JP6357030B2 - Thermoplastic resin composition and molded article thereof - Google Patents

Description

  The present invention is a thermoplastic resin composition comprising an alloy of a polycarbonate resin and a rubber-reinforced aromatic vinyl resin, and problems such as squeaking are suppressed even when used for a long time under high temperature and high humidity. , It relates to a material excellent in moisture and heat aging resistance.

  Rubber-reinforced aromatic vinyl resin, represented by ABS resin, is a material with excellent mechanical strength and moldability, but it can be used for materials such as automobile parts and OA parts that require heat resistance and high impact resistance. There are cases where heat resistance and impact resistance are insufficient to use, and its use is limited. Polycarbonate resins, on the other hand, have excellent heat resistance and impact resistance, so they are used in a wide range of fields such as automotive parts, electrical / electronic parts, and precision machine parts. However, moldability may be insufficient. , Its use is limited.

  As a method for compensating for these disadvantages, it is known that a polycarbonate resin and an ABS resin are blended to form a polymer alloy (PC / ABS alloy). By this method, the moldability, which was sometimes insufficient with the polycarbonate resin, was improved, and the heat resistance and impact resistance, which were sometimes insufficient with the ABS resin, were improved. As a result, the obtained PC / ABS alloy is excellent in moldability, impact resistance, mechanical strength and heat resistance. Housing materials for OA equipment such as electrical products, computers and word processors, automotive components, furniture components such as office furniture, residential components, etc. Widely used.

  On the other hand, a molded product made of PC / ABS alloy may generate a squeaking noise when the molded products contact each other. In order to reduce this squeaking noise, the ABS resin component of the PC / ABS alloy is added to AES. It is conventionally known to substitute with a resin (see Patent Document 1).

  This squeaking noise is known as an abnormal noise caused by a stick-slip phenomenon that occurs when two objects rub against each other, and is a property different from the sliding property of the resin. As shown in FIG. 13, the stick-slip phenomenon is understood as a phenomenon in which the frictional force periodically fluctuates greatly, and more specifically occurs as shown in FIG. That is, as shown in the model of FIG. 14A, when an object M connected by a spring is placed on a driving table that moves at a driving speed V, the object M first moves at the driving speed V by the action of a static frictional force. It moves to the right as shown in FIG. 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. 14C 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. 14 (d)). This is called a stick-slip phenomenon. As shown in FIG. 13, it is said that if the difference Δμ between the static friction coefficient μs and the friction coefficient μl at the lower end of the sawtooth waveform is large, a squeaking noise is likely to occur. The dynamic friction coefficient is an intermediate value between μs and μl. Therefore, even if the absolute value of the static friction coefficient is small, if Δμ is large, a squeaking noise is likely to occur. These squeaking noises are a major cause of impairing the comfort and quietness in automobiles, offices, and residential rooms, and there is a strong demand for reducing squeaking noises.

Known methods for producing rubber-reinforced aromatic vinyl resins such as ABS resins and AES resins used in PC / ABS alloys include emulsion polymerization, solution polymerization, bulk polymerization, and suspension polymerization. High rubber component content and high design freedom, excellent appearance of molded products, rubber component deterioration due to excessive heat deterioration, low coloration, and small lot single product production It is desired to use a product produced by emulsion polymerization because it can be used.
However, as described above, a molded product obtained from a resin obtained by replacing the ABS resin of PC / ABS alloy with an AES resin produced by emulsion polymerization has a high effect of suppressing squeaking noise immediately after molding or under high temperature and high humidity. When used for a long time, it has been found that problems such as squeaking may occur.

  Conventionally, it has been reported that wet heat aging resistance can be improved by reducing the amount of residual alkali metal or residual emulsifier of PC / ABS alloy (Patent Document 2 and Patent Document 3). No mention is made of solving the problem of wet heat aging resistance in the case of replacing AES resin with AES resin, in particular, the generation of squeaking noise after wet heat aging.

JP 2012-046669 A JP-A-11-130954 JP 2006-169461 A

  In view of such a situation, the present invention is a thermoplastic resin composition obtained by replacing the ABS resin of PC / ABS alloy with an AES resin obtained by emulsion polymerization, and it can be used even when used for a long time under high temperature and high humidity. An object of the present invention is to provide a resin that suppresses problems such as the generation of sound and gives a molded article excellent in wet heat aging resistance.

  As a result of intensive studies to solve the above problems, the present inventor, in the thermoplastic resin composition (X) comprising the polycarbonate resin (A) and the rubber-reinforced aromatic vinyl resin (B), When the component (B) contains a rubber-reinforced aromatic vinyl resin (B1) obtained by emulsion polymerization, which contains an ethylene / α-olefin rubber (b1) as a rubber component, the composition (X) The inventors have found that the above problems can be solved by making the total amount of alkali metal and alkaline earth metal contained therein constant or less, and have completed the present invention.

Thus, according to one aspect, the present invention is a thermoplastic resin composition (X) comprising a polycarbonate resin (A) and a rubber-reinforced aromatic vinyl resin (B), wherein the component (B) ) Includes the following component (B1), and the total amount of alkali metal and alkaline earth metal contained in the composition (X) is 200 ppm or less.
Component (B1): A rubber-reinforced aromatic vinyl resin obtained by emulsion polymerization containing ethylene / α-olefin rubber (b1) as a rubber component.

Moreover, this invention provides the molded article which consists of a thermoplastic resin composition of the said invention according to another situation.
Since the thermoplastic resin composition of the present invention can suppress the occurrence of squeaking noise in molded products even when used under high temperature and high humidity for a long time, the molding material for articles having parts that contact each other by fitting or the like Useful as.

  Therefore, according to still another aspect of the present invention, there is provided an article comprising at least two parts that are in contact with each other, wherein at least one of the parts comprises the molded article of the present invention. provide.

  According to the present invention, in the thermoplastic resin composition (X) comprising the polycarbonate resin (A) and the rubber-reinforced aromatic vinyl resin (B), the component (B) is ethylene. When the rubber-reinforced aromatic vinyl resin (B1) obtained by emulsion polymerization containing the α-olefin rubber (b1) is included, the total amount of alkali metal and alkaline earth metal contained in the composition is Since it is set to 200 ppm or less, hydrolysis of the polycarbonate-based resin is suppressed, and generation of a squeaking noise can be suppressed even when a molded product molded from the resin composition is used for a long time under high temperature and high humidity. .

It is sectional drawing which shows the one aspect | mode of the contact part of the articles | goods of this invention. It is sectional drawing which shows the other one aspect | mode of the contact part of the articles | goods of this invention. It is sectional drawing which shows the other one aspect | mode of the contact part of the articles | goods of this invention. It is sectional drawing which shows the other one aspect | mode of the contact part of the articles | goods of this invention. It is sectional drawing which shows the other one aspect | mode of the contact part of the articles | goods of this invention. It is sectional drawing which shows the other one aspect | mode of the contact part of the articles | goods of this invention. It is a schematic perspective view which shows the component 20 of the article | item of FIG. (A) is a top view which shows an example of the article | item of this invention which consists of the components 10 and the components 20 which mutually fit, (B) is a right view of (A), (C) is (A). It is AA 'sectional drawing. It is a figure similar to FIG. 8 which shows the modification of the article | item of this invention shown in FIG. It is a figure similar to FIG. 8 which shows the other modification of the article | item of this invention shown in FIG. 8, and the unit of the dimension shown in a figure is mm. It is a schematic perspective view which shows the component 18 of the article | item of this invention shown in FIG. (A) is a top view showing an example of an article of the present invention comprising a part 18 and a frame-like part 28 that supports the part 18 so as to be rotatable around an axis 19, and (B) is a right side of (A). (C) is AA 'sectional drawing of (A). FIG. 13 is an explanatory diagram of the stick-slip phenomenon. 14A, 14B, 14C, and 14D are model diagrams of the stick-slip phenomenon.

  The present invention will be described in detail below. In the present invention, “(co) polymerization” means homopolymerization and / or copolymerization, “(meth) acryl” means acryl and / or methacryl, and “(meth) acrylate” Acrylate and / or methacrylate.

1. Thermoplastic resin (X)
The thermoplastic resin (X) used in the present invention contains the polycarbonate resin (A) and the rubber-reinforced aromatic vinyl resin (B) as essential components, and the rubber-reinforced aromatic vinyl resin (B) A rubber-reinforced aromatic vinyl resin (B1) obtained by emulsion polymerization, which contains ethylene / α-olefin rubber (b1) as a rubber component, is contained as an essential component.
Hereinafter, the said resin component which comprises this thermoplastic resin (X) is explained in full detail.

1-1. Polycarbonate resin (A)
As described above, the thermoplastic resin (X) used in the present invention can contain the polycarbonate resin (A). In the present invention, the polycarbonate resin (A) is not particularly limited as long as it has a carbonate bond in the main chain, and examples thereof include aromatic polycarbonate, aliphatic polycarbonate, and aliphatic-aromatic polycarbonate. You may use these individually or in combination of 2 or more types. Among these, aromatic polycarbonate is preferable from the viewpoint of impact resistance, heat resistance, and the like. In addition, these polycarbonate resins may have a terminal modified with an R—CO— group and an R′—O—CO— group (R and R ′ each represents an organic group).

  Examples of the aromatic polycarbonate include those obtained by transesterification (transesterification reaction) of an aromatic dihydroxy compound and a carbonic acid diester, those obtained by an interfacial polycondensation method using phosgene, and a reaction product of pyridine and phosgene. What was obtained by the pyridine method using a thing can be used.

  The aromatic dihydroxy compound may be a compound having two hydroxyl groups in the molecule.

  Of the aromatic dihydroxy compounds, compounds having a hydrocarbon group between two benzene rings are preferred. In this compound, the hydrocarbon group may be a halogen-substituted hydrocarbon group. Further, the benzene ring may be one in which a hydrogen atom contained in the benzene ring is substituted with a halogen atom. Therefore, the above compounds include bisphenol A, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl-3-methylphenyl) propane, 2,2 -Bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) methane, 1,1-bis ( p-hydroxyphenyl) ethane, 2,2-bis (p-hydroxyphenyl) butane and the like. These can be used alone or in combination of two or more. Of these, bisphenol A is particularly preferable.

  Examples of the carbonic acid diester used for obtaining the aromatic polycarbonate by transesterification include dimethyl carbonate, diethyl carbonate, di-tert-butyl carbonate, diphenyl carbonate, and ditolyl carbonate. These can be used alone or in combination of two or more.

  The viscosity average molecular weight of the polycarbonate resin (A) is preferably 15,000 to 40,000, more preferably 17,000 to 30,000, and particularly preferably 18,000 to 28,000. The higher the viscosity average molecular weight, the higher the impact resistance. On the other hand, the fluidity is not sufficient and the molding processability may be insufficient. In addition, as long as the viscosity average molecular weight as a whole falls in the above range, two or more kinds of polycarbonate resins having different viscosity average molecular weights may be mixed and used.

1-2. Rubber reinforced aromatic vinyl resin (B)
In the present invention, examples of the rubber-reinforced aromatic vinyl resin (B) include aromatic vinyl resins having improved mechanical strength such as impact resistance by containing dispersed particles of rubber. Specific examples of the rubber-reinforced aromatic vinyl resin (B) include a rubber-reinforced aromatic vinyl graft resin (B-1) dispersed in the aromatic vinyl copolymer resin (B-2). Can be mentioned.
The rubber-reinforced aromatic vinyl resin (B) is a rubber obtained by emulsion polymerization containing the component (B1) (that is, the ethylene / α-olefin rubber (b1) as a rubber component as described in detail below). (Reinforced aromatic vinyl-based resin) alone or a rubber-reinforced aromatic vinyl-based resin other than the component (B1).

1-2-1. Rubber reinforced aromatic vinyl resin (B1)
The rubber-reinforced aromatic vinyl resin (B1) in the present invention is a rubber-reinforced aromatic vinyl resin obtained by emulsion polymerization, which contains an ethylene / α-olefin rubber (b1) as a rubber component.
The rubber-reinforced aromatic vinyl resin (B1) contains an aromatic vinyl monomer in the presence of a latex of a rubbery polymer (b) containing, for example, an ethylene / α-olefin rubber (b1). It can be obtained by emulsion polymerization of the vinyl monomer (a).
The rubber-reinforced aromatic vinyl resin (B1) thus obtained has a polymer formed from a structural unit derived from the vinyl monomer (a) as a rubber polymer (b) (that is, ethylene α- The rubber-reinforced aromatic vinyl-based graft resin (B1-1) graft-polymerized to the rubber component derived from the rubbery polymer (b) containing the olefin-based rubber (b1) and the rubber component was not graft-polymerized. It is obtained as a mixture mainly containing the aromatic vinyl copolymer resin (B1-2) made of the above polymer.

  As an alpha olefin which comprises the said component (b1), a C3-C20 alpha olefin is mentioned, for example, Specifically, propylene, 1-butene, 1-pentene, 1-hexene, 4- Examples include methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene, 1-eicosene and the like. These α-olefins can be used alone or in 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 in the component (b1) 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. ~ 90: 30-10. If the mass ratio of α-olefin is in the above range, the rubber elasticity of ethylene: α-olefin is sufficient, and thus the resulting thermoplastic resin composition containing the rubber-reinforced aromatic vinyl resin (B1) is molded. The molded product obtained in this way is preferable because it has sufficient impact resistance.

  Moreover, the Mooney viscosity (ML14, 100 degreeC; based on JISK6300) of the said component (b1) is 5-80 normally, Preferably it is 10-65, More preferably, it is 10-45. When the Mooney viscosity is in the above range, the rubber-reinforced aromatic vinyl resin (B1) to be obtained has sufficient fluidity, which is preferable because moldability is sufficient.

  The ethylene / α-olefin rubber (b1) used in the present invention preferably has Tm (melting point) from the viewpoint of reducing squeaking noise. 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 above Tm is preferably 0 to 120 ° C., more preferably 10 to 100 ° C., particularly preferably 20 to 80 ° C. When Tm is less than 0 ° C., molding obtained by molding the thermoplastic resin of the present invention. The effect of reducing the squeaking noise of the product may be insufficient. In the DSC measurement, those that did not clearly show the endothermic change peak were judged to have substantially no crystallinity and no Tm.

  The ethylene / α-olefin rubber (b1) having a melting point (Tm) means that the rubber has a crystalline part. If there is a crystalline part in the rubber, it is considered that the occurrence of the squeaking noise is suppressed since the occurrence of the stick-slip phenomenon is suppressed.

  Further, the glass transition temperature (Tg) of the ethylene / α-olefin rubber (b1) is preferably −20 ° C. or lower, more preferably −30 ° C. or lower, and particularly preferably −40 ° C. or lower. It is. When the glass transition temperature is −20 ° C. or less, the impact resistance of a molded product formed by molding the thermoplastic resin of the present invention is sufficient, which is preferable. 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).

  In addition to ethylene and α-olefin, the ethylene / α-olefin rubber (b1) may contain a non-conjugated diene component as another component copolymerizable therewith. Usually, the content of the non-conjugated diene component is preferably small, and more preferably an ethylene / α-olefin copolymer containing no non-conjugated diene. Examples of the non-conjugated diene component include 1,4-hexadiene, 1,5-hexadiene, 5-ethylidene-2-norbornene, and dicyclopentadiene. The blending amount of the non-conjugated diene component is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less, based on 100% by mass of ethylene and α-olefin. If the blending amount of the non-conjugated diene component exceeds 10% by mass, the crystallinity of the rubber may be lowered, and the effect of reducing the squeaking noise may not be sufficient. The ethylene / α-olefin rubber (b1) is preferably an ethylene / propylene copolymer, an ethylene / 1-butene copolymer, or an ethylene / 1-octene copolymer, and more preferably an ethylene / propylene copolymer.

  The weight average molecular weight of the said component (b1) is 50,000-1,000,000 normally, Preferably it is 80,000-800,000, More preferably, it is 80,000-500,000. The weight average molecular weight can be typically measured by using gel permeation chromatography (GPC). When the weight average molecular weight is within the above range, the moldability of the thermoplastic resin composition of the present invention, and the impact resistance and appearance of a molded product obtained by molding it are preferable.

  The rubber polymer (b) may contain a diene rubber (b2) in addition to the component (b1). In this case, since the molded product obtained by molding the thermoplastic resin composition of the present invention becomes ductile fracture at the time of impact fracture even under a very low temperature environment such as −30 ° C., the heat of the present invention. The plastic resin composition is suitable as a molding material for molded articles such as automobile parts that require safety.

  Diene rubber (b2) includes homopolymers such as polybutadiene and polyisoprene; styrene / butadiene copolymer, styrene / butadiene / styrene copolymer, acrylonitrile / styrene / butadiene copolymer, acrylonitrile / butadiene copolymer Butadiene copolymers such as styrene / isoprene, styrene / isoprene / styrene copolymers, and isoprene copolymers such as acrylonitrile / styrene / isoprene copolymers. These may be random copolymers or block copolymers. The diene rubbery polymer may be a crosslinked polymer or an uncrosslinked polymer. Further, the diene rubber may be a (co) polymer obtained by hydrogenating a (co) polymer containing a unit composed of a conjugated diene compound. The hydrogenation rate with respect to the diene rubber is usually 95% or more, preferably 98% or more. These can be used alone or in combination of two or more.

  The component (B1) is a vinyl containing an aromatic vinyl compound in the presence of a latex of a rubbery polymer (b) containing an ethylene / α-olefin rubber (b1) and, optionally, a diene rubber (b2). It can be obtained by emulsion polymerization of the system monomer (a). Examples of the method for producing the latex include a method of homogenizing a molten rubber polymer in water by stirring shear force, a method of emulsion polymerization of a polymerizable monomer in the presence of an emulsifier, and the like. (See Japanese Patent Publication No. 4-30970, Japanese Patent No. 3403828, Japanese Patent Laid-Open No. 11-269206, etc.).

  As the vinyl monomer (a), an aromatic vinyl compound is used as an essential component, and preferably at least one selected from a vinyl cyanide compound and a (meth) acrylic acid ester compound is additionally used. Further, if necessary, other vinyl monomers copolymerizable with these compounds can be additionally used. Such other vinyl monomers include maleimide compounds, unsaturated acid anhydrides, carboxyl group-containing unsaturated compounds, hydroxyl group-containing unsaturated compounds, oxazoline group-containing unsaturated compounds, epoxy group-containing unsaturated compounds, and the like. These may be used alone or in combination of two or more.

  Specific examples of the aromatic vinyl compound constituting the vinyl monomer (a) include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, β-methylstyrene, ethylstyrene, p-tert- Examples include butyl styrene, vinyl toluene, vinyl xylene, and vinyl naphthalene. These compounds can be used alone or in combination of two or more. Of these, styrene and α-methylstyrene are preferred, and styrene is particularly preferred.

  Specific examples of the vinyl cyanide compound include acrylonitrile, methacrylonitrile, ethacrylonitrile, α-ethylacrylonitrile, α-isopropylacrylonitrile and the like. These compounds can be used alone or in combination of two or more. Of these, acrylonitrile is preferred. When a vinyl cyanide compound is used as a compound copolymerizable with an aromatic vinyl compound, the molded article obtained by molding the thermoplastic resin composition of the present invention is preferably excellent in chemical resistance and toughness.

  Specific examples of the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and (meth) acrylate n. -Butyl, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, hexyl (meth) acrylate, n-octyl (meth) acrylate, (meth) acrylic acid 2 -Ethylhexyl, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate and the like. These compounds can be used alone or in combination of two or more. Of these, methyl methacrylate is preferred.

  Specific examples of the maleimide compound include N-phenylmaleimide and N-cyclohexylmaleimide. These compounds can be used alone or in combination of two or more.

  Specific examples of the unsaturated acid anhydride include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. These compounds can be used alone or in combination of two or more.

  Specific examples of the carboxyl group-containing unsaturated compound include (meth) acrylic acid, ethacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, cinnamic acid and the like. These compounds can be used alone or in combination of two or more.

  Specific examples of the hydroxyl group-containing unsaturated compound include 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 (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and the like. These compounds can be used alone or in combination of two or more.

  The said vinylic monomer (a) comprises the structural unit of a component (B1-1) and a component (B1-2) after superposition | polymerization. The lower limit of the content of the structural unit derived from the aromatic vinyl compound in component (B1-1) or component (B1-2) is the same as the structural unit derived from the aromatic vinyl compound and the aromatic vinyl compound. When the total of structural units derived from the polymerizable compound is 100% by mass, it is preferably 40% by mass, more preferably 50% by mass, and still more preferably 60% by mass. The upper limit is usually 100% by mass.

  When the component (B1) includes a structural unit derived from an aromatic vinyl compound and a vinyl cyanide compound as a structural unit, the content of the structural unit derived from the aromatic vinyl compound is 100% by mass in total. In this case, it is usually 40 to 90% by mass, preferably 55 to 85% by mass, and the content of the structural unit derived from the vinyl cyanide compound is 10 to 10% when the total of both is 100% by mass. It is 60 mass%, Preferably it is 15-45 mass%.

    For the above emulsion polymerization, polymerization initiators, chain transfer agents, emulsifiers and the like that are usually used can be used. The vinyl monomer (a) may be polymerized by adding it all at once in the presence of the latex of the rubbery polymer containing the component (b1), or in small portions continuously or continuously. It may be added and polymerized. Moreover, you may superpose | polymerize by the method which combined these. Furthermore, all or part of the latex of the rubbery polymer may be added during the polymerization to polymerize.

    Examples of the polymerization initiator for the emulsion polymerization include organic peroxides such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramentane hydroperoxide, and reducing agents such as sugar-containing pyrophosphoric acid and sulfoxylate. Combined redox initiators; persulfates such as potassium persulfate; benzoyl peroxide (BPO), azobisisobutyronitrile, lauroyl peroxide, t-butylperoxylaurate, t-butylperoxymonocarbonate, etc. And the like. The polymerization initiator may be oil-soluble or water-soluble, and may be used in combination. A polymerization initiator can be used individually by 1 type or in combination of 2 or more types. The amount of the polymerization initiator used is preferably 0.1 to 1.5 parts by mass, more preferably 0.2 to 0.7 parts by mass with respect to 100 parts by mass of the total amount of monomer components. The polymerization initiator can be added to the polymerization system all at once or continuously.

    Examples of the chain transfer agent include mercaptans such as octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexamethyl mercaptan, n-tetradecyl mercaptan, t-tetradecyl mercaptan; terpinolenes; α-methyl Examples include styrene dimers. A chain transfer agent can be used individually by 1 type or in combination of 2 or more types. The upper limit of the amount of chain transfer agent used is usually 5 parts by mass or less, preferably 3 parts by mass with respect to 100 parts by mass of the total amount of monomer components. The chain transfer agent can be added to the reaction system all at once or continuously.

    Examples of the emulsifier include anionic surfactants and nonionic surfactants. Examples of anionic surfactants include sulfates of higher alcohols; alkylbenzene sulfonates such as dodecylbenzene sulfonic acid; fatty acid sulfonates such as sodium lauryl sulfate; higher aliphatic sulfonates and aliphatic phosphates. It is done. Examples of nonionic surfactants include polyethylene glycol alkyl ester compounds and alkyl ether compounds. An emulsifier can be used individually by 1 type or in combination of 2 or more types. The usage-amount of an emulsifier is 0.3-5 mass parts normally with respect to 100 mass parts of monomer components whole quantity.

    The emulsion polymerization can be carried out under known conditions according to the type of vinyl monomer, polymerization initiator and the like. In the latex obtained by this emulsion polymerization, the polymer component is usually recovered by coagulation, washing with water, filtration and drying. In the present invention, the alkali metal contained in the thermoplastic resin composition (X) is recovered. Further, since the total amount of alkaline earth metal needs to be 200 ppm or less, further details will be described later.

  The graft ratio of component (B1) is usually 10 to 150% by mass, preferably 15 to 120% by mass, more preferably 20 to 100% by mass, and particularly preferably 30 to 80% by mass. When the graft ratio of the component (B1) is within the above range, the impact resistance and moldability of the resin composition are further improved, which is preferable.

The graft ratio can be determined by the following mathematical formula (1).
Graft rate (mass%) = ((S−T) / T) × 100 (1)
In the above formula, 1 g of component (B1) is added to 20 ml of acetone, shaken with a shaker for 2 hours under a temperature condition of 25 ° C., and then subjected to a centrifuge (5 ° C. temperature condition). Rotational speed: 23,000 rpm) for 60 minutes, the mass (g) of insoluble matter obtained by separating the insoluble matter and the soluble matter, T is a rubber component contained in 1 gram of component (B) Mass (g). The mass of the rubber component can be obtained by a method such as a method of calculating from a polymerization prescription and a polymerization conversion rate, an infrared absorption spectrum (IR), pyrolysis gas chromatography, CHN elemental analysis and the like.

  The graft ratio is, for example, the type and amount of chain transfer agent used in emulsion polymerization of component (B1), the type and amount of polymerization initiator, the amount of monomer component added during polymerization, the method of addition, and the addition It can adjust by selecting time, superposition | polymerization temperature, etc. suitably.

  The intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) of the component (B1-2) in the rubber-reinforced aromatic vinyl resin (B1) is usually 0.1 to 1.5 dl / g, preferably 0.15 to It is 1.2 dl / g, More preferably, it is 0.15-1.0 dl / g. When the intrinsic viscosity [η] is in the above range, the molded article obtained by molding the thermoplastic resin composition of the present invention is preferably improved in impact resistance and moldability.

  The intrinsic viscosity [η] was measured by the following method. First, the acetone-soluble component of component (B1) was dissolved in methyl ethyl ketone to prepare 5 measurement samples having different concentrations. Next, the intrinsic viscosity [η] was determined from the result of measuring the reduced viscosity of the measurement sample at each concentration at 30 ° C. using an Ubbelohde viscosity tube. The unit is dl / g.

  The intrinsic viscosity [η] is, for example, the type and amount of a chain transfer agent used in emulsion polymerization of the component (B1), the type and amount of a polymerization initiator, and the method and addition of a monomer component during polymerization It can be adjusted by appropriately selecting time, polymerization temperature, polymerization time and the like. Moreover, it can also adjust by selecting and mixing suitably 2 or more types of components (B1) from which intrinsic viscosity [(eta)] differs. The intrinsic viscosity [η] can also be adjusted by mixing an aromatic vinyl (co) polymer (B3) described later with the component (B1).

1-2-2. Rubber reinforced aromatic vinyl resin (B2)
As described above, the thermoplastic resin (X) used in the present invention may contain a rubber-reinforced aromatic vinyl resin other than the component (B1), typically a diene rubber-reinforced aromatic vinyl resin. A rubber-reinforced aromatic vinyl resin obtained by polymerizing a vinyl monomer (a) containing an aromatic vinyl monomer in the presence of a resin, that is, a latex of a diene rubber (b2) ( B2) can be contained. When the thermoplastic resin (X) contains the rubber-reinforced aromatic vinyl resin (B2), the molded product obtained by molding the thermoplastic resin composition of the present invention has a very low temperature environment such as −30 ° C. The thermoplastic resin composition of the present invention is suitable as a molding material for molded articles such as automobile parts that require safety because it undergoes ductile fracture at the time of impact fracture.

  As the diene rubber (b2) and the vinyl monomer (a) used as raw materials for the rubber-reinforced aromatic vinyl resin (B2), all of those described for the component (B1) can be used. What has been said about component (B1) applies equally to component (B2). Regarding the graft ratio and intrinsic viscosity of the rubber-reinforced aromatic vinyl resin (B2), the same applies to the component (B2) as described for the component (B1).

  The polymerization method of the rubber-reinforced aromatic vinyl resin (B2) is not particularly limited, and a known method can be applied. As a polymerization method, emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, or a combination of these can be used. In these polymerization methods, known polymerization initiators, chain transfer agents (molecular weight regulators), emulsifiers and the like can be appropriately used.

1-2-3. Aromatic vinyl (co) polymer (B3)
The rubber-reinforced aromatic vinyl resin (B) may further contain an aromatic vinyl (co) polymer (B3). The aromatic vinyl (co) polymer (B3) can be produced by polymerizing the vinyl monomer (a) containing the aromatic vinyl compound in the absence of the rubbery polymer. In addition, the polymerization method may be the same method as component (B1) and component (B2), and in addition to emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, or a combination of these may be used. it can. The aromatic vinyl-based (co) polymer (B3) has the same form as the aromatic vinyl-based copolymer resin (B1-2) in that it is not grafted to the rubbery polymer, and is usually rubber-reinforced aromatic. It is used for diluting a vinyl resin or preparing the above intrinsic viscosity [η].

  As the vinyl monomer (a) used as a raw material for the aromatic vinyl (co) polymer (B3), all of those described for the component (B1) can be used. As for the intrinsic viscosity of the aromatic vinyl-based (co) polymer (B3), the same applies to the component (B3) as to the component (B1).

1-3. Composition of thermoplastic resin (X) In the thermoplastic resin (X) of the present invention, the content of the rubber component is preferably 3 to 20% by mass with respect to 100% by mass of the component (X) from the viewpoint of mechanical strength. 4-15 mass% is more preferable, and 5-12 mass% is still more preferable. The rubber component in the thermoplastic resin (X) of the present invention is derived from a rubber-reinforced aromatic vinyl resin (B), that is, a rubbery polymer that is a raw material of the components (B1) and (B2). However, from the viewpoint of preventing squeaking noise, the total amount of the rubber component is preferably composed of ethylene / α-olefin rubber (b1). On the other hand, as described above, in the case of molded products that require safety, such as automobile parts, a diene rubber (b2) is contained as a rubber component of the component (B1) in order to impart ductile fracture characteristics, The component (B2) is included in the plastic resin (X). Thus, when component (X) contains diene rubber (b2) as a rubber component, the content of component (b1) is based on 100% by mass in total of component (b1) and component (b2). It is preferable that it is 90-15 mass%, and it is preferable that content of a component (b2) is 10-85 mass% with respect to a total of 100 mass% of a component (b1) and a component (b2). In addition, as a method of incorporating the diene rubber (b2) into the component (X), a method of mixing the latex of the component (b1) and the latex of the component (b2) at the time of emulsion polymerization, emulsification in the presence of the component (b1) A method of mixing the latex of component (B1) after polymerization and the latex of component (B2) after emulsion polymerization in the presence of component (b2), coagulation after emulsion polymerization in the presence of component (b1) And a method of mixing the component (B1) washed with water and dried with the component (B2) coagulated, washed with water and dried after emulsion polymerization in the presence of the component (b2).

  The content of the polycarbonate resin (A) in the thermoplastic resin (X) is determined according to the required mechanical strength, rigidity, molding processability, heat resistance, etc., but the content of the polycarbonate resin (A) is It is preferable that it is 30-90 mass% with respect to the total 100 mass% of the said component (A) and the said component (B), and it is more preferable that it is 40-80 mass%. The content of the component (B) is preferably 10 to 70% by mass and more preferably 20 to 60% by mass with respect to 100% by mass in total of the component (A) and the component (B). Within this range, a resin composition having sufficient performance such as impact strength, molding processability, appearance, heat resistance, etc. in addition to the effect of suppressing squeaking noise can be obtained.

In the present invention, the total amount of alkali metal and alkaline earth metal contained in the thermoplastic resin composition (X) needs to be 200 ppm or less. In order to make the total amount of alkali metal and alkaline earth metal contained in the thermoplastic resin composition (X) of the present invention 200 ppm or less, as the component (B1),
(i) using a product obtained by sufficiently washing an alkali metal or an alkaline earth metal after coagulating a latex obtained by emulsion polymerization with methanol;
(ii) using a latex obtained by mechanically coagulating or freeze-coagulating a latex obtained by emulsion polymerization and then thoroughly washing the alkali metal or alkaline earth metal;
(iii) using a product obtained by sufficiently washing an alkali metal or an alkaline earth metal after coagulating a latex obtained by emulsion polymerization with an acid and / or an inorganic salt;
(iv) using an emulsifier that does not contain an alkali metal or alkaline earth metal, for example, one obtained using a nonionic surfactant;
Such a method can be used.

  In the above (iii), as the coagulant, usually, for example, inorganic acids such as sulfuric acid, phosphoric acid and nitric acid, organic acids such as acetic acid and lactic acid, inorganic salts such as magnesium sulfate, calcium chloride, magnesium chloride and sodium chloride, etc. However, the component (B1) suitable for use in the thermoplastic resin composition (X) of the present invention is the type and amount of these coagulants and the washing of the coagulum. It is obtained by optimizing the conditions. The coagulation in (iii) is preferably coagulation using an acid and an inorganic salt or acid coagulation, and more preferably acid coagulation. When salting out using the inorganic salt alone as a coagulant in (iii) above, a corresponding metal component may remain in the final product.

The method for recovering the polymer with the acid and / or inorganic salt of the latex obtained by emulsion polymerization is not particularly limited. A method of coagulating by introducing the latex into an acidic aqueous solution or an inorganic salt aqueous solution, and a method of collecting the polymer; a method of introducing an acidic aqueous solution or an inorganic salt aqueous solution into the latex and coagulating it; A method of recovering a polymer by dividing it into two or more stages by applying a temperature gradient from low temperature to high temperature, and a solidification process from weakly acidic to strongly acidic or from acidic to weakly acidic with a gradient of acidity to two or more stages A method of collecting the polymer by coagulating separately, a method in which the latex is mixed with a coagulant aqueous solution to form a paste, and then extruding from the pores into warm water and coagulating to recover the polymer. It can also collect | recover by selecting and combining two or more types from said method.
Thereafter, the polymer can be recovered by dehydration and drying using a known method such as a centrifugal dehydrator or a fluid dryer. At this time, if necessary, various antioxidants and various stabilizers may be added to the polymer latex in advance, and these may be further emulsified and added.

  Since the alkali metals contained in the thermoplastic resin composition (X) are mainly sodium and potassium, and a small amount of lithium, rubidium, cesium, frangium and the like, the thermoplastic resin composition (X) of the present invention. The amount of alkali metal contained therein is limited to the amount of sodium and potassium. Similarly, most of the alkaline earth metals contained in the thermoplastic resin composition (X) are magnesium and calcium, and the amounts of beryllium, strontium, barium, radium, etc. are very small. The amount of alkaline earth metal contained in the product (X) is limited to the amount of magnesium and calcium.

  In the present invention, the total amount of alkali metal and alkaline earth metal contained in the thermoplastic resin composition (X) is 200 ppm or less, preferably 100 ppm or less, more preferably 50 ppm or less, particularly preferably 15 ppm or less. is there. If it is this range, even when it is used for a long time under high temperature and humidity, generation | occurrence | production of the squeaking sound of a molded article can be suppressed.

  In the present invention, the total amount of the alkaline earth metal contained in the thermoplastic resin composition (X) is preferably 200 ppm or less, more preferably 100 ppm or less, still more preferably 20 ppm or less, particularly preferably 5 ppm or less. It is. If it is this range, even when it is used for a long time under high temperature and humidity, generation | occurrence | production of the squeaking sound of a molded article can be suppressed. In particular, the calcium contained in the thermoplastic resin composition (X) is preferably 200 ppm or less, more preferably 100 ppm or less, still more preferably 20 ppm or less, even more preferably 15 ppm or less, and particularly preferably 5 ppm or less. is there. If it is this range, even when it is used for a long time under high temperature and humidity, generation | occurrence | production of the squeaking sound of a molded article can be suppressed.

  These alkali metals and alkaline earth metals contained in the thermoplastic resin composition (X) can be quantified by a known analysis method. For example, after recovering a metal by a method such as dry ashing, it can be measured using a method such as atomic emission, atomic absorption, Inductively Coupled Plasma (ICP).

2. Thermoplastic resin composition and production method thereof The thermoplastic resin composition (X) of the present invention contains various additives in addition to the above components (A) and (B) as long as the object of the present invention is not impaired. You may do it. Specific examples of additives include UV absorbers, weathering agents, fillers, antioxidants, anti-aging agents, antistatic agents, flame retardants, antifogging agents, lubricants, antibacterial agents, tackifiers, plasticizers, and coloring. Agents and the like.

  The thermoplastic resin composition (X) of the present invention is obtained by mixing the component (A) and the component (B), which are resin components, to obtain a thermoplastic resin, and then mixing other components with the thermoplastic resin. Alternatively, it may be produced, or all components may be mixed and produced, and the mixing method is not particularly limited. For example, in the thermoplastic resin composition (X) of the present invention, each component is mixed with a tumbler mixer or Henschel mixer at a predetermined blending ratio, and then a single screw extruder, twin screw extruder, Banbury mixer, kneader, roll It can be produced by melt-kneading under suitable conditions using a mixer such as a feeder 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. After kneading with a Banbury mixer, a kneader or the like, it can be pelletized 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.

3. Molded product There is no limitation on the method for producing a molded product from the thermoplastic resin composition (X) of the present invention. Examples include injection molding, injection compression molding, gas assist molding, press molding, blow molding, and profile extrusion molding. In addition, known methods such as film and sheet molding represented by calendar molding and T-die extrusion molding can be used.

  The molded article of the present invention is suitable, for example, as an electrical or electronic device, an optical device, a lighting device, an office device, a home appliance component, an automotive component, a residential component, or the like.

  The molded article molded with the thermoplastic resin composition of the present invention can be suitably used as at least one part of an article including at least two parts that are in contact with each other. In particular, since the thermoplastic resin composition (X) of the present invention contains ethylene / α-olefin rubber (b1) as a rubber component, at least one part of the article is formed as a molded product of the thermoplastic resin composition. By doing so, it is possible to suppress the occurrence of squeaking noise in the article, and it is preferable that two or more parts are molded articles of the thermoplastic resin composition of the present invention, and all the parts are of the present invention. It is particularly preferable that the molded article is a thermoplastic resin composition.

  In the thermoplastic resin composition (X) of the present invention containing ethylene / α-olefin rubber (b1) as a rubber component, at least two parts of the above-mentioned parts are always or intermittently in contact with each other. It is suitable as a molding material for an article such that when an external force such as twisting or impact is applied to the article, the contact portions of both parts slightly move or collide with each other. The contact mode of the contact portion may be any of surface contact, line contact, point contact, etc., and may be partially bonded. Specifically, as shown in FIG. 1, an article that is in contact with one surface of the component 10 and one surface of the component 20 being in contact with each other, as shown in FIGS. For example, an article that is in contact with a recess formed in the component 20 may be used.

  As a specific example of an article that is in contact with each other in a state in which the parts are fitted, as shown in FIG. 2, the one end of the part 10 is in contact with a complementary recess formed in the part 20. The article in contact with each of the two complementary recesses formed in the corners of the part 20 with each end of the part 10 fitted tightly, as shown in FIG. As shown in FIG. 4, an article in which each end of the part 20 is in close contact with a complementary recess formed in each of two parts 10 arranged substantially in parallel, FIG. As shown in FIG. 2, a part 20 having an outer surface dimension that is the same as the inner surface dimension of the part 10 is inserted into the part 10 in a nested manner, and the inner surface and the outer surface of both the parts 10 are closely fitted. For example, an article in contact.

  Further, the two parts in the article of the present invention do not need to be closely fitted to each other, and are fitted to each other with a certain amount of gap or play as shown in FIG. The article may repeat contact and non-contact with each other when the external force is applied to the article.

  An article as shown in FIG. 8 is an example of an article that is provided with a composite of the contact portions as described above. In the article shown in FIG. 8, the part 10 is a bowl-shaped part having a rectangular parallelepiped shape whose bottom is open, and the part 20 has a shape similar to that of the part 10 and has a rectangular opening formed at the center of the top surface. It is. Then, as shown in FIG. 8, the component 20 can be fitted into the component 10, and the outer peripheral surface of the component 20 and the inner peripheral surface of the component 10 are in contact with each other, and both receive external force such as vibration. Slightly deform and repeat contact and non-contact. As shown well in FIG. 7, the component 20 includes protrusions 30 on the opposite outer surfaces, and as illustrated in FIG. 8, the component 10 includes holes for receiving the protrusions 30 of the component 20 on two opposite sides. ing. When the component 10 is fitted to the component 20, the projection 30 snap-fits into the hole so that the fitting of both components is not easily removed. By molding at least one of the component 10 and the component 20 with the thermoplastic resin of the present invention, for example, even when an external force is applied in the direction of the arrow in FIG. it can. The direction of the external force is not limited to the direction shown in FIG. 8C. Even when an external force is applied from another direction, at least one of the component 10 and the component 20 is used as the thermoplastic resin of the present invention. In the case of molding with, stagnation noise is prevented. It is also possible to change the cross-sectional shape of the projection 30 and the shape of the hole of the component 10 in FIG.

  FIG. 9 is a view except that the parts 10 and 20 are bonded to each other by using an adhesive 31 in place of the protrusions 30 and the holes in which the parts 20 snap fit. 8 shows an aspect similar to that of the article 8. Further, instead of the adhesive 31, the component 10 and the component 20 can be welded to each other by laser welding or the like, and this method is convenient when both components are thermoplastic resin molded articles. In particular, in laser welding, it is preferable to combine a transparent thermoplastic resin that transmits laser light and a component made of a thermoplastic resin that absorbs laser light. Specific products include instruments such as in-vehicle speedometers, and illumination lamps. Etc.

  In the example of FIG. 10, holes are formed at opposing positions on opposite side surfaces of the component 10 and the component 20, and the two components are fixed by fastening with bolts and nuts through the two holes. Other than this, the same mode as the article of FIG. 8 is shown. The parts 10 and 20 may be fixed using screws, pins, screws, rivets, bushes, brackets, hinges, nails or the like instead of the bolts and nuts.

  Further, as shown in FIG. 11, a part 18 having a shape in which a cylindrical shaft 19 protrudes longitudinally outward from both ends of a rectangular plate-like main body, and the part 19 is inserted by inserting the shaft 19 of the part 18. An article as shown in FIG. 12 including a frame-like component 28 that is rotatably supported around the shaft 19 is also suitable for molding with the thermoplastic resin composition of the present invention. When at least one of the component 18 and the component 28 is molded with the thermoplastic resin composition of the present invention, the component 18 is rotated around the shaft 19 or an external force such as vibration is applied to the article. Can be suppressed.

  As shown in FIG. 12, when the frame-shaped component 28 includes a plurality of openings 29, the article can be suitably used as a device that adjusts the amount and direction of air flow according to the angle of the component 18. Examples of such devices include household and vehicle-mounted air conditioners, air purifiers, blowers and the like.

  In the above article, it is possible to remarkably reduce the generation of squeaking noise by forming at least one of the parts 10, 18 and the parts 20, 28 from the thermoplastic resin composition of the present invention. The other article may also be a molded article made of the thermoplastic resin composition of the present invention. When the other article is a part made of a material other than the thermoplastic resin composition of the present invention, the material is not particularly limited. For example, a thermoplastic resin, a thermosetting resin, rubber, an organic material, an inorganic material Examples thereof include materials and metal materials.

  Examples of the thermoplastic resin constituting the component made of a material other than the thermoplastic resin composition of the present invention include polyvinyl chloride, polyethylene, polypropylene, AS resin, ABS resin, AES resin, ASA resin, and polymethyl methacrylate resin. , Polystyrene resin, impact polystyrene resin, ethylene-vinyl acetate (EVA) resin, polyamide (PA) resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polycarbonate (PC) resin, polylactic acid resin, PC / ABS resin, PC / AES resin, PA / ABS resin, PA / AES resin and the like. These can be used alone or in combination of two or more.

  As said thermosetting resin which comprises components consisting of materials other than the thermoplastic resin composition of this invention, a phenol resin, an epoxy resin, a urea resin, a melamine resin, an unsaturated polyester resin etc. are mentioned, for example. These can be used alone or in combination of two or more.

  Examples of the rubber constituting the parts made of materials other than the thermoplastic resin composition of the present invention 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 constituting the component made of a material other than the thermoplastic resin composition of the present invention include, for example, insulation board, MDF (medium fiber board), hard pod, particle board, lumbar core, LVL (single plate laminate) ), OSB (orientation board), PSL (pararam), WB (wafer board), hard fiber board, soft fiber board, lumbar core plywood, board core plywood, special core plywood, veneer core veneer board, paper impregnated with tap resin Laminated sheets / plates, boards made by heating and compressing adhesives mixed with small pieces / linear bodies of crushed (old) paper, etc., and various kinds of wood. These can be used alone or in combination of two or more.

  Examples of the inorganic material constituting the component made of a material other than the thermoplastic resin composition of the present invention include, for example, calcium silicate board, flexible board, homo-cement board, gypsum board, sizing gypsum board, reinforced gypsum board, gypsum lath board. , Decorative gypsum board, composite gypsum board, various ceramics, glass and the like. These can be used alone or in combination of two or more.

  Furthermore, iron, aluminum, copper, various alloys, etc. are mentioned as said metal material which comprises components consisting of materials other than the thermoplastic resin composition of this invention. These can be used alone or in combination of two or more.

  Among these, thermosetting resins, thermosetting resins, and rubbers are preferable, and ABS resins, AES resins, PC resins, ABS resins, PC / AES resins, and polymethyl methacrylate resins are particularly preferable.

  When the article according to the present invention is formed from the thermoplastic resin composition of the present invention containing at least one of its parts as a rubber component, ethylene / α-olefin rubber, vibration, sliding, etc. Since the generation of the squeaking noise is suppressed even when the components repeatedly contact and non-contact, they can be suitably used for automotive parts, office equipment parts, residential parts, home appliance parts, and the like.

  When the automotive part is a molded article of the thermoplastic resin composition of the present invention, even if the part repeatedly contacts and non-contacts with other parts due to vibration during traveling of the vehicle, for example, a squeaking noise is generated. It is possible to greatly reduce the occurrence. In addition, when the thermoplastic resin composition of the present invention contains a diene rubber, it is particularly suitable for automotive interior parts because of its excellent fracture characteristics at low temperatures. Such automotive parts include door trim, door lining, pillar garnish, console, door pocket, ventilator, duct, air conditioner plate blade, valve shutter, louver, meter visor, instrument panel upper garnish, instrument panel garnish, A / T indicator, ON / OFF switches (slide part, slide plate), grill front defroster, grill side defroster, lid cluster, cover intro, masks (mask switch, mask radio, etc.), grope box, pockets (pocket deck, pocket) Card), steering wheel horn pad, switch parts, car navigation exterior parts, and the like. Among them, it can be particularly suitably used as a ventilator, a plate blade of an air conditioner, a valve shutter, a louver, a switch part, an exterior part for car navigation, and the like.

  When the office equipment part is a molded product of the thermoplastic resin composition of the present invention, the part repeatedly contacts and does not contact other parts due to, for example, vibration during operation of the equipment and opening / closing of the desk drawer. Even in this case, it is possible to significantly reduce the generation of stagnation noise. Examples of such office equipment parts include exterior parts, interior parts, parts around switches, parts of movable parts, desk lock parts, desk drawers, and the like.

  When a residential part is a molded product of the thermoplastic resin composition of the present invention described above, for example, when the door and the sliding door are opened and closed, even when the part and the other part repeatedly contact and non-contact, the squeak noise It is possible to greatly reduce the occurrence. Examples of such residential parts include shelf doors, chair dampers, table folding leg movable parts, door opening / closing dampers, sliding door rails, curtain rails, and the like.

  When the home appliance part is a molded product of the thermoplastic resin composition of the present invention described above, for example, even when the part and other parts are repeatedly brought into and out of contact with each other due to vibration during operation of the equipment, the squeaking noise is not generated. It is possible to greatly reduce the occurrence. Examples of such home appliance parts include exterior parts such as cases and housings, interior parts, parts around switches, parts of movable parts, and the like.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited only to a following example. In the examples, parts and% are based on mass unless otherwise specified.

1. Evaluation method
1-1. Itching sound evaluation -1 (abnormal noise risk index)
The thermoplastic resin composition shown in Table 1 was injected under the conditions of a cylinder temperature of 260 ° C., an injection pressure of 50 MPa, and a mold temperature of 60 ° C. using an injection molding machine “IS-170FA” (trade name) manufactured by Toshiba Machine. From a molded product having a length of 150 mm, a width of 100 mm and a thickness of 4 mm obtained by molding, a small test piece having a length of 50 mm, a width of 25 mm and a thickness of 4 mm was cut out with a disc saw. Next, after chamfering the end of the test piece with sandpaper of count # 100, fine burrs were removed with a cutter knife to obtain a small test piece for evaluation of stagnation.

  Instead of the thermoplastic resin composition shown in Table 1, a PC / ABS alloy “Excelloy CK20” (trade name) manufactured by Techno Polymer Co., Ltd. was used in the same manner as described above, 60 mm in length, 100 mm in width, A large test piece for evaluation of stagnation sound having a thickness of 4 mm was obtained.

  The evaluation test piece was left to stand (wet heat treatment) for 200, 300, and 400 hours in a constant temperature and humidity chamber controlled at 80 ° C. and 95% RH, and then cooled and cooled at 25 ° C. for 24 hours. Obtained. The obtained large test piece, which is a test piece for evaluation, is set on the movable side stage of a stick-slip tester SSP-02 manufactured by ZIEGLER, and the small test piece is set on a fixed side stage. The temperature is 23 ° C. and the humidity is 50%. Under the conditions of RH, load 40N, speed 10 mm / second, the noise risk index was measured when rubbing three times with an amplitude of 20 mm.

The higher the abnormal noise risk index, the more likely it is to itch. In addition, the evaluation criteria of the result of Table 1 are as follows. According to the German Automobile Manufacturers Association standard (VDA 203-260), if the abnormal noise risk index is 3 or less, the risk of squeaking is reduced, and the product is considered acceptable.
<Evaluation criteria>
○: The highest abnormal noise risk index under the tested conditions is 1-3.
(Triangle | delta): The highest abnormal noise risk index | exponent in the tested conditions is 4-5.
X: The highest abnormal noise risk index is 6 to 10 under the tested conditions.

1-2. Itching Sound Evaluation-2 (Practical Evaluation 1)
Using an injection molding machine “J-100E” (model name) manufactured by Nippon Steel Co., Ltd., five ISO dumbbell test pieces made of the thermoplastic resin composition shown in Table 1 were injection molded. The substrate was allowed to stand for 300 hours (wet heat treatment) in a constant temperature and humidity chamber controlled at 80 ° C. and 95% RH, and then cooled at 25 ° C. for 24 hours.
Next, as a part to be in contact with five ISO dumbbell test pieces made of the thermoplastic resin composition shown in Table 1, the PC / ABS alloy “Excelloy CK20” (trade name) manufactured by Techno Polymer Co., Ltd. is used. Then, after standing in a thermo-hygrostat controlled at 80 ° C. and 95% RH for 300 hours (moisture heat treatment), 5 ISO dumbbell specimens cooled at 25 ° C. for 24 hours were alternately stacked, and both ends were manually Twist to evaluate the situation of itchiness. Evaluation was performed 5 times, and determination was performed based on the following evaluation criteria.
<Evaluation of itchiness>
○: In all five evaluations, the occurrence of itching was slight.
(Triangle | delta): The case where generation | occurrence | production of a squeaking sound was remarkable was contained in five evaluations.
X: In all five evaluations, the generation of itching sound was significant.

1-3. Itching Sound Evaluation-3 (Practical Evaluation 2)
Except for using methacrylic resin “ACRYPET VH-004” (trade name) manufactured by Mitsubishi Rayon Co., Ltd. as the part to be contacted, the situation of the generation of stagnation sound is evaluated in the same manner as the stagnation sound evaluation-2. did. Evaluation was performed 5 times, and determination was performed based on the following evaluation criteria.
<Evaluation of itchiness>
○: In all five evaluations, the occurrence of itching was slight.
(Triangle | delta): The case where generation | occurrence | production of a squeaking sound was remarkable was contained in five evaluations.
X: In all five evaluations, the generation of itching sound was significant.

1-4. Itching Sound Evaluation-4 (Practical Evaluation 3)
Using an injection molding machine “J-100E” (model name) manufactured by Nippon Steel Co., Ltd., 10 ISO dumbbell specimens made of the thermoplastic resin composition shown in Table 1 were injection molded, and then the specimens were tested. Was allowed to stand for 300 hours in a thermo-hygrostat controlled at 80 ° C. and 95% RH (wet heat treatment), and then cooled at 25 ° C. for 24 hours. Ten obtained ISO dumbbell test pieces were overlapped, and both ends were twisted by hand to evaluate the state of occurrence of itching sound. Evaluation was performed 5 times, and determination was performed based on the following evaluation criteria.
<Evaluation of itchiness>
○: In all five evaluations, the occurrence of itching was slight.
(Triangle | delta): The case where generation | occurrence | production of a squeaking sound was remarkable was contained in five evaluations.
X: In all five evaluations, the generation of itching sound was significant.

1-5. Alkali Metal and Alkaline Earth Metal Content The alkali metal content and alkaline earth metal content of the thermoplastic resin compositions obtained in the following examples and comparative examples were measured based on the metal analysis ICP method. The obtained resin was dry ashed, and then analyzed by ICP-AES method using a solution obtained by dissolving the ashed product in nitric acid. The quantification was performed by preparing a calibration curve with an element standard solution with a known concentration in advance and using the calibration curve method.

2. Raw materials used
2-1. Polycarbonate resin (A)
A polycarbonate resin “Makrolon 2800” (trade name) manufactured by Bayer was used. The viscosity average molecular weight was 22.000.

2-2. Ethylene-propylene rubber reinforced aromatic vinyl resin (AES-1)
As the ethylene / α-olefin rubbery polymer (b1), ethylene / propylene / dicyclopentadiene rubber (ethylene / propylene / dicyclopentadiene = 63/32/5 (%) Mooney viscosity (ML _{1 + 4} , 100 ° C.) 33) After 100 parts were dissolved in 566 parts of n-hexane, 10 parts of acid-modified polyethylene (High Wax 2203A) manufactured by Mitsui Chemicals, Inc. was added, and 4.5 parts of oleic acid was further added and completely dissolved. Separately, 0.6 parts of ethylene glycol was added to an aqueous solution in which 0.9 parts of potassium hydroxide was dissolved in 700 parts of water, and the mixture was kept at 60 ° C., and the polymer solution prepared above was added little by little to emulsify. Stir with a mixer. Next, part of the solvent and water was distilled off to obtain a latex having a particle size of 400 to 600 nm. To this latex, 1.5 parts of divinylbenzene and 1.0 part of di-tert-butylperoxytrimethylcyclohexane are added to 100 parts of the rubber component and reacted at 120 ° C. for 1 hour to form an EPDM-containing crosslink. Latex was obtained.

  Subsequently, a 20-liter stainless steel autoclave equipped with a ribbon stirrer, auxiliary agent addition device, thermometer, etc. was purged with nitrogen, and then the EPDM latex 60 parts (solid content), ion exchange in a nitrogen stream 200 parts of water, 2 parts of potassium oleate, 0.004 part of ferrous sulfate, 0.2 part of sodium pyrophosphate and 0.2 part of dextrose were charged. Polymerization is carried out while continuously adding 2 parts of acrylonitrile, 28 parts of styrene and 0.5 part of cumene hydroperoxide as a vinyl monomer (a) at a constant temperature of 70 ° C. for 2 hours, While maintaining the polymerization temperature, the polymerization was continued for 1 hour to obtain a polymer latex. The polymer conversion rate of the obtained latex was 98%. To this latex, 0.2 part of 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) was added to complete the polymerization. The graft ratio of the obtained polymer was 35%, and the intrinsic viscosity [η] (30 ° C. in methyl ethyl ketone) of the acetone-soluble component was 0.25 dl / g.

    The obtained rubber-reinforced aromatic vinyl resin latex is poured into a large amount of methanol to precipitate, filtered through a 150 mesh stainless steel wire mesh, washed with an appropriate amount of methanol, and further washed with a large amount of pure water. Filtration and drying gave an ethylene-propylene rubber reinforced aromatic vinyl resin (AES-1).

2-3. Ethylene-propylene rubber reinforced aromatic vinyl resin (AES-2)
A rubber-reinforced aromatic vinyl-based resin latex was produced in the same manner as in 2-2 except that it was coagulated with an aqueous sulfuric acid solution, washed with water, and dried.

2-4. Ethylene-propylene rubber reinforced aromatic vinyl resin (AES-3)
A rubber-reinforced aromatic vinyl-based resin latex was produced in the same manner as in 2-2 above, except that it was coagulated, washed, filtered and dried with a coagulant aqueous solution having a molar ratio of sulfuric acid to magnesium sulfate of 1: 1.

2-5. Ethylene-propylene rubber reinforced aromatic vinyl resin (AES-4)
A rubber-reinforced aromatic vinyl-based resin latex was produced in the same manner as in the above 2-2, except that it was coagulated, washed with water, filtered and dried with an aqueous magnesium sulfate solution.

2-6. Ethylene-propylene rubber reinforced aromatic vinyl resin (AES-5)
A rubber-reinforced aromatic vinyl resin latex was produced in the same manner as in the above 2-2 except that it was coagulated, washed, filtered and dried with an aqueous calcium chloride solution.

2-7. Styrene-acrylonitrile copolymer (AS)
Two stainless steel autoclaves having a ribbon wing with an internal volume of 30 liters were connected and purged with nitrogen, and then 70 parts of styrene, 30 parts of acrylonitrile and 20 parts of toluene were continuously added to the first reaction vessel. A solution of 0.12 part of tert-dodecyl mercaptan and 5 parts of toluene as a molecular weight regulator, and 0.1 part of 1,1′-azobis (cyclohexane-1-carbonitrile) and 5 parts of toluene as a polymerization initiator Solution was continuously fed. The polymerization temperature of the first group was controlled at 110 ° C., the average residence time was 2.0 hours, and the polymerization conversion was 57%. The obtained polymer solution was continuously taken out from the first reaction vessel by the same amount as the styrene, acrylonitrile, toluene, molecular weight regulator and polymerization initiator supplied by the pump provided in the second reaction vessel. The reaction vessel was fed. The polymerization temperature of the second reaction vessel was 130 ° C., and the polymerization conversion was 75%. The copolymer solution obtained in the second reaction vessel was directly devolatilized from the unreacted monomer and solvent using a twin-screw, three-stage vented extruder, and the intrinsic viscosity [η] 0.48 dl / g of polymer was obtained.

3. Manufacture and evaluation of compacts
Examples 1 to 4, Comparative Examples 1 and 2
After mixing the components shown in Table 1 with a Henschel mixer at the blending ratio shown in each table, the mixture is melt-kneaded using a vented twin screw extruder (manufactured by Nippon Steel Works, TEX44, barrel setting temperature 260 ° C.), pellets Turned into. After sufficiently drying the obtained pellet, a test piece was molded by the above method using this pellet, and evaluated by the above method using the obtained test piece. The evaluation results are shown in Table 1.

From Table 1, the following can be understood.
Contains the components (A) and (B) of the present application, the total amount of alkali metal and alkaline earth metal is 200 ppm or less, in particular, the total amount of alkaline earth metal is 100 ppm or less, and the amount of calcium is 15 ppm In the following Examples 1 to 4, the generation of stagnation noise was well suppressed after the wet heat treatment.

  On the other hand, in Comparative Examples 1 and 2, which contain the components (A) and (B) of the present application and the total amount of alkali metal and alkaline earth metal exceeds 200 ppm, the generation of stagnation noise was significant after wet heat treatment. It was.

  The thermoplastic resin composition of the present invention is excellent in moisture and heat aging resistance, and particularly prevents the generation of squeaking noise caused by use in a humid heat environment, so that it is a molding material for articles used in harsh environments. Useful as.

Claims (3)

The total content of alkali metal and alkaline earth metal is 200 ppm or less, including mixing polycarbonate resin (A) and rubber-reinforced aromatic vinyl resin (B) (excluding bulk polymerized ABS) A method for producing a thermoplastic resin composition (X), wherein the component (B) comprises the following component (B1).
Component (B1): A rubber-reinforced aromatic vinyl resin containing ethylene / α-olefin rubber (b1) as a rubber component and obtained by any of the following methods (i) to (iv).
(i) After coagulating the latex obtained by emulsion polymerization with methanol, washing the alkali metal or alkaline earth metal,
(ii) After the latex obtained by emulsion polymerization is mechanically coagulated or freeze-coagulated, the alkali metal or alkaline earth metal is washed,
(iii) after coagulating the latex obtained by emulsion polymerization with an acid and / or an inorganic salt, washing the alkali metal or alkaline earth metal,
(iv) Emulsion polymerization using an emulsifier containing no alkali metal or alkaline earth metal. The production method according to claim 1 , wherein the component (B1) is obtained by the method (iii). The production method according to claim 2 , wherein in the method (iii), the latex is coagulated by an acid or a combination of an acid and an inorganic salt.

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