JP2018141077A - Polycarbonate resin composition and molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a slidable, polycarbonate resin composition that shows high slidability, excellent in both dynamic friction coefficient and wear amount, while maintaining mechanical properties such as strength and impact resistance, and gives a molding a good appearance, and provide a molding.SOLUTION: A polycarbonate resin composition contains a polycarbonate resin (A) 100 pts.mass, and an ethylene or ethylene-vinyl acetate copolymer (B) having a styrenic (co) polymer segment of 4-15 pts.mass and an acid-modified polyethylene resin (C) of 1-5 pts.mass, and contains, optionally, a release agent (D). If it contains the release agent, its content is less than 0.1 pts.mass.SELECTED DRAWING: None

Description

  The present invention relates to a polycarbonate resin composition and a molded product, and more particularly, to a polycarbonate resin composition and a molded product that have a small amount of gas generated from the molded product and a bleed-out and are excellent in slidability.

  Polycarbonate resin is excellent in impact resistance, heat resistance, electrical insulation, dimensional stability, etc. and has a good balance of these characteristics, so it can be used for automobile interior parts, electrical / electronic equipment parts, OA equipment parts, precision machine parts. Widely used in such fields.

For example, parts installed in automobiles, such as console panels, dashboards, car navigation systems, etc., are often manufactured by fitting and assembling resin molded parts for the purpose of weight reduction. The temperature change from low temperature to high temperature is intense in the car interior under the environment, and the resin molded product is likely to be deformed due to shrinkage and expansion due to thermal fluctuations. The polycarbonate resin parts are rubbed and a squeaking noise is likely to occur.
In order to eliminate the squeaking noise, it is necessary to impart slidability to the polycarbonate resin.

  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 techniques cannot be said to be sufficient, and high slidability excellent in both the dynamic friction coefficient and the wear amount is required while sufficiently maintaining the mechanical properties of the polycarbonate resin. More recently, interior parts are required to generate less gas from molded products due to VOC regulations. In addition, the generated gas is concerned about the influence on the contact failure of the relay in electrical parts.
In view of the above-mentioned problems of the prior art, the object (object) of the present invention is to reduce the amount of gas generated from a molded product and bleed out while maintaining good mechanical properties, both in terms of dynamic friction coefficient and wear. An object of the present invention is to provide a polycarbonate resin composition and a molded product having excellent high slidability.

As a result of intensive studies to achieve the above-mentioned problems, the present inventor has obtained an ethylene or ethylene-vinyl acetate copolymer having a styrene-based (co) polymer segment in a polycarbonate resin, an acid-modified polyethylene resin, and a mold release. It has been found that a polycarbonate resin composition containing a specific amount of each agent has a small amount of gas generated from a molded product and bleed-out, and is excellent in slidability, thus completing the present invention.
That is, the present invention relates to the following polycarbonate resin composition and molded article.

[1] 4 to 15 parts by mass of ethylene or ethylene-vinyl acetate copolymer (B) having a styrene-based (co) polymer segment with respect to 100 parts by mass of the polycarbonate resin (A), acid-modified polyethylene resin (C) 1 to 5 parts by mass, and the release agent (D) is not contained, or the content when it is contained is less than 0.1 parts by mass.
[2] A molded product obtained by molding the polycarbonate resin composition according to [1].

  The polycarbonate resin composition of the present invention maintains high mechanical properties such as strength and impact resistance, has a small amount of gas generated from the molded product and bleed out, and has high slidability excellent in both dynamic friction coefficient and wear amount. Have Therefore, a molded product obtained by molding the polycarbonate resin composition of the present invention can be suitably used as a product that requires various slidability.

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 comprises 4 to 15 parts by mass of an ethylene or ethylene-vinyl acetate copolymer (B) having a styrene-based (co) polymer segment with respect to 100 parts by mass of the polycarbonate resin (A), an acid. It contains 1 to 5 parts by mass of the modified polyethylene resin (C) and does not contain the mold release agent (D) or the content when it is contained is less than 0.1 parts by mass.

[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).

[Ethylene or ethylene-vinyl acetate copolymer (B) having a styrene-based (co) polymer segment]
The copolymer (B) contained in the polycarbonate resin composition of the present invention is an ethylene or ethylene-vinyl acetate copolymer having a styrenic (co) polymer segment. The copolymer (B) may be a copolymer comprising a styrene-based (co) polymer part (segment) and an ethylene (co) polymer part (segment) or an ethylene-vinyl acetate copolymer part (segment). However, it is preferably a graft copolymer composed of a styrene-based (co) polymer segment and an ethylene (co) polymer segment or an ethylene-vinyl acetate copolymer segment. A graft copolymer having a copolymer or an ethylene (co) polymer segment as a main chain and a styrene (co) polymer segment as a side chain is preferred.

The proportion of vinyl acetate units in the ethylene-vinyl acetate copolymer part (segment) is preferably 1 to 20% by mass, more preferably 3 to 10% by mass.
The ethylene (co) polymer segment is preferably composed of an ethylene polymer or a copolymer of ethylene and another olefin. Other olefins are preferably propylene, butene, hexene, octene and the like, and the other olefin copolymerization amount is 0 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 (co) polymer segment is 10 to 50 parts by mass with respect to 100% by mass of the entire ethylene-vinyl acetate copolymer (B). It is preferable that

  The ethylene or ethylene-vinyl acetate copolymer (B) having a styrene (co) polymer segment can be produced by various known methods. As a preferred method, an ethylene-vinyl acetate copolymer or an aqueous suspension obtained by adding a suspending agent to an ethylene (co) polymer, a styrene monomer, or another vinyl monomer and Produced by mixing radical-polymerizable organic peroxide, heating and stirring, impregnating ethylene-vinyl acetate copolymer or ethylene (co) polymer with the above components, and then heating to polymerize. A method can be mentioned.

  In addition, ethylene or ethylene-vinyl acetate copolymer (B) having a styrene-based (co) polymer segment is commercially available. For example, it is obtained by selecting from the brand name “Modiper” series of NOF Corporation. can do.

The content of ethylene or ethylene-vinyl acetate copolymer (B) having a styrenic (co) polymer segment is 4 to 15 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A). When the content is less than 4 parts by mass, the friction coefficient and the amount of wear are not sufficiently improved. When the content exceeds 15 parts by mass, the mechanical properties, particularly the Charpy impact strength, are reduced.
The content of the copolymer (B) is preferably 4 to 10 parts by mass.

[Acid-modified polyethylene resin (C)]
The acid-modified polyethylene resin (C) contained in the polycarbonate resin composition of the present invention is a polyethylene resin modified with an acid such as an unsaturated carboxylic acid or a derivative thereof.
Examples of the acid used for acid modification include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, citraconic acid, sorbic acid, mesaconic acid, and angelic acid. Also, derivatives of these unsaturated carboxylic acids can be used. Examples of the derivatives include acid anhydrides, esters, amides, imides, and metal salts. Specific examples include maleic anhydride, itaconic anhydride, methyl acrylate, methyl methacrylate, ethyl acrylate, acrylic acid. Examples include propyl, butyl acrylate, ethyl maleate, acrylamide, maleic amide, sodium acrylate, and sodium methacrylate.

Among these, unsaturated dicarboxylic acids or derivatives thereof are preferable, and maleic acid and maleic anhydride are more preferable. Unsaturated carboxylic acid or its derivative (s) may be used alone or in combination of two or more.
There is no particular limitation on the modification method, and a known method may be used. For example, there are a method in which a polyethylene resin is dissolved in a solvent, an unsaturated carboxylic acid or a derivative thereof and a radical generator are added and heated and stirred, and a method in which the above components are supplied to an extruder and graft copolymerized.

The acid content in the acid-modified polyethylene resin (C) is preferably 0.1 to 10% by mass, more preferably 0.8 to 8% by mass.
The intrinsic viscosity [η] measured in tetralin at 135 ° C. of the acid-modified polyethylene resin (C) is preferably 0.1 to 3.0 dL / g.

  As the acid-modified polyethylene resin (C), a maleic acid-modified polyethylene resin is more preferable.

Content of acid-modified polyethylene resin (C) is 1-5 mass parts with respect to 100 mass parts of polycarbonate resin (A). When the content is less than 1 part by mass, the slidability is poor, and particularly when the amount exceeds 5 parts by mass, poor appearance tends to occur.
The content of the acid-modified polyethylene resin (C) is preferably 1 to 3 parts by mass.

[Release agent (D)]
The polycarbonate resin composition of the present invention does not contain a mold release agent or the content when it is contained is less than 0.1 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A).
Examples of the release agent (D) include aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15,000, and polysiloxane silicone oils. .

  Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic monovalent, divalent or trivalent carboxylic acid. Here, the aliphatic carboxylic acid includes alicyclic carboxylic acid. Among these, preferable aliphatic carboxylic acids are monovalent or divalent carboxylic acids having 6 to 36 carbon atoms, and aliphatic saturated monovalent carboxylic acids having 6 to 36 carbon atoms are more preferable. Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, mellicic acid, tetrariacontanoic acid, montanic acid, adipine Examples include acids and azelaic acid.

  As aliphatic carboxylic acid in ester of aliphatic carboxylic acid and alcohol, the same thing as the said aliphatic carboxylic acid can be used, for example. On the other hand, examples of the alcohol include saturated or unsaturated monohydric or polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these, monovalent or polyvalent saturated alcohols having 30 or less carbon atoms are preferable, and aliphatic saturated monohydric alcohols or aliphatic saturated polyhydric alcohols having 30 or less carbon atoms are more preferable. In addition, an aliphatic includes an alicyclic compound here.

  Specific examples of such alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol, and the like. Is mentioned.

  In addition, said ester may contain aliphatic carboxylic acid and / or alcohol as an impurity. Moreover, although said ester may be a pure substance, it may be a mixture of a plurality of compounds. Furthermore, the aliphatic carboxylic acid and alcohol which combine to form one ester may be used alone or in combination of two or more in any combination and ratio.

  Specific examples of esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture based on myricyl palmitate), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, glycerin monostearate Examples thereof include rate, glycerol distearate, glycerol tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate and the like.

  Examples of the aliphatic hydrocarbon having a number average molecular weight of 200 to 15,000 include liquid paraffin, paraffin wax, microwax, polyethylene wax, Fischer-Tropsch wax, and α-olefin oligomer having 3 to 12 carbon atoms. Here, the aliphatic hydrocarbon includes alicyclic hydrocarbons. Further, these hydrocarbons may be partially oxidized. The number average molecular weight is preferably 5,000 or less. The aliphatic hydrocarbon may be a single substance, but even a mixture of various constituent components and molecular weights can be used as long as the main component is within the above range.

  Among these, paraffin wax, polyethylene wax, or a partial oxide of polyethylene wax is preferable, paraffin wax and polyethylene wax are more preferable, and polyethylene wax is particularly preferable.

In addition, when it contains a mold release agent, 1 type may contain and 2 or more types may contain it by arbitrary combinations and ratios.
When the mold release agent (D) is contained, the content is less than 0.1 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A). If the mold release agent (D) is contained in an amount of 0.1 parts by mass or more, it will bleed out during pre-drying before molding, causing problems such as fusion of pellets into a lump, and bleeding out from the molded product during product use. The surface becomes sticky. The preferable content in the case of containing the release agent (D) is 0.05 parts by mass or less, more preferably 0.01 parts by mass or less with respect to 100 parts by mass of the polycarbonate resin (A).

[Other ingredients]
In the polycarbonate resin composition of the present invention, in addition to the above-mentioned (A) to (D), other resins and resin additives may be contained, but even when they are contained, the resins (A) to (C) The content of the resin other than) is preferably 1% by mass or less in 100% by mass of the polycarbonate resin composition. Moreover, it is preferable that the sum total content of components other than said resin (A)-(C) and a mold release agent (D) shall be 1 mass% or less in 100 mass% of polycarbonate resin composition.
Examples of other components include resins other than those described above and various resin additives other than those described above.

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.

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, Examples thereof include a lubricant, an antiblocking agent, a fluidity improver, a plasticizer, a dispersant, and an antibacterial agent.

[Production of polycarbonate resin composition]
There is no limitation on the method for producing the polycarbonate resin composition of the present invention, and a known method for producing a polycarbonate resin composition can be widely adopted. After the above components are mixed in advance using various mixers such as a tumbler or a Henschel mixer, for example. And a melt kneading method using a mixer such as a Banbury mixer, a roll, a Brabender, a single-screw kneading extruder, a twin-screw kneading extruder, or a kneader. 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 molded from polycarbonate resin compositions are suitable for parts in the automotive interior field, OA equipment field, home appliances, electrical and electronic fields, etc. because they generate less gas and bleed out from the molded product and have excellent slidability. Can be used for

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 4, Comparative Examples 1 to 14]
Each of the above components were blended in the proportions shown in Table 2 below, mixed for 20 minutes with a tumbler, then fed to a Nippon Steel Works twin screw extruder (TEX30α) equipped with 1 vent, screw rotation speed 200 rpm, Polycarbonate resin composition that is melt-kneaded at a discharge rate of 20 kg / hour, a resin temperature of 280 to 300 ° C. (measured value), the molten resin composition extruded in a strand form is rapidly cooled in a water tank, and pelletized using a pelletizer. Pellets were obtained.

<Evaluation of various physical properties>
[Preparation of test piece]
Further, after drying the obtained pellets at 120 ° C. for 5 hours, using an injection molding machine (NEX80III) manufactured by Nissei Plastic Industry Co., Ltd. under conditions of a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C. An ISO multipurpose test piece (4 mm thick), an ISO multipurpose test piece for Charpy impact test (3 mm thickness), and a 100 × 100 × 3 mm test piece for appearance evaluation and slidability evaluation were injection molded.

[Bending elastic modulus and bending strength]
Using the ISO multipurpose test piece (4 mm thickness), the flexural modulus (unit: MPa) and the flexural strength (unit: MPa) were measured in an environment of 23 ° C. in accordance with ISO178.

[Charpy impact strength]
Using the ISO multipurpose test piece (3 mm thick), the Charpy impact strength with notch (unit: kJ / m ² ) was measured in an environment of 23 ° C. according to ISO 179-1.

[Amount of generated gas]
After putting 5 g of the obtained pellets into a glass vial with an internal volume of 26 ml and heating at 150 ° C. for 2 hours, a sample was taken from the gas phase part using a microsyringe, analyzed by gas chromatography, The converted concentration (ppm) with toluene as the standard sample was calculated, and the amount of generated gas was determined according to the following criteria.
○: Toluene equivalent concentration of peak total area is 50 ppm or less Δ: Toluene equivalent concentration of peak total area is 51 to 200 ppm
×: Toluene equivalent concentration of peak total area is 201 ppm or more

[Evaluation of appearance]
The appearance of the test piece for appearance evaluation obtained above was visually judged according to the following criteria.
○: The dispersion state is good and the surface is glossy.
Δ: Uneven portions and irregularities are observed in the vicinity of the gate and the like.
X: A state in which uneven portions are observed in the entire molded product and there are many irregularities.

[Slidability]
<Dynamic friction coefficient μ, wear amount>
The test piece for slidability evaluation obtained above was subjected to 1000 times of load 1000g and distance 20mm 1000 times with Shinto Kagaku surface quality measuring device Tribogear Type: 38. The amount of wear (unit: mg) was measured.

The above evaluation results are shown in Table 2 below.

  The polycarbonate resin composition of the present invention maintains high mechanical properties such as strength and impact resistance, has a small amount of gas generated from the molded product and bleed out, and has high slidability excellent in both dynamic friction coefficient and wear amount. Since the appearance of the molded product is good, it can be widely used as various parts and products in the automotive interior field, OA equipment field, home appliance, electrical and electronic field, etc., and the industrial utility value is extremely high.

Claims (2)

  4 to 15 parts by mass of ethylene or ethylene-vinyl acetate copolymer (B) having a styrene-based (co) polymer segment and 1 to 1 of acid-modified polyethylene resin (C) with respect to 100 parts by mass of the polycarbonate resin (A). A polycarbonate resin composition containing 5 parts by mass and containing no release agent (D) or having a content of less than 0.1 parts by mass.   A molded product formed by molding the polycarbonate resin composition according to claim 1.