 dl / g. If the intrinsic viscosity [η] is within the above range, it is preferable because it is excellent in the balance of physical properties of molding processability and impact resistance.

The intrinsic viscosity [η] was measured by the following method. First, the above (co) polymer [B] was dissolved in methyl ethyl ketone to prepare 5 samples having different concentrations. The intrinsic viscosity [η] was determined from the results of measuring the reduced viscosity of each concentration at 30 ° C. using an Ubbelohde viscosity tube. The unit is dl / g.
The intrinsic viscosity can be adjusted by appropriately selecting the type and amount of chain transfer agent used during production, the type and amount of polymerization initiator, the polymerization temperature, and the like.

3. Thermoplastic resin composition [X]:
The thermoplastic resin composition [X] in the present invention is obtained by mixing the above-mentioned component [A1] and, if desired, the above-mentioned component [B] at a predetermined blending ratio, and melt-kneading. The blending amount of the component [A1] and the component [B] (component [A1] / component [B]) is preferably 10 with respect to 100% by mass in total of the component [A1] and the component [B]. It is -90 mass% / 10-90 mass%, More preferably, it is 20-80 mass% / 20-80 mass%.

The thermoplastic resin composition [X] of the present invention has a specific amount of free rubber present in the rubber-reinforced vinyl resin [A] at the interface where the parts are in contact with each other. It is possible to suppress the occurrence of the stick-slip phenomenon. Further, the tensile strength (T _S ), elongation at break (E _B ), hardness (type A durometer) and Mooney viscosity (ML _{1 + 4} , ₁₀₀ ° C.) of the ethylene / α-olefin rubber polymer [a1] By setting each in a specific range, it can be considered that the rubber is deformed when the parts are in contact with each other, thereby suppressing the occurrence of a stick-slip phenomenon that causes stagnation.
The above-described stick-slip phenomenon considered to be the cause of the squeaking noise has been difficult to evaluate by the conventional sliding test, but is evaluated by using a stick slip tester “SSP-002” manufactured by ZIEGLER. It is possible.
The free rubber content of the thermoplastic resin composition [X] is 1 to 30% by mass, preferably 1 to 25% by mass, and more preferably 2 to 20% by mass. When the free rubber content is within the above range, the squeaking noise reduction effect is excellent.
The free rubber content in the thermoplastic resin composition [X] can be adjusted by adjusting the free rubber content of the rubber-reinforced vinyl resin [A1].

Further, the intrinsic viscosity [η] (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. When the intrinsic viscosity [η] is within the above range, the physical property balance between molding processability and impact resistance is excellent.
The intrinsic viscosity can be adjusted by appropriately selecting the type and amount of chain transfer agent used in the production of the components [A1] and [B], the type and amount of polymerization initiator, the polymerization temperature, and the like.

  The intrinsic viscosity [η] 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 [η] was determined from the results of measuring the reduced viscosity of each concentration at 30 ° C. using an Ubbelohde viscosity tube. The unit is dl / g.

  The content of the ethylene / α-olefin rubber polymer [a1] in the thermoplastic resin composition [X] is 5 to 30% by mass with respect to 100% by mass of the thermoplastic resin composition [X]. Yes, preferably 5 to 25% by mass, particularly preferably 5 to 20% by mass. If the content of the component [a1] is less than 5% by mass, the effect of reducing the squeaking noise and the impact resistance are inferior, whereas if it exceeds 30% by mass, the heat resistance is lowered.

The thermoplastic resin composition [X] in the present invention is optionally filled with a filler, a nucleating agent, a lubricant, a heat stabilizer, an antioxidant, an ultraviolet absorber, a flame retardant, an anti-aging agent, a plasticizer, and an antibacterial agent. Various additives such as a coloring agent and a coloring agent can be contained within a range not impairing the object of the present invention.
The silicon content in the thermoplastic resin composition [X] is preferably 0.15% by mass or less, more preferably 0.1% by mass or less, and more preferably 0.1% by mass or less with respect to 100% by mass of the thermoplastic resin composition. Preferably it is 0.07 mass% or less, Most preferably, it is 0.03 mass% or less. When the silicon content in the thermoplastic resin composition [X] exceeds 0.15% by mass, a squeaking noise is generated when the contact parts made of the same material are used in combination, or the molded appearance is insufficient. There is a possibility.

  Furthermore, the 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.

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

4). Contact Parts The thermoplastic resin composition [X] of the present invention is various contact parts described later. There is no limitation on the method for producing the contact part from the thermoplastic resin composition [X], and injection molding, injection compression molding, gas assist molding, press molding, calendar molding, T-die extrusion molding, profile extrusion molding, It can be produced by a known method such as film forming.
5. Structure:
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]. Preferably, all the contact parts are molded from the thermoplastic resin composition [X]. Consists of the body.

There are no particular restrictions on the material of the other parts with which the contact parts included in the structure of the present invention come into contact. For example, a thermoplastic resin containing the thermoplastic resin composition [X] of the present invention and / or thermosetting Resin, other thermoplastic resin and / or thermosetting resin not containing the thermoplastic resin composition [X] of the present invention, rubber, organic material, inorganic material, metal material, etc. It is effective when the contact parts are made of the thermoplastic resin composition [X] of the present invention. Furthermore, when all of the contact parts are made of the thermoplastic resin composition [X] of the present invention, It is effective.
Examples of the thermoplastic resin 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.
Examples of the thermosetting resin 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.
Examples of 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.
Furthermore, 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 automobiles, office equipment, parts for homes, parts for home appliances, and the like that have parts where the parts come into contact, join, and fit.
For automobile 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, since it is excellent in impact resistance, it is also excellent in safety at the time of collision. Such automotive parts include door trims, door linings, pillar garnishes, consoles, door pockets, ventilators, ducts, air conditioners, instrument visors, instrument panel upper garnishes, instrument panel garnishes, A / T indicators, on / off switches (slide parts, Slide plate), grill front defroster, grill side defroster, lid cluster, cover intro, masks (mask switch, mask radio, etc.), glove box, pockets (pocket deck, pocket card, etc.), steering wheel horn pad, switch Examples include parts and exterior parts for car navigation. Among them, it can be particularly suitably used as a ventilator for automobiles, plate blades 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 caused by contacting and rubbing with other parts by, for example, vibration during equipment operation and opening / closing of the desk drawer. Such office equipment parts 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 parts can greatly reduce the squeaking noise generated by contacting and rubbing with other parts, for example, by opening and closing doors and sliding doors. Such residential 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 greatly reduce the squeaking noise generated by contacting and rubbing with other parts due to, for example, 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.

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

(1) Evaluation method:
(1-1) Iodine value The iodine value was measured by an infrared absorption spectrum method.
(1-2) Mooney viscosity Measured according to JIS K6300 under the conditions of a measurement temperature of 100 ° C., a preheating of 1 minute, and a measurement of 4 minutes.
(1-3) Tensile strength (T _S ) and elongation at break (E _B )
In accordance with JIS K6251, a No. 3 type test piece was used, and the tensile strength T _S (MPa) and the elongation at break E _B (%) were measured under the conditions of a measurement temperature of 25 ° C. and a tensile speed of 500 mm / min.
(1-4) Hardness (Type A durometer)
The measurement was performed according to JIS K6253.
(1-5) Graft rate It measured using the said method.
(1-6) Intrinsic viscosity It was measured using the above method.
(1-7) Measurement of free rubber content Thermoplastic resin composition [X] (Here, the amount of rubber in the thermoplastic resin composition (X) component is W1 grams. The amount of rubber is calculated from the compounding recipe, Can be obtained by IR analysis etc.) using a Soxhlet extractor and refluxing cyclohexane for 8 hours under normal pressure. The cyclohexane solution is dried and the weight of the extract is measured (W2 grams), and the dissolved amount of hot cyclohexane (free rubber content) is calculated by the following formula.
Free rubber content (%) = W2 / W1 × 100
(1-8) Itching sound evaluation I (abnormal noise risk value):
Each thermoplastic resin composition [X] shown in Table 3 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 IS170FA injection molding machine manufactured by Toshiba Machine. After cutting a large and small test piece 60 mm long, 100 mm wide, 4 mm thick, 50 mm long, 25 mm wide, 4 mm thick from a 4 mm thick injection molded plate with a disc saw and chamfering the edge with sandpaper of count # 100 Fine burrs are removed with a cutter knife, and two large and small plates are prepared as test pieces for contact parts. The two large and small test pieces were held in an oven adjusted to 80 ° C. ± 5 ° C. for 400 hours, cooled at 25 ° C. for 24 hours, and then fixed to a stick slip tester SSP-002 manufactured by ZIEGLER, with a load of 5N and 40N. The noise risk value is measured by rubbing three times under the conditions of speeds of 1 mm / sec and 10 mm / sec and an amplitude of 20 mm, and the highest value is defined as the noise risk value. The abnormal noise risk value shown in 10 steps increases as the value increases. The results are shown in Table 3.
○: Highest abnormal noise risk value under the tested conditions 1-3
Δ: Highest abnormal noise risk value under the tested condition 4-5
X: Highest abnormal noise risk value under tested conditions 6 to 10

(1-9) Itching Sound Evaluation II (Practical Evaluation):
Each thermoplastic resin composition [X] shown in Table 3 was injection-molded with 10 ISO dumbbell test pieces, each using an injection molding machine “J-100E” (model name) manufactured by Nippon Steel Co., Ltd. These test pieces were left in a gear oven at 80 ° C. for 400 hours. Next, 10 ISO dumbbell test pieces, which are contact parts, were overlapped to form a structure, and the both ends were twisted by hand to evaluate the state of generation of squeaking noise. Evaluation was performed 5 times, and determination was performed based on the following evaluation criteria. The results are shown in Table 3.
Evaluation of squeaking noise reduction effect:
○: In all five evaluations, the occurrence of itching was slight.
(Triangle | delta): The case where generation | occurrence | production of a stagnation sound was remarkable in 5 times evaluation was contained 1 time or more and less than 5 times.
X: In all five evaluations, the generation of itching sound was significant.

(1-10) Evaluation of Molding Appearance Each of the thermoplastic resin compositions [X] shown in Table 3 is a disk-shaped test having a diameter of 80 mm and a thickness of 2 mm having a center pin gate having a diameter of 1 mm using an EC40 injection molding machine manufactured by Toshiba Machine. Five pieces of each piece were injection molded. The injection molding conditions were a cylinder temperature of 250 ° C., an injection pressure of 80 MPa, and a mold temperature of 60 ° C. 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 3.
○: No molding defect occurred in all of the five test pieces.
X: A molding defect occurred in one or more of the five test pieces.

(1-11) Charpy impact strength Measured according to JIS K 7111. The results are shown in Table 3.

(2-1) Component [a1] Ethylene / α-olefin rubbery polymer:
As shown in Table 1, ethylene / α-olefin rubbery polymers [a1] (EP-1 to EP-6) were produced.

EP-1
After adding 60 mmol methylaluminoxane in terms of aluminum atoms dissolved in 8 L of toluene and 40 ml of toluene in a nitrogen-substituted 20 L autoclave and raising the temperature to 40 ° C., ethylene was 3.2 L / hour and propylene was 2.0 L / hour. Continuously fed.
Then, 12 μmol of dicyclopentadienylzirconium dichloride dissolved in 12 ml of toluene was added to initiate polymerization.
During the reaction, the temperature was kept at 40 ° C., and the reaction was continued for 20 minutes while continuously supplying ethylene and propylene. Thereafter, methanol was added to stop the reaction, and a crumb-like rubbery polymer (EP-1) was obtained by steam distillation.

EP-2
After adding 60 mmol methylaluminoxane in terms of aluminum atoms dissolved in 8 L of toluene and 40 ml of toluene in a nitrogen-substituted 20 L autoclave and raising the temperature to 40 ° C., ethylene was 3.1 L / hour and propylene was 2.1 L / hour. Continuously fed.
Then, 12 μmol of dicyclopentadienylzirconium dichloride dissolved in 12 ml of toluene was added to initiate polymerization.
During the reaction, the temperature was kept at 40 ° C., and the reaction was continued for 20 minutes while continuously supplying ethylene and propylene. Thereafter, methanol was added to stop the reaction, and a crumb-like rubbery polymer (EP-2) was obtained by steam distillation.

EP-3
Copolymerization was performed using a continuous polymerization apparatus having an internal volume of 5 L. In a polymerization vessel sufficiently substituted with nitrogen gas, ethyl sesquialuminum chloride 15 mmol / hour, oxyvanadium trichloride 1 mol / hour, n-hexane 4 L / hour, propylene 2.5 L / minute, ethylene 5 L / minute, hydrogen 0 It was continuously supplied at a flow rate of 0.05 L / min, maintained at a temperature of 35 ° C., and a pressure of 0.5 MPaG. During the polymerization, the reaction product was continuously withdrawn so that the content of the polymerization vessel was maintained at 2.5 L. The copolymer thus obtained is quenched with isopropyl alcohol, solidified with an alcohol containing an antioxidant, and dried with a hot roll at 100 ° C. to obtain a rubbery polymer (EP-3). Got.

EP-4
In a polymerization vessel sufficiently substituted with nitrogen gas, ethyl sesquialuminum chloride 15 mmol / hour, oxyvanadium trichloride 1 mol / hour, n-hexane 4 L / hour, propylene 4.9 L / minute, ethylene 2.25 L / minute, A rubbery polymer (EP-4) was obtained in the same manner as EP-3 except that hydrogen was continuously supplied at a flow rate of 0.5 L / min.

EP-5
In a polymerization vessel sufficiently substituted with nitrogen gas, ethyl sesquialuminum chloride 15 mmol / hour, oxyvanadium trichloride 1 mol / hour, n-hexane 4 L / hour, propylene 2.5 L / minute, ethylene 5 L / minute, hydrogen 0 A rubbery polymer (EP-5) was obtained in the same manner as EP-3, except that it was continuously supplied at a flow rate of 0.05 L / min and dicyclopentadiene 25 mmol / hour.

EP-6
In a polymerization vessel sufficiently substituted with nitrogen gas, ethyl sesquialuminum chloride 15 mmol / hour, oxyvanadium trichloride 1 mol / hour, n-hexane 4 L / hour, propylene 2.5 L / minute, ethylene 5 L / minute, hydrogen 0 A rubbery polymer (EP-6) was obtained in the same manner as EP-3, except that it was continuously supplied at a flow rate of 0.05 L / min and further ethylidene nylbornene 25 mmol / hr.

(2-2) Component [A] Rubber-reinforced vinyl resin:
As shown in Table 2, using the ethylene / α-olefin rubbery polymer [a1] (EP-1 to EP-6) of Table 1, rubber-reinforced vinyl resin [A] (AES-1 to AES-) 9) was produced. Further, a rubber reinforced vinyl resin (ABS-1) using a butadiene rubber polymer (PBD) [a2] was produced.
AES-1
In a 20 liter stainless steel autoclave equipped with a ribbon-type stirrer blade, an auxiliary agent continuous addition device, a thermometer, etc., 22 parts of an ethylene / α-olefin rubber polymer [EP-1], 55 parts of styrene, acrylonitrile 23 Part, 0.5 part of t-dodecyl mercaptan and 110 parts of toluene, the internal temperature was raised to 75 ° C., and the contents of the autoclave were stirred for 1 hour to obtain a homogeneous solution. Thereafter, 0.5 part of t-butylperoxyisopropyl monocarbonate was added, the internal temperature was further raised, and after reaching 100 ° C., the polymerization reaction was carried out at a stirring speed of 100 rpm while maintaining this temperature. went. From 4 hours after the start of the polymerization reaction, the internal temperature was raised to 120 ° C., and the reaction was further continued for 2 hours while maintaining this temperature to complete the polymerization reaction. Thereafter, the internal temperature was cooled to 100 ° C., and 0.2 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 mmφ vent (cylinder temperature 220 ° C., degree of vacuum) 760 mmHg) was used to substantially degas the volatiles and pelletize.

AES-2
AES-2 was produced in the same manner as AES-1, except that 25 parts of ethylene / α-olefin rubbery polymer [EP-1], 53 parts of styrene and 22 parts of acrylonitrile were used.

AES-3
AES-3 was produced in the same manner as AES-1, except that [EP-2] was used instead of the ethylene / α-olefin rubbery polymer [EP-1].

AES-4
AES-4 was produced in the same manner as AES-1 except that [EP-3] was used in place of the ethylene / α-olefin rubbery polymer [EP-1].

AES-5
AES-5 was produced in the same manner as AES-1, except that [EP-4] was used instead of the ethylene / α-olefin rubbery polymer [EP-1].

AES-6
AES-6 was produced in the same manner as AES-1 except that [EP-5] was used instead of the ethylene / α-olefin rubbery polymer [EP-1].

AES-7
AES-7 was produced in the same manner as AES-1, except that 30 parts of ethylene / α-olefin rubbery polymer [EP-5], 45 parts of styrene, 25 parts of acrylonitrile and 140 parts of toluene were used.

AES-8
AES-8 was produced in the same manner as AES-1, except that [EP-6] was used in place of the ethylene / α-olefin rubbery polymer [EP-1].

AES-9
In a 20 liter stainless steel autoclave equipped with a ribbon-type stirrer blade, an auxiliary agent continuous addition device, a thermometer, etc., 22 parts of an ethylene / α-olefin rubber polymer [EP-1], 55 parts of styrene, acrylonitrile 23 Part, 0.5 part of t-dodecyl mercaptan and 110 parts of toluene, the internal temperature was raised to 75 ° C., and the contents of the autoclave were stirred for 1 hour to obtain a homogeneous solution. Thereafter, 0.05 part of t-butylperoxyisopropyl monocarbonate was added, the internal temperature was further raised, and after reaching 85 ° C., the polymerization reaction was carried out at a stirring speed of 100 rpm while maintaining this temperature. went. While maintaining this temperature, the reaction was carried out for 6 hours to complete the polymerization reaction. Then, 0.2 parts of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenol) -propionate, dimethyl silicone oil; KF-96-100 cSt (trade name: manufactured by Shin-Etsu Silicone Co., Ltd.) After adding 02 parts, the reaction mixture was extracted from the autoclave, unreacted substances and the solvent were distilled off by steam distillation, and the volatile matter was substantially removed using a 40 mmφ vented extruder (cylinder temperature 220 ° C., vacuum degree 760 mmHg). Was degassed and pelletized.

ABS-1
In a polymerizer with a stirrer, 280 parts of water and diene rubber polymer [a2], 60 parts of polybutadiene latex having a weight average particle diameter of 0.26 μm and a gel fraction of 90% (in terms of solid content), sodium formaldehyde sulfoxylate 0.3 parts, 0.0025 parts of ferrous sulfate and 0.01 parts of disodium ethylenediaminetetraacetate were added, and after deoxidation, the mixture was heated to 60 ° C. with stirring in a nitrogen stream, and then 10 parts of acrylonitrile and 30 parts of styrene. Part, t-dodecyl mercaptan 0.2 part, and a monomer mixture consisting of cumene hydroperoxide 0.3 part were continuously added dropwise at 60 ° C. over 5 hours. After completion of the dropwise addition, the polymerization temperature was set to 65 ° C. and stirring was continued for 1 hour, and then the polymerization was terminated to obtain a latex of a graft copolymer. The polymerization conversion rate was 98%. Thereafter, 0.2 part of 2,2′-methylene-bis (4-ethylene-6-tert-butylphenol) is added to the obtained latex, and calcium chloride is added to coagulate, washing, filtering and drying steps. After that, a powdery resin composition was obtained. This component [ABS-1] had an intrinsic viscosity of 0.38 dl / g and a free rubber content of 0%.

(2-3) Component [B] Copolymer:
Copolymers [B] shown in Table 3 were produced.
Copolymer [B]
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%.
Next, 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. In the second reactor, polymerization was performed at 130 ° C. for 2 hours, and the polymerization conversion after 2 hours was 74%.
Thereafter, 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].
The intrinsic viscosity [η] of this component [B] (in methyl ethyl ketone, 30 ° C.) was 0.60 dl / g.

(2-4) Component [C] additive:
C-1: Ethylene bis-stearic acid amide; Kao wax EB-P (trade name: manufactured by Kao Corporation)
C-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)
C-3: Bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite; ADK STAB PEP-24G (trade name: manufactured by ADEKA Corporation)

Examples 1-3 and Comparative Examples 1-8
After mixing the above components [A] to [C] with a Henschel mixer at the blending ratio shown in Table 3, they were melt-kneaded with a twin-screw extruder (manufactured by Nippon Steel Works, TEX44α, barrel setting temperature 250 ° C.), The thermoplastic resin composition [X] was obtained by pelletizing.
With respect to the obtained thermoplastic resin composition [X], various physical properties, squeaking noise, molded appearance, and Charpy impact strength were evaluated by the methods described above. The evaluation results are shown in Table 3.

As shown in Table 3, each of the thermoplastic resin compositions [X] shown in Examples 1 to 3 is excellent in the squeaking noise reduction effect, and has a good molded appearance and impact strength.
On the other hand, Comparative Example 1 is an example in which the Mooney viscosity of component [a1] is higher than the range of the present invention. Moreover, the effect of reducing itchiness is insufficient.
Comparative Example 2 is an example in which the tensile strength and hardness of component [a1] are lower than the range of the present invention, but it is inferior in the effect of reducing squeaking noise.
Comparative Examples 3 and 4 are examples in which the tensile strength of the component [a1] is higher than the range of the present invention and the elongation at break is lower than the range of the present invention, but is inferior in the effect of reducing squeaking noise.
Comparative Example 5 is an example in which the tensile strength of the component [a1] is higher than the range of the present invention, but is inferior in the effect of reducing the squeaking noise.
Comparative Example 6 is an example in which the content of free rubber in the rubber-reinforced vinyl resin [A] is larger than the range of the present invention, but is inferior in the squeaking noise reduction effect and impact resistance. Further, silver streaks and peeling occur on the surface of the molded product, and the molded appearance is poor.
Comparative Example 7 is an example in which the content of the component [a1] is less than the range of the present invention, but is inferior in the effect of reducing squeaking noise.
Comparative Example 8 is an example in which the component [a1] uses a polybutadiene rubber other than the ethylene / α-olefin rubber, but is inferior in the effect of reducing the squeaking noise.

  As is clear from the above, the thermoplastic resin composition of the present invention is suitable for automotive parts, office equipment, residential parts, household appliance parts, etc. having parts to be contacted, joined and fitted to each other. I understand that.

  The thermoplastic resin composition for reducing squeaking noise according to the present invention 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 composed of contact parts that are maintained without being damaged, and have excellent impact resistance, parts for automobiles, office equipment, and housings having parts where the parts contact, join, and fit with each other. It can be suitably used for parts for home use, parts for home appliances and the like.

M Object V Drive speed μs Coefficient of static friction at the top of the sawtooth waveform μl Coefficient of friction at the bottom of the sawtooth waveform Δμ μs−μl

Claims (14)

Rubber-reinforced vinyl resin [A] obtained by polymerizing vinyl monomer [b1] containing aromatic vinyl compound and vinyl cyanide compound in the presence of ethylene / α-olefin rubber polymer [a1] A thermoplastic resin composition [X] comprising
The content of the ethylene / α-olefin rubber polymer [a1] is 5 to 30% by mass with respect to 100% by mass of the thermoplastic resin composition [X],
The crystallinity of the ethylene / α-olefin rubbery polymer [a1] is 1 to 20%,
The ethylene / α-olefin rubbery polymer [a1] has a tensile strength (T _S ) of 0.5 to 7 MPa, an elongation at break (E _B ) of 500% or more, and a hardness (type A durometer) of 40 to 40. 85, Mooney viscosity (ML _{1 + 4} , ₁₀₀ ° C.) is 5 to 60,
The free rubber content of the ethylene / α-olefin rubber polymer [a1] in which the vinyl monomer [b1] in the thermoplastic resin composition [X] is not polymerized is 1 to 30% by mass. A thermoplastic resin composition for reducing squeaking noise, which is characterized in that it exists.   The thermoplastic resin composition for reducing squeaking noise according to claim 1, wherein the Tm (melting point) of the ethylene / α-olefin rubbery polymer [a1] is 0 ° C or higher.   The content of the ethylene / α-olefin-based rubbery polymer [a1] is 5 to 20% by mass with respect to 100% by mass of the thermoplastic resin composition [X]. The thermoplastic resin composition for reducing squeaking noises as described.   The thermoplastic resin composition for reducing squeaking noise according to any one of claims 1 to 3, wherein the graft ratio of the rubber-reinforced vinyl resin [A] is 30 to 70 mass%.   The thermoplastic resin composition for reducing squeaking noise according to any one of claims 1 to 4, wherein the content of free rubber in the thermoplastic resin composition [X] is 2 to 20% by mass. A thermoplastic resin composition [X] polymerizes a vinyl monomer [b1] containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of an ethylene / α-olefin rubber polymer [a1]. It comprises a rubber-reinforced vinyl resin [A1] obtained and a (co) polymer [B] of a vinyl monomer [b2] containing an aromatic vinyl compound and a vinyl cyanide compound. The thermoplastic resin composition for reducing squeaking noise according to any one of claims 1 to 5.   The thermoplastic resin composition for reducing squeaking noise according to any one of claims 1 to 6, wherein the ethylene / α-olefin rubbery polymer [a1] is an ethylene / propylene copolymer. .   The ethylene / α-olefin rubbery polymer [a1] is composed of 5 to 95% by mass of ethylene and 95 to 5% by mass of α-olefin (however, the total of ethylene and α-olefin is 100% by mass). The thermoplastic resin composition for reducing stagnation noise according to any one of claims 1 to 7.   The rubber-reinforced vinyl resin [A1] is 10 to 90% by mass, and the (co) polymer [B] is 10 to 90% by mass (however, the total of both is 100% by mass). The thermoplastic resin composition for reducing squeaking noise as described in 1.   A contact component comprising the thermoplastic resin composition [X] according to any one of claims 1 to 9. The contact part according to claim 10, wherein an abnormal noise risk value of the contact part measured under the following conditions is 5 or less.
〔Measurement condition〕
From an injection-molded plate 150mm long, 100mm wide, 4mm thick, injection-molded at a cylinder temperature of 250 ° C, an injection pressure of 50MPa, and a mold temperature of 60 ° C using a Toshiba Machine IS170FA injection molding machine. Cut out a large and small test piece of 4mm in length, 50mm in length, 25mm in width and 4mm in thickness with a disc saw, chamfer the end with sandpaper of count # 100, and remove fine burrs with a cutter knife. Prepare the plate as a test piece for the contact part. The two large and small test pieces are held in an oven adjusted to 80 ° C. ± 5 ° C. for 400 hours, cooled at 25 ° C. for 24 hours, and then fixed to a stick slip tester SSP-002 manufactured by ZIEGLER, with a load of 40 N and a speed. The abnormal noise risk value is measured by rubbing three times under the conditions of 10 mm / second and an amplitude of 20 mm, and the highest value is defined as the abnormal noise risk value.   A structure including at least two contact parts, wherein the at least two contact parts include the contact parts according to claim 10 or 11.   All the parts for contact consist of parts for contact of Claim 10 or 11, The squeaking sound reduction structure characterized by the above-mentioned.   14. The squeaking noise reducing structure according to claim 12 or 13, wherein the structure is an automobile part, an office equipment part, a house part, or a home appliance part.

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