JP2018141078A - Polycarbonate resin composition and molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate resin composition that has excellent slidability, reduces the occurrence of unusual noise and wear under high temperature environment, and has a good appearance, and provide a molding.SOLUTION: A polycarbonate resin composition contains a polycarbonate resin (A) 55-90 pts.mass and a rubber-reinforced styrenic resin (B) 10-45 pts.mass. Relative to the total of (A) and (B) of 100 pts.mass, it further contains an ethylene or ethylene-vinyl acetate copolymer (B) having a styrenic (co) polymer segment of 3-15 pts.mass and a polyethylene oxide wax (C) of 0.05 pts.mass or more and less than 1.5 pts.mass.SELECTED DRAWING: None

Description

  The present invention relates to a polycarbonate resin composition and a molded article, and more particularly, to a polycarbonate resin composition and a molded article that are excellent in slidability, have less abnormal noise and wear under a high temperature environment, and have an excellent appearance of the molded article. .

Polycarbonate resin is a resin excellent in heat resistance, mechanical properties, and electrical characteristics. For example, it is widely used for parts manufacturing materials in automobiles, electrical / electronic equipment, housing related and other industrial fields. An alloy composition in which an ABS resin is blended with a resin is suitably used as a component or member for electric / electronic devices such as vehicles, computers, notebook computers, various portable terminals, printers, copiers, and OA / information devices. ing.
Particularly in automobiles and the like, conventionally, resin parts have been frequently used as interior materials for reasons such as ease of molding and weight reduction, and polycarbonate resin / ABS resin alloy has also been used.

  In addition, products such as console panels, dashboards, car navigation systems, and the like that are installed in automobiles are manufactured by fitting and assembling resin molded parts for the purpose of weight reduction. For example, in the case of a case structure, usually, a fitting part for fitting is integrally formed in each part of a container-shaped molded part that is half-cracked in the upper and lower parts, so that screws are hardly used or used for a minimum use. The casing molded product is manufactured by fastening and fitting the outer peripheral edges of the upper and lower molded parts facing each other.

However, when such a molded product is mounted on a vehicle, the temperature change from low to high temperature is severe under the environment in the automobile interior, and the resin molded product is likely to be deformed due to contraction and expansion due to thermal fluctuation, and the fitting part is deformed. If even a slight amount of noise occurs, stagnation noise is likely to occur due to vibrations during driving of the automobile. The stagnation sound greatly impairs the comfort when riding, but the higher level of indoor quietness is particularly demanded for high-end cars, so prevention of stagnation noise is an extremely important issue.
Generation of such a squeaking noise occurs when the members are rubbed with each other. As an effective means for preventing or reducing the squeaking noise, it has been practiced for a long time to apply grease or a fluororesin to the surface of the molded product. However, this method is difficult to automate and relies on manual work, and since the effect does not last, it is not a permanent measure.

  As a method for imparting slidability to a polycarbonate resin material, for example, in Patent Document 1, a polycarbonate resin is made of a nonpolar α-olefin (co) polymer and a vinyl (co) polymer, and the particle diameter of the dispersion resin Has proposed a resin composition with improved sliding properties, which is blended with a multiphase thermoplastic resin having a thickness of 0.001 to 10 μm. Patent Document 2 discloses a method of blending a silane-modified polyethylene resin with a polycarbonate resin.

Japanese Patent Laid-Open No. 4-211447 Japanese Patent Laid-Open No. 5-247236

However, the slidability of these technologies cannot be said to be sufficient. Particularly, in recent years, the generation of abnormal noise and wear under high-temperature environments is required, and the appearance of molded products is good. Is also required.
An object (object) of the present invention is a polycarbonate resin composition and a molded article that are excellent in slidability, have less noise and wear in a high-temperature environment, and have a good appearance in view of the above-described problems of the prior art. Is to provide.

As a result of intensive investigations to achieve the above-mentioned problems, the present inventors have found that in a system in which a rubber-reinforced styrene resin is blended with a polycarbonate resin, an ethylene-vinyl acetate copolymer having a styrene (co) polymer segment. It has been found that a polycarbonate resin composition containing both a coalesced acid and an acid-modified polyethylene wax in a specific amount is excellent in slidability and good appearance, and has completed the present invention.
That is, the present invention relates to the following polycarbonate resin composition and molded article.

[1] 55 to 90 parts by mass of polycarbonate resin (A) and 10 to 45 parts by mass of rubber-reinforced styrene resin (B) with respect to a total of 100 parts by mass of (A) and (B), styrene (co) A polycarbonate resin comprising 3 to 15 parts by mass of an ethylene-vinyl acetate copolymer (B) having a polymer segment, and 0.05 parts by mass or more and less than 1.5 parts by mass of oxidized polyethylene wax (C). Composition.
[2] The polycarbonate resin composition according to the above [1], wherein the rubber-reinforced styrene resin (B) is an ABS resin.
[3] A molded product obtained by molding the polycarbonate resin composition according to [1] or [2].
[4] The molded product according to [3], wherein the molded product is an automobile interior part.

  The polycarbonate resin composition of the present invention is excellent in slidability, generates less abnormal noise and wear in a high temperature environment, and has a good appearance. Therefore, the molded product obtained by molding the polycarbonate resin composition of the present invention is a product that requires various slidability, particularly as an automotive interior part that is required to generate less abnormal noise or wear at high temperatures. It can be preferably used.

Hereinafter, although an embodiment, an example thing, etc. are shown and explained in detail about the present invention, the present invention is not limited to an embodiment, an example, etc. shown below.
In the specification of the present application, “to” is used in the sense of including the numerical values described before and after it as the lower limit value and the upper limit value.

  The polycarbonate resin composition of the present invention is composed of 55 to 90 parts by mass of the polycarbonate resin (A) and 10 to 45 parts by mass of the rubber-reinforced styrene resin (B), and a total of 100 parts by mass of (A) and (B). 3-15 parts by mass of an ethylene-vinyl acetate copolymer (B) having a styrene-based (co) polymer segment and 0.05 parts by mass or more and less than 1.5 parts by mass of oxidized polyethylene wax (C) It is characterized by.

[Polycarbonate resin (A)]
The type of the polycarbonate resin (A) contained in the polycarbonate resin composition of the present invention is not limited, and only one type may be used, and two or more types are used in any combination and in any ratio. May be.
The polycarbonate resin is a polymer having a basic structure having a carbonic acid bond represented by a general formula: — [— O—X—O—C (═O) —] —. In the above formula, X is generally a hydrocarbon, but for imparting various properties, X into which a hetero atom or hetero bond is introduced may be used.

  As the polycarbonate resin (A), an aromatic polycarbonate resin is particularly preferable. The aromatic polycarbonate resin refers to a polycarbonate resin in which carbons directly bonded to carbonic acid bonds are aromatic carbons. Aromatic polycarbonate is superior from various polycarbonates in terms of heat resistance, mechanical properties, electrical characteristics, and the like.

  Although there is no restriction | limiting in the specific kind of aromatic polycarbonate resin, For example, the aromatic polycarbonate polymer formed by making a dihydroxy compound and a carbonate precursor react is mentioned. At this time, in addition to the dihydroxy compound and the carbonate precursor, a polyhydroxy compound or the like may be reacted. Further, a method of reacting carbon dioxide with a cyclic ether using a carbonate precursor may be used. The aromatic polycarbonate polymer may be linear or branched. Furthermore, the aromatic polycarbonate polymer may be a homopolymer composed of one type of repeating unit, or may be a copolymer having two or more types of repeating units. At this time, the copolymer can be selected from various copolymerization forms such as a random copolymer and a block copolymer. Normally, such an aromatic polycarbonate polymer is a thermoplastic resin.

Among monomers used as raw materials for aromatic polycarbonate resins, examples of aromatic dihydroxy compounds include:
Dihydroxybenzenes such as 1,2-dihydroxybenzene, 1,3-dihydroxybenzene (ie, resorcinol), 1,4-dihydroxybenzene;

Dihydroxybiphenyls such as 2,5-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl;

2,2′-dihydroxy-1,1′-binaphthyl, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, , 7-dihydroxynaphthalene, dihydroxynaphthalene such as 2,7-dihydroxynaphthalene;

2,2′-dihydroxydiphenyl ether, 3,3′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dimethyldiphenyl ether, 1,4-bis (3-hydroxyphenoxy) Dihydroxy diaryl ethers such as benzene and 1,3-bis (4-hydroxyphenoxy) benzene;

2,2-bis (4-hydroxyphenyl) propane (ie, bisphenol A),
1,1-bis (4-hydroxyphenyl) propane,
2,2-bis (3-methyl-4-hydroxyphenyl) propane,
2,2-bis (3-methoxy-4-hydroxyphenyl) propane,
2- (4-hydroxyphenyl) -2- (3-methoxy-4-hydroxyphenyl) propane,
1,1-bis (3-tert-butyl-4-hydroxyphenyl) propane,
2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane,
2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane,
2- (4-hydroxyphenyl) -2- (3-cyclohexyl-4-hydroxyphenyl) propane,
α, α′-bis (4-hydroxyphenyl) -1,4-diisopropylbenzene,
1,3-bis [2- (4-hydroxyphenyl) -2-propyl] benzene,
Bis (4-hydroxyphenyl) methane,
Bis (4-hydroxyphenyl) cyclohexylmethane,
Bis (4-hydroxyphenyl) phenylmethane,
Bis (4-hydroxyphenyl) (4-propenylphenyl) methane,
Bis (4-hydroxyphenyl) diphenylmethane,
Bis (4-hydroxyphenyl) naphthylmethane,
1,1-bis (4-hydroxyphenyl) ethane,
1,1-bis (4-hydroxyphenyl) -1-phenylethane,
1,1-bis (4-hydroxyphenyl) -1-naphthylethane,
1,1-bis (4-hydroxyphenyl) butane,
2,2-bis (4-hydroxyphenyl) butane,
2,2-bis (4-hydroxyphenyl) pentane,
1,1-bis (4-hydroxyphenyl) hexane,
2,2-bis (4-hydroxyphenyl) hexane,
1,1-bis (4-hydroxyphenyl) octane,
2,2-bis (4-hydroxyphenyl) octane,
4,4-bis (4-hydroxyphenyl) heptane,
2,2-bis (4-hydroxyphenyl) nonane,
1,1-bis (4-hydroxyphenyl) decane,
1,1-bis (4-hydroxyphenyl) dodecane,
Bis (hydroxyaryl) alkanes such as;

1,1-bis (4-hydroxyphenyl) cyclopentane,
1,1-bis (4-hydroxyphenyl) cyclohexane,
1,1-bis (4-hydroxyphenyl) -3,3-dimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3,4-dimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3,5-dimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane,
1,1-bis (4-hydroxy-3,5-dimethylphenyl) -3,3,5-trimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3-propyl-5-methylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3-tert-butyl-cyclohexane,
1,1-bis (4-hydroxyphenyl) -4-tert-butyl-cyclohexane,
1,1-bis (4-hydroxyphenyl) -3-phenylcyclohexane,
1,1-bis (4-hydroxyphenyl) -4-phenylcyclohexane,
Bis (hydroxyaryl) cycloalkanes such as;

9,9-bis (4-hydroxyphenyl) fluorene,
Cardio structure-containing bisphenols such as 9,9-bis (4-hydroxy-3-methylphenyl) fluorene;

4,4′-dihydroxydiphenyl sulfide,
Dihydroxydiaryl sulfides such as 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide;

Dihydroxydiaryl sulfoxides such as 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide;

4,4′-dihydroxydiphenyl sulfone,
Dihydroxydiaryl sulfones such as 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfone;
Etc.

Among these, bis (hydroxyaryl) alkanes are preferable, and bis (4-hydroxyphenyl) alkanes are preferable, and 2,2-bis (4-hydroxyphenyl) propane (ie, from the viewpoint of impact resistance and heat resistance). Bisphenol A) is preferred.
In addition, 1 type may be used for an aromatic dihydroxy compound and it may use 2 or more types together by arbitrary combinations and a ratio.

In addition, when an example of a monomer that is a raw material of the aliphatic polycarbonate resin is given,
Ethane-1,2-diol, propane-1,2-diol, propane-1,3-diol, 2,2-dimethylpropane-1,3-diol, 2-methyl-2-propylpropane-1,3- Alkanediols such as diol, butane-1,4-diol, pentane-1,5-diol, hexane-1,6-diol, decane-1,10-diol;

Cyclopentane-1,2-diol, cyclohexane-1,2-diol, cyclohexane-1,4-diol, 1,4-cyclohexanedimethanol, 4- (2-hydroxyethyl) cyclohexanol, 2,2,4, Cycloalkanediols such as 4-tetramethyl-cyclobutane-1,3-diol;

  Glycols such as ethylene glycol, 2,2'-oxydiethanol (ie, diethylene glycol), triethylene glycol, propylene glycol, spiro glycol and the like;

  1,2-benzenedimethanol, 1,3-benzenedimethanol, 1,4-benzenedimethanol, 1,4-benzenediethanol, 1,3-bis (2-hydroxyethoxy) benzene, 1,4-bis ( 2-hydroxyethoxy) benzene, 2,3-bis (hydroxymethyl) naphthalene, 1,6-bis (hydroxyethoxy) naphthalene, 4,4′-biphenyldimethanol, 4,4′-biphenyldiethanol, 1,4- Aralkyl diols such as bis (2-hydroxyethoxy) biphenyl, bisphenol A bis (2-hydroxyethyl) ether, bisphenol S bis (2-hydroxyethyl) ether;

  1,2-epoxyethane (ie ethylene oxide), 1,2-epoxypropane (ie propylene oxide), 1,2-epoxycyclopentane, 1,2-epoxycyclohexane, 1,4-epoxycyclohexane, 1-methyl And cyclic ethers such as -1,2-epoxycyclohexane, 2,3-epoxynorbornane, and 1,3-epoxypropane;

  Among the monomers used as the raw material for the polycarbonate resin, carbonyl halides, carbonate esters and the like are used as examples of the carbonate precursor. In addition, 1 type may be used for a carbonate precursor and it may use 2 or more types together by arbitrary combinations and a ratio.

Specific examples of carbonyl halides include phosgene; haloformates such as bischloroformate of dihydroxy compounds and monochloroformate of dihydroxy compounds.
Specific examples of the carbonate ester include diaryl carbonates such as diphenyl carbonate and ditolyl carbonate; dialkyl carbonates such as dimethyl carbonate and diethyl carbonate; biscarbonate bodies of dihydroxy compounds, monocarbonate bodies of dihydroxy compounds, and cyclic carbonates. And carbonate bodies of dihydroxy compounds such as

  The method for producing the polycarbonate resin is not particularly limited, and any known method can be adopted. Examples thereof include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid phase transesterification method of a prepolymer.

  The molecular weight of the polycarbonate resin (A) is arbitrary and may be appropriately selected and determined. However, the viscosity average molecular weight [Mv] is preferably 10,000 to 40,000. When the viscosity average molecular weight is less than 10,000, the mechanical strength tends to be insufficient, and when the viscosity average molecular weight exceeds 40,000, the fluidity is poor and the moldability tends to be deteriorated. The viscosity average molecular weight is more preferably 16,000 to 40,000, further preferably 18,000 to 30,000, particularly 18,500 to 25,000. The molecular weight can be adjusted to such a range by a known method such as controlling the amount of the molecular weight regulator as described later.

Here, the viscosity average molecular weight [Mv] is obtained by using methylene chloride as a solvent and obtaining an intrinsic viscosity [η] (unit dl / g) at a temperature of 20 ° C. using an Ubbelohde viscometer, Schnell's viscosity formula, That is, it means a value calculated from η = 1.23 × 10 ⁻⁴ Mv ^0.83 . The intrinsic viscosity [η] is a value calculated from the following equation by measuring the specific viscosity [ηsp] at each solution concentration [C] (g / dl).

Other Matters Related to Polycarbonate Resin The terminal hydroxyl group concentration of the polycarbonate resin is arbitrary and may be appropriately selected and determined, but is usually 1,000 ppm or less, preferably 800 ppm or less, more preferably 600 ppm or less. By doing in this way, the residence heat stability and color tone of a polycarbonate resin composition can be improved more. In addition, the lower limit is usually 10 ppm or more, preferably 30 ppm or more, more preferably 40 ppm or more, particularly for polycarbonate resins produced by the melt transesterification method. Thereby, the fall of molecular weight can be suppressed and the mechanical characteristic of a polycarbonate resin composition can be improved more.
In addition, the unit of a terminal hydroxyl group density | concentration represents the mass of the terminal hydroxyl group with respect to the mass of polycarbonate resin in ppm. The measuring method is performed by colorimetric determination (method described in Macromol. Chem. 88 215 (1965)) by a titanium tetrachloride / acetic acid method.

  The polycarbonate resin (A) is not limited to an embodiment containing only one type of polycarbonate resin, and two or more types of polycarbonate resins having different monomer compositions, molecular weights, terminal hydroxyl group concentrations, and the like may be mixed and used. Moreover, you may use combining as an alloy (mixture) which mixed other thermoplastic resin with polycarbonate resin.

  Further, for example, for the purpose of further improving flame retardancy and impact resistance, a polycarbonate resin is copolymerized with an oligomer or polymer having a siloxane structure; for the purpose of further improving thermal oxidation stability and flame retardancy A monomer, oligomer or polymer having a copolymer; a monomer, oligomer or polymer having a dihydroxyanthraquinone structure for the purpose of improving thermal oxidation stability; A copolymer with an oligomer or polymer having an olefin structure; a copolymer with a polyester resin oligomer or polymer for the purpose of improving chemical resistance; Good.

  Further, in order to improve the appearance of the molded product and improve the fluidity, the polycarbonate resin may contain a polycarbonate oligomer. The viscosity average molecular weight [Mv] of this polycarbonate oligomer is usually 1,500 or more, preferably 2,000 or more, and usually 9,500 or less, preferably 9,000 or less. Furthermore, the polycarbonate ligomer contained is preferably 30% by mass or less of the polycarbonate resin (including the polycarbonate oligomer).

Further, the polycarbonate resin may be not only a virgin raw material but also a polycarbonate resin regenerated from a used product (so-called material-recycled polycarbonate resin). Examples of the used products include: optical recording media such as optical disks; light guide plates; vehicle window glass, vehicle headlamp lenses, windshields and other vehicle transparent members; water bottles and other containers; eyeglass lenses; Examples include architectural members such as glass windows and corrugated sheets. Also, non-conforming products, pulverized products obtained from sprues, runners, etc., or pellets obtained by melting them can be used.
However, the regenerated polycarbonate resin is preferably 80% by mass or less, more preferably 50% by mass or less, among the polycarbonate resins contained in the polycarbonate resin composition. Recycled polycarbonate resin is likely to have undergone deterioration such as heat deterioration and aging deterioration, so when such polycarbonate resin is used more than the above range, hue and mechanical properties can be reduced. It is because there is sex.

[Rubber reinforced styrene resin (B)]
The rubber-reinforced styrene-based resin (B) contained in the polycarbonate resin composition of the present invention is preferably an vinyl vinyl monomer copolymerizable with an aromatic vinyl monomer and, if necessary, in the presence of a rubber-like polymer. It is a resin obtained by polymerizing a monomer.

Examples of the aromatic vinyl monomer (b1) used in the rubber-reinforced styrene resin (B) include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, vinylxylene, ethylstyrene, dimethylstyrene, p. Examples thereof include styrene derivatives such as -tert-butylstyrene, vinylnaphthalene, methoxystyrene, monobromostyrene, dibromostyrene, fluorostyrene, and tribromostyrene, and styrene is particularly preferable.
These may be used alone or in combination of two or more.

  The other vinyl monomer copolymerizable with these aromatic vinyl monomers (b1) is preferably a vinyl cyanide monomer (b2), and examples thereof include acrylonitrile and methacrylonitrile.

Other monomers (b3) other than vinyl cyanide monomer (b2) that can be copolymerized include aryl esters of acrylic acid such as phenyl acrylate and benzyl acrylate; methyl acrylate, ethyl acrylate, propyl acrylate Alkyl esters of acrylic acid such as butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, cyclohexyl acrylate, dodecyl acrylate; aryl methacrylates such as phenyl methacrylate, benzyl methacrylate; methyl methacrylate, ethyl methacrylate, propyl Methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate Methacrylic acid alkyl esters such as octyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate; epoxy group-containing methacrylic acid esters such as glycidyl methacrylate; maleimide monomers such as maleimide, N-methylmaleimide, N-phenylmaleimide; acrylic acid, Examples include α, β-unsaturated carboxylic acids such as methacrylic acid, maleic acid, maleic anhydride, phthalic acid, and itaconic acid, and anhydrides thereof. Preferred are alkyl acrylates and alkyl methacrylates.
One of these other monomers (b3) may be used alone, or two or more thereof may be mixed and used.

The rubbery polymer (b4) copolymerizable with these monomers is preferably a rubber having a glass transition temperature of 10 ° C. or lower. Specific examples of such rubbery polymers include diene rubber, acrylic rubber, ethylene / propylene rubber, silicone rubber, polyorganosiloxane rubber component and polyalkyl (meth) acrylate rubber component so that they cannot be separated from each other. Composite rubber (IPN type rubber) having a structure entangled with each other is preferable, and diene rubber, acrylic rubber and the like are preferable.
In this specification, “(meth) acrylate” refers to one or both of “acrylate” and “methacrylate”, and the same applies to “(meth) acryl” and “(meth) acrylo”.

Examples of the diene rubber include polybutadiene, styrene-butadiene random copolymer and block copolymer, acrylonitrile-butadiene copolymer, polyisoprene, butadiene-isoprene copolymer, and ethylene-propylene-hexadiene copolymer. Examples thereof include a copolymer of ethylene, propylene and a non-conjugated diene, a lower alkyl ester copolymer of butadiene- (meth) acrylic acid, a lower alkyl ester copolymer of butadiene-styrene- (meth) acrylic acid, and the like.
Examples of the lower alkyl ester of (meth) acrylic acid include methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate.
The proportion of the lower alkyl ester of (meth) acrylic acid in the lower alkyl ester copolymer of butadiene- (meth) acrylic acid or the lower alkyl ester copolymer of butadiene-styrene- (meth) acrylic acid is that of the rubber polymer. It is preferable that it is 30 mass% or less of quantity.

  Examples of the acrylic rubber include acrylic acid alkyl ester rubber, and the carbon number of the alkyl group is preferably 1-8. Specific examples of the alkyl acrylate include ethyl acrylate, butyl acrylate, hexyl acrylate and the like. An ethylenically unsaturated monomer may optionally be used in the acrylic acid alkyl ester rubber. Specific examples of such compounds include di (meth) acrylate, divinylbenzene, trivinylbenzene, triallyl cyanurate, allyl (meth) acrylate, butadiene, isoprene and the like. Examples of the acrylic rubber include a core-shell type polymer having a crosslinked diene rubber as a core.

  These rubbery polymers may also be used alone or in combination of two or more.

  The rubber-reinforced styrene resin (B) is composed of 45 to 80% by mass of the aromatic vinyl monomer component (b1), 10 to 30% by mass of the vinyl cyanide monomer component (b2), and other monomers. It is preferably composed of 0 to 40% by mass of the component (b3), 10 to 25% by mass of the rubbery polymer component (b4), 55 to 70% by mass of the aromatic vinyl monomer component (b1), and a single amount of vinyl cyanide. More preferably, it comprises 15 to 25% by mass of the body component (b2), 0 to 5% by mass of the other monomer component (b3), and 15 to 20% by mass of the rubbery polymer component (b4).

  Specific examples of the rubber-reinforced styrene resin (B) used in the present invention include, for example, acrylonitrile-butadiene-styrene copolymer (ABS resin), impact-resistant polystyrene (HIPS), and acrylonitrile-styrene copolymer. Polymer (AS resin), acrylonitrile-styrene-acrylic rubber copolymer (ASA resin), styrene-butadiene-styrene copolymer (SBS resin), hydrogenated styrene-butadiene-styrene copolymer (hydrogenated) SBS), hydrogenated styrene-isoprene-styrene copolymer (SEPS), acrylonitrile-acrylic rubber-styrene copolymer (AAS resin), acrylonitrile-ethylenepropylene rubber-styrene copolymer (AES resin) and Resin such as styrene-IPN type rubber copolymer, or a mixture of these Thing, and the like.

  Among these, acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene-acrylic rubber copolymer (ASA resin), and acrylonitrile-ethylenepropylene rubber-styrene copolymer (AES resin). The ABS resin is particularly preferable.

  There is no restriction | limiting in particular as a manufacturing method of rubber reinforcement | strengthening styrene-type resin (B), All can be employ | adopted by well-known methods, such as an emulsion polymerization method, solution polymerization method, suspension polymerization method, and block polymerization method.

  The rubber-reinforced styrene resin (B) may be used alone or in combination of two or more.

  The content of the rubber-reinforced styrene resin (B) is 10 to 45 parts by weight, preferably 12 parts by weight or more, based on a total of 100 parts by weight of the polycarbonate resin (A) and the rubber-reinforced styrene resin (B). More preferably, it is 15 parts by mass or more, preferably 42 parts by mass or less, more preferably 40 parts by mass or less. When the amount of the rubber-reinforced styrene resin (B) exceeds 45 parts by mass, the heat resistance decreases, and when it is less than 10 parts by mass, the fluidity decreases.

[Ethylene-vinyl acetate copolymer (C) having a styrene (co) polymer segment]
The copolymer (C) contained in the polycarbonate resin composition of the present invention is an ethylene-vinyl acetate copolymer having a styrenic (co) polymer segment. The copolymer (C) is not limited as long as it is a copolymer comprising a styrene-based (co) polymer part (segment) and an ethylene-vinyl acetate copolymer part (segment), but is preferably a styrene-based (copolymer). ) A graft copolymer comprising a polymer segment and an ethylene-vinyl acetate copolymer segment is preferred, with the ethylene-vinyl acetate copolymer as the main chain and the styrene (co) polymer segment as the side chain. Graft copolymers are preferred.

  The proportion of vinyl acetate units in the ethylene-vinyl acetate copolymer is preferably 1 to 20% by mass, more preferably 3 to 10% by mass.

  The styrene (co) polymer segment is a homopolymer of a styrene monomer or a copolymer with another vinyl monomer.

  Examples of the styrene monomer include styrene, methyl styrene, dimethyl styrene, ethyl styrene, isopropyl styrene, chlorostyrene, and the like, and styrene is particularly preferable.

  Preferred examples of other vinyl monomers include vinyl cyanide monomers; glycidyl esters of acrylic acid or methacrylic acid; alkyl esters of acrylic acid or methacrylic acid.

Examples of the vinyl cyanide monomer include acrylonitrile and methacrylonitrile, and acrylonitrile is particularly preferable.
Examples of the glycidyl ester of acrylic acid or methacrylic acid include glycidyl acrylate and glycidyl methacrylate, and glycidyl methacrylate is preferred.
The alkyl ester of acrylic acid or methacrylic acid is preferably an alkyl ester having 1 to 8 carbon atoms, such as methyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, Examples include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, and isobutyl methacrylate.

  As other vinyl monomers, among them, acrylic acid or methacrylic acid glycidyl ester and vinyl cyanide monomer are preferable, acrylic acid or methacrylic acid glycidyl ester is more preferable, and methacrylic acid glycidyl ester is particularly preferable. preferable.

The content of the styrene monomer and the other vinyl monomer in the styrene (co) polymer segment is not particularly limited, but a total of 100 parts by mass of the styrene monomer and the other vinyl monomer. On the basis, the content of the styrene monomer is preferably 50 to 100 parts by mass.
The content of the styrene-based (co) polymer segment is 10 to 50 parts by mass with respect to 100% by mass of the total ethylene-vinyl acetate copolymer (C). It is preferable that

  The ethylene-vinyl acetate copolymer (C) having a styrene (co) polymer segment can be produced by various known methods. As a suitable method thereof, an aqueous suspension obtained by adding a suspending agent to an ethylene-vinyl acetate copolymer, a styrene monomer, or another vinyl monomer and a radical polymerizable organic peroxide are used. And a method in which the mixture is heated and stirred to impregnate the ethylene-vinyl acetate copolymer with the above components, followed by polymerization at an elevated temperature.

  In addition, the ethylene-vinyl acetate copolymer (C) having a styrene-based (co) polymer segment is commercially available, for example, by selecting from the product name “Modiper” series of NOF Corporation. Can do.

The content of the ethylene-vinyl acetate copolymer (C) having a styrene (co) polymer segment is 3 to 15 with respect to 100 parts by mass in total of the polycarbonate resin (A) and the rubber-reinforced styrene resin (B). Part by mass. If the content is less than 3 parts by mass, the squeaking noise suppression effect and slidability are reduced, the wear amount is increased, and even if the content exceeds 15 parts by mass, the heat resistance and rigidity are greatly reduced.
Content of a copolymer (B) becomes like this. Preferably it is 3-13 mass parts, More preferably, it is 4-12 mass parts.

[Oxidized polyethylene wax (D)]
The polycarbonate resin composition of the present invention contains an oxidized polyethylene wax (D).
Examples of the oxidized polyethylene wax (D) include, but are not limited to, an oxide of polyethylene wax produced by a low pressure polymerization method, an oxide of polyethylene wax produced by a high pressure polymerization method, and a high density polyethylene polymer. The oxide of this is mentioned. These oxidized polyethylene waxes may be used alone or in combination of two or more.

The dropping point of the oxidized polyethylene wax (D) is preferably 100 ° C. or higher and 140 ° C. or lower, more preferably 110 ° C. or higher and 130 ° C. or lower. The dropping point can be measured by a method based on ASTM D127.
The acid value of the oxidized polyethylene wax (D) is preferably 10 mgKOH / g or more and 50 mgKOH / g or less, more preferably 15 mgKOH / g or more and 40 mgKOH / g or less. The acid value can be measured by a method based on JIS K3504.
The number average molecular weight of the oxidized polyethylene wax (D) is preferably 500 or more and 5000 or less, more preferably 1000 or more and 4000 or less.

  The content of the oxidized polyethylene wax (D) is 0.05 parts by mass or more and less than 1.5 parts by mass with respect to 100 parts by mass in total of the polycarbonate resin (A) and the rubber-reinforced styrene resin (B). By containing the oxidized polyethylene wax (D) in such an amount, it is possible to improve the releasability and reduce the surface wear. The content of the oxidized polyethylene wax (D) is preferably 0.3 parts by mass or more, more preferably 0.5 parts by mass or more, preferably 1.3 parts by mass or less, more preferably 1.0 parts by mass or less. .

[Other ingredients]
The polycarbonate resin composition of the present invention may contain other components in addition to those described above as necessary, as long as the desired physical properties are not significantly impaired. Examples of other components include resins other than those described above and various resin additives other than those described above. In addition, 1 type may contain other components and 2 or more types may contain them by arbitrary combinations and ratios.

[Other resins]
Examples of other resins include thermoplastic polyester resins such as polyethylene terephthalate resin (PET resin), polytrimethylene terephthalate (PTT resin), and polybutylene terephthalate resin (PBT resin);
Polystyrene resin (PS resin), high impact polystyrene resin (HIPS), acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene-acrylic rubber copolymer (ASA) Resin), styrene resin such as acrylonitrile-ethylene propylene rubber-styrene copolymer (AES resin);

Polyolefin resins such as polyethylene resin (PE resin), polypropylene resin (PP resin), cyclic cycloolefin resin (COP resin), cyclic cycloolefin copolymer (COP) resin;
Polyamide resin (PA resin); Polyimide resin (PI resin); Polyetherimide resin (PEI resin); Polyurethane resin (PU resin); Polyphenylene ether resin (PPE resin); Polyphenylene sulfide resin (PPS resin); Polysulfone resin (PSU) Resin); polymethacrylate resin (PMMA resin); and the like.
In addition, 1 type may contain other resin and 2 or more types may contain it by arbitrary combinations and a ratio.

[Resin additive]
Examples of the resin additive include a heat stabilizer, an antioxidant, an ultraviolet absorber, a dye / pigment (including titanium oxide and carbon black), an antistatic agent, a filler, a flame retardant, an antifogging agent, a lubricant, and an anti-static agent. Examples include blocking agents, fluidity improvers, plasticizers, dispersants, antibacterial agents, and the like.
In addition, 1 type may contain resin additive and 2 or more types may contain it by arbitrary combinations and a ratio.

[Stabilizer]
It is preferable that the polycarbonate resin composition of the present invention further contains a stabilizer because it has an effect of improving thermal stability and preventing deterioration of mechanical strength, transparency and hue. As the stabilizer, a phosphorus stabilizer and a phenol stabilizer are preferable.
Examples of the phosphorus stabilizer include phosphorous acid, phosphoric acid, phosphite ester, phosphate ester, etc. Among them, phosphite and phosphonite are preferable.

  Examples of the phosphite include triphenyl phosphite, tris (nonylphenyl) phosphite, dilauryl hydrogen phosphite, triethyl phosphite, tridecyl phosphite, tris (2-ethylhexyl) phosphite, tris (tridecyl) phosphite. Phyto, tristearyl phosphite, diphenyl monodecyl phosphite, monophenyl didecyl phosphite, diphenyl mono (tridecyl) phosphite, tetraphenyldipropylene glycol diphosphite, tetraphenyltetra (tridecyl) pentaerythritol tetraphosphite, water Bisphenol A phenol phosphite polymer, diphenyl hydrogen phosphite, 4,4′-butylidene-bis (3-methyl-6-tert-butyl) Ruphenyldi (tridecyl) phosphite), tetra (tridecyl) 4,4'-isopropylidene diphenyldiphosphite, bis (tridecyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, dilaurylpentaerythritol diphosphite Phosphite, distearyl pentaerythritol diphosphite, tris (4-tert-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, hydrogenated bisphenol A pentaerythritol phosphite polymer, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite 2,2'-methylenebis (4,6-di -tert- butylphenyl) octyl phosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite and the like.

  Examples of phosphonites include tetrakis (2,4-di-iso-propylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-n-butylphenyl) -4,4′-biphenyl. Range phosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylene diphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3'-biphenylene diphospho Knight, tetrakis (2,4-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite, tetrakis (2,6-di-iso-propylphenyl) -4,4'-biphenylenediphosphonite, Tetrakis (2,6-di-n-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,6- -Tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,3'-biphenylenediphosphonite, and tetrakis (2,6-di-) tert-butylphenyl) -3,3′-biphenylenediphosphonite.

Examples of the phosphate include methyl acid phosphate, ethyl acid phosphate, propyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate, butoxyethyl acid phosphate, octyl acid phosphate, 2-ethylhexyl acid phosphate, decyl acid phosphate, and lauryl acid phosphate. , Stearyl acid phosphate, oleyl acid phosphate, behenyl acid phosphate, phenyl acid phosphate, nonyl phenyl acid phosphate, cyclohexyl acid phosphate, phenoxyethyl acid phosphate, alkoxy polyethylene glycol acid phosphate, bisphenol A acid phosphate , Dimethyl acid phosphate, diethyl acid phosphate, dipropyl acid phosphate, diisopropyl acid phosphate, dibutyl acid phosphate, dioctyl acid phosphate, di-2-ethylhexyl acid phosphate, dioctyl acid phosphate, dilauryl acid phosphate, distearyl acid phosphate, Acid phosphate, bisnonylphenyl acid phosphate, etc. are mentioned.
One type of phosphorous stabilizer may be contained, or two or more types may be contained in any combination and ratio.

  Specific examples of the phenol-based stabilizer include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl- 4-hydroxyphenyl) propionate, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexane-1,6-diylbis [3- (3 5-di-tert-butyl-4-hydroxyphenyl) propionamide], 2,4-dimethyl-6- (1-methylpentadecyl) phenol, diethyl [[3,5-bis (1,1-dimethylethyl)- 4-hydroxyphenyl] methyl] phosphoate, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert- Til-a, a ′, a ″-(mesitylene-2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3 5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert -Butyl-4- (4,6-bis (octylthio) -1,3,5-triazin-2-ylamino) phenol and the like.

Of these, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate are preferable. .
In addition, 1 type may contain the phenol type stabilizer, and 2 or more types may contain it by arbitrary combinations and a ratio.

  The content of the stabilizer is usually 0.001 parts by mass or more, preferably 0.01 parts by mass or more with respect to 100 parts by mass in total of the polycarbonate resin (A) and the rubber-reinforced styrene resin (B). The amount is usually 1.5 parts by mass or less, preferably 1 part by mass or less. If the amount is less than 0.001 part by mass, the effect as a stabilizer is insufficient, and molecular weight reduction and hue deterioration during molding are likely to occur. Deterioration tends to occur more easily.

[Production of polycarbonate resin composition]
There is no restriction | limiting in the manufacturing method of the polycarbonate resin composition of this invention, The manufacturing method of a well-known polycarbonate resin composition can be employ | adopted widely, and above-mentioned (A)-(D) component and others mix | blended as needed Are mixed in advance using various mixers such as a tumbler and a Henschel mixer, and then melt-kneaded with a mixer such as a Banbury mixer, roll, brabender, single-screw kneading extruder, twin-screw kneading extruder, kneader or the like. A method is mentioned. The temperature for melt kneading is not particularly limited, but is usually in the range of 240 to 320 ° C.

[Molded body]
There is no restriction | limiting in the method of manufacturing a molded object from the obtained resin composition pellet, The shaping | molding method generally employ | adopted about the polycarbonate resin composition can be employ | adopted arbitrarily. For example, injection molding method, ultra-high speed injection molding method, injection compression molding method, two-color molding method, hollow molding method such as gas assist, molding method using heat insulating mold, rapid heating mold were used. Examples of the molding method include foam molding (including supercritical fluid), insert molding, and IMC (in-mold coating molding) molding method. Injection molding and injection compression molding are preferred from the viewpoint of easy molding and productivity.

  Molded products made of polycarbonate resin composition are excellent in slidability, have less noise and wear under high temperature environment, and have a good appearance. Therefore, automobile field, OA equipment field, home appliance, electric / electronic It can be suitably used as a part in a field or the like, and can be particularly suitably used as an automobile interior part.

Hereinafter, the present invention will be described with reference to examples.
Each raw material component used in Examples and Comparative Examples is as shown in Table 1 below.

[Examples 1 to 3, Comparative Examples 1 to 12]
Each component described in Table 1 above was blended at the ratio (mass ratio) described in Table 2, mixed for 20 minutes with a tumbler, and then added to a twin-screw extruder (TEM26SX) manufactured by Toshiba Machine Co., Ltd. equipped with 1 vent. Supplied. Kneaded under the conditions of a screw speed of 230 rpm, a discharge rate of 30 kg / hour, and a barrel temperature of 250 ° C., the molten resin extruded into a strand is rapidly cooled in a water tank, pelletized using a pelletizer, and a polycarbonate resin composition pellet is obtained. Obtained.

[Preparation of ISO multipurpose test pieces and appearance evaluation test pieces]
After the pellets obtained by the above production method were dried at 100 ° C. for 5 hours, the cylinder temperature was 250 ° C. using an injection molding machine (PLASTAR Si-80-6, mold clamping force 80T) manufactured by Toyo Machine Metal Co., Ltd. , ISO multi-purpose test piece (3mm thick, 4mm thick molded product) and stepped (2 step) plate molded product (50 x 45mm, 3mm / 2mm thick, 2 stages under the condition of mold temperature 70 ℃ Shape) was injection molded.

[Production of ring specimen]
The pellet obtained above was dried at 100 ° C. for 5 hours, and then cylinder temperature 250 ° C. and mold temperature 70 using an injection molding machine (J55AD-60H, clamping force 55T) manufactured by Nippon Steel Works. A ring-shaped test piece (inner diameter 20.5 mm, outer diameter 26 mm, height 15 mm) was injection-molded under the condition of ° C.

<Evaluation of various physical properties>
[Appearance of molded product]
The appearance and jetness of the step boundary of the obtained stepped plate molded product were visually evaluated.
That is, a stain-like appearance defect occurs at the step boundary, or the molded product is severely whitened (L ^* value when measured with a color difference meter SE6000 manufactured by Nippon Denshoku Co., Ltd. in a 2 ° visual field of C light source is 15). .Times. Or more) was marked with "X", and the case where jetness was maintained and no remarkable appearance defect occurred was marked with "O".

[Fluidity (Q value)]
The flow value was measured with a flow tester (manufactured by Shimadzu Corporation) under the conditions of a cylinder temperature of 260 ° C. and a load of 160 kgf, and the fluidity (Q value, unit: cc / 10 min) was evaluated.

[Charpy impact strength]
Using the ISO multipurpose test piece (3 mm thickness) obtained by the above method, the Charpy impact strength with notch (unit: kJ / m ² ) was measured under the condition of 23 ° C. in accordance with ISO179.

[Deflection temperature under load (DTUL, heat resistance evaluation)]
The deflection temperature under load (DTUL, unit: ° C.) was measured using the above-mentioned ISO multipurpose test piece (4 mm thickness) according to ISO 75-1 & 2 under the condition of load 1.80 MPa (Method A).

[Abnormal sound evaluation method (thrust ring method)]
An abnormal noise evaluation was performed using a thrust type frictional wear tester (Orientec Co., Ltd., EFM-III-E). A force with a surface pressure of 150 N was applied to the upper ring-shaped test piece, and the test was performed for 3 minutes under the condition of a linear velocity of 25 mm / s, and the presence or absence of abnormal noise was evaluated.
The case where sound of 80 dB or more was generated during the test was determined as “X”, and the case where sound was not generated was determined as “◯”. If no abnormal noise is heard during the test, it is judged as “◯”.
The test temperatures were 23 ° C and 85 ° C. The noise level in the test environment was 54 to 59 dB.

[Abrasion evaluation method (thrust ring method)]
Similar to the above-described abnormal noise evaluation method, a test was performed under the same conditions using a thrust type frictional wear tester. Abrasion resistance was evaluated at three levels.
The frictional surface of the ring after the test was visually confirmed, and “×” indicates that the wear was remarkable, “Δ” indicates that the wear was slightly observed, and “◯” indicates that the wear was not confirmed.
The above evaluation results are shown in Table 2 below.

  The polycarbonate resin composition of the present invention is excellent in slidability, generates less abnormal noise and wear in a high temperature environment, and has a good appearance. Therefore, the automotive field, OA equipment field, home appliance, electrical / electronic field, etc. It can be widely used as a component of the above, and the industrial utility value is extremely high.

Claims (4)

  Styrene (co) polymer segment with respect to a total of 100 parts by mass of (A) and (B) containing 55 to 90 parts by mass of polycarbonate resin (A) and 10 to 45 parts by mass of rubber-reinforced styrene resin (B) A polycarbonate resin composition comprising 3 to 15 parts by mass of an ethylene-vinyl acetate copolymer (B) having a content of 0.05 to 1.5 parts by mass of an oxidized polyethylene wax (C).   The polycarbonate resin composition according to claim 1, wherein the rubber-reinforced styrene resin (B) is an ABS resin.   A molded product formed by molding the polycarbonate resin composition according to claim 1.   The molded article according to claim 3, wherein the molded article is an automobile interior part.