JPH08208973A - Polycarbonate resin composition and automotive door handle made using the same - Google Patents

Abstract

PURPOSE: To obtain a composition capable of imparting an excellent appearance, high heat resistance, rigidity, sliding properties, and impact properties to a polycarbonate resin molding. CONSTITUTION: This composition comprises 30-89 pts.wt. polycarbonate resin (A), 10-50 pts.wt. aromatic polyester resin (B), 0-50 pts.wt. rubbery elastomer (C), 1-30 pts.wt. talc (D), and 0.1-5 pts.wt. polyolefin resin (E), the sum of (A) to (D) being 100 pts.wt.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polycarbonate resin composition and an automobile exterior member using the same, and more particularly to solvent resistance, impact resistance, rigidity and sliding properties without impairing the appearance of the polycarbonate resin molding. TECHNICAL FIELD The present invention relates to a polycarbonate resin composition having improved kinematics, and a door handle for an automobile, which has a rotary sliding portion formed by using the improved resin composition and has excellent properties.

[0002]

2. Description of the Related Art Conventionally, polycarbonate resins provide molded products having excellent mechanical properties such as impact strength and tensile strength as well as electrical properties and transparency, and are used as engineering plastics in the fields of automobiles, electric and electronic devices, It is widely used in various fields such as OA equipment field, but when polycarbonate resin is used for automobile interior and exterior materials that require solvent resistance and impact resistance, polyester resin alone or rubber-like elastic body Are used in combination. Recently, in a molded article for automobile parts using the above-mentioned polyester resin alone or a polycarbonate resin composition to which a rubber-like elastic material is further added, in order to improve rigidity, fine inorganic particles such as talc, mica and potassium titanate whiskers are further added. Attempts have been made to incorporate fillers. Although these inorganic fillers have some auxiliary effects, since these fillers usually show alkalinity, they accelerate the hydrolysis of the polycarbonate-based resin or polyester resin during molding and lower their molecular weight. In some cases, the appearance may be impaired due to skin roughness and yellowing of the molded body, which is not always preferable in terms of long-term practical characteristics. In order to suppress this resin deterioration, it has been attempted to further blend a phosphite compound (Japanese Patent Laid-Open No. 5-222283).

On the other hand, a molded product using the above composition has insufficient slidability, and a rotary shaft made of metal, ceramic, plastic or the like is inserted into the perforated portion of the molded product to continuously rotate or reciprocate. When the rotation is repeated, the amount of wear of the sliding portion is large. When it is used in the rotary sliding part of a door handle for an automobile and the door is repeatedly opened / closed (opening / closing operation by vertical movement of the lever, etc.), a large amount of wear of the sliding part causes shaft runout and The opening / closing operation cannot be performed smoothly.
In fact, as a result of a durability test in which the door was repeatedly opened and closed with the door handle lever, it was found that the sliding portion of the molded body had a large amount of wear.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a polycarbonate resin capable of imparting excellent slidability and low temperature impact characteristics to a molded article of an aromatic polyester resin or a polycarbonate resin composition further containing a rubber-like elastic material and talc. It is an object of the present invention to find a composition and to provide a door handle for an automobile having excellent long-term durability performance by using this resin composition.

[0005]

The inventors of the present invention have conducted extensive studies to complete a polycarbonate resin composition having the above-mentioned preferable properties and an automobile door handle using the resin composition. It has been found that the above problems can be solved by mixing a resin, an aromatic polyester resin, a rubber-like elastic material that is used in some cases, and talc and a polyolefin resin at a predetermined ratio. The present invention has been completed based on such findings. That is, the gist of the present invention is as follows. (First) (A) polycarbonate resin, (B) aromatic polyester resin, (C) rubber-like elastic material, (D) talc and (E) polyolefin, copolymer of polyolefin and unsaturated carboxylic acid, and polyolefin (A), (B), (C) and (D) is a polycarbonate resin composition prepared by blending at least one polyolefin resin selected from copolymers of unsaturated carboxylic acid anhydrides.
Of (A) is 30 to 89% by weight,
(B) is 10 to 50% by weight, (C) is 0 to 50% by weight,
(D) is 1 to 30% by weight, and (A), (B),
With respect to 100 parts by weight of the total of (C) and (D), (E) is
The polycarbonate resin composition is 0.1 to 5 parts by weight. (2nd) The polycarbonate resin composition according to the above-mentioned 1st, wherein the average particle diameter of (D) talc is 0.3 to 1.0 µm as measured by a light transmission type particle size distribution analyzer. (3rd) The polycarbonate resin composition according to the above 1st, wherein the polyolefin of (E) is polyethylene. (Fourth) An automobile door handle having a rotary sliding portion formed by using the polycarbonate resin composition according to any one of the first to third aspects.

The contents of the present invention will be described in detail below. There are various types of polycarbonate resin as the component (A) that constitutes the resin composition of the present invention, preferably the general formula (I)

[0007]

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[Wherein R¹And R²Is the hydrogen source
Child, halogen atom (chlorine, bromine, fluorine, iodine) or
An alkyl group having 1 to 8 carbon atoms (eg, methyl group, ethyl group
Group, n-propyl group, isopropyl group, n-butyl group,
Isobutyl group, amyl group, isoamyl group, hexyl group
), Whether they are the same or different
Good. Also R¹If there are multiple R¹Are the same
May be different, R ²If there are multiple R²
May be the same or different. m and n are respectively
It is an integer of 1 to 4. Y is a single bond or an alkyl group having 1 to 8 carbon atoms.
Rukilen group or alkylidene group having 2 to 8 carbon atoms (for example,
For example, methylene group, ethylene group, propylene group, butylene
Group, pentylene group, hexylene group, ethylidene group, iso
Propylidene group), cycloalkyl having 5 to 15 carbon atoms
Ren group or cycloalkylidene group having 5 to 15 carbon atoms (eg,
For example, cyclopentylene group, cyclohexylene group, cyclo
Lopentylidene group, cyclohexylidene group, etc.), or
-S-, -SO-, -SO₂-, -O-, -CO- bond
Or formula (II) or (II ')

[0009]

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The bond represented by ] The polymer containing the structural unit represented by these can be mentioned. This polycarbonate resin has the general formula (III)

[0011]

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( ¹ ) wherein R ¹ , R ² , Y, m and n are the same as defined above, and easily produced by reacting a dihydric phenol with phosgene or a carbonic acid diester compound. Is something that can be done. That is, for example, by reacting a dihydric phenol with a carbonate precursor such as phosgene in a solvent such as methylene chloride in the presence of a known acid acceptor or a molecular weight regulator, or by reacting dihydric phenol with diphenyl carbonate. It is produced by a transesterification reaction with another carbonate precursor.

Here, there are various dihydric phenols represented by the general formula (III), and in particular,
2,2-bis (4-hydroxyphenyl) propane [common name: bisphenol A] is preferable. Examples of dihydric phenols other than bisphenol A include bis (4-
Hydroxyphenyl) methane; Bis (4-hydroxyphenyl) phenylmethane; Bis (4-hydroxyphenyl) naphthylmethane; Bis (4-hydroxyphenyl)
-(4-isopropylphenyl) methane; bis (3,5
-Dichloro-4-hydroxyphenyl) methane; bis (3,5-dimethyl-4-hydroxyphenyl) methane; 1,1-bis (4-hydroxyphenyl) ethane;
1-naphthyl-1,1-bis (4-hydroxyphenyl) ethane; 1-phenyl-1,1-bis (4-hydroxyphenyl) ethane; 1,2-bis (4-hydroxyphenyl) ethane; 2-methyl -1,1-bis (4-hydroxyphenyl) propane; 2,2-bis (3,5-
Dimethyl-4-hydroxyphenyl) propane; 1-ethyl-1,1-bis (4-hydroxyphenyl) propane; 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane; 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane; 2,2-bis (3-chloro-4-hydroxyphenyl) propane;
2,2-bis (3-methyl-4-hydroxyphenyl)
Propane; 2,2-bis (3-fluoro-4-hydroxyphenyl) propane; 1,1-bis (4-hydroxyphenyl) butane; 2,2-bis (4-hydroxyphenyl) butane; 1,4-bis (4-Hydroxyphenyl) butane; 2,2-bis (4-hydroxyphenyl)
Pentane; 4-methyl-2,2-bis (4-hydroxyphenyl) pentane; 2,2-bis (4-hydroxyphenyl) hexane; 4,4-bis (4-hydroxyphenyl) heptane; 2,2-bis (4-Hydroxyphenyl) nonane; 1,10-bis (4-hydroxyphenyl) decane; 1,1-bis (4-hydroxyphenyl)
-3,3,5-Trimethylcyclohexane; 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3
Dihydroxydiaryl alkanes such as 3-hexafluoropropane, 1,1-bis (4-hydroxyphenyl) cyclohexane; 1,1-bis (3,5-dichloro-4-hydroxyphenyl) cyclohexane; 1,1-
Dihydroxydiarylcycloalkanes such as bis (4-hydroxyphenyl) cyclodecane, bis (4-hydroxyphenyl) sulfone; bis (3,5-dimethyl-4-hydroxyphenyl) sulfone; bis (3-chloro-4-hydroxyphenyl) ) Dihydroxydiarylsulfones such as sulfones, bis (4-hydroxyphenyl) ether; dihydroxydiarylethers such as bis (3,5-dimethyl-4-hydroxyphenyl) ether, 4,4′-dihydroxybenzophenone;
3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxydiarylketones such as dihydroxybenzophenone, bis (4-hydroxyphenyl) sulfide;
Bis (3-methyl-4-hydroxyphenyl) sulfide; dihydroxydiaryl sulfides such as bis (3,5-dimethyl-4-hydroxyphenyl) sulfide, dihydroxydiaryl sulfoxides such as bis (4-hydroxyphenyl) sulfoxide, 4 , 4 '
-Dihydroxydiphenyls such as dihydroxydiphenyl, and dihydroxyarylfluorenes such as 9,9-bis (4-hydroxyphenyl) fluorene. In addition to the dihydric phenols represented by the general formula (III), dihydroxybenzenes such as hydroquinone, resorcinol and methylhydroquinone, 1,5-dihydroxynaphthalene; dihydroxynaphthalene such as 2,6-dihydroxynaphthalene, etc. Is mentioned.
These dihydric phenols may be used alone or in combination of two or more.

Examples of the carbonic acid diester compound include diaryl carbonate such as diphenyl carbonate and dialkyl carbonate such as dimethyl carbonate and diethyl carbonate. As the molecular weight regulator, those usually used for polymerization of polycarbonate may be used, and various types may be used. Specifically, as the monohydric phenol, for example, phenol, p-cresol, p-tret-butylphenol, p
-Tret-octylphenol, p-cumylphenol,
Examples include bromophenol, tribromophenol and nonylphenol. Also, in some cases,
The polycarbonate resin as the component (A) has the general formula (I) above.

[0015]

[Chemical 4]

(In the formula, R ¹ , R ² , Y, m and n are the same as above.) A polycarbonate part having a repeating unit having a structure represented by the general formula (IV)

[0017]

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[Wherein R ³ , R ⁴ and R ⁵ are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, propyl group, n-butyl group, isobutyl group, amyl group). Groups, isoamyl groups, hexyl groups, etc.) or phenyl groups, which may be the same or different. Further, p and q are 0 or 1 respectively.
Both are integers above, but both are not 0. ] A polycarbonate-polyorganosiloxane copolymer composed of a polyorganosiloxane part having a repeating unit represented by the following formula may be used. The polyorganosiloxane part preferably has a degree of polymerization of 5 or more.

In the present invention, the polycarbonate resin as the component (A) may optionally contain a branched polycarbonate. Examples of the branching agent used for obtaining the branched polycarbonate include phloroglucin, mellitic acid, trimellitic acid, trimellitic acid chloride, trimellitic anhydride, gallic acid, and gallic acid n-.
Propyl, protocatechuic acid, pyromellitic acid, pyromellitic dianhydride, α-resorcinic acid, β-resorcinic acid, resorcinaldehyde, trimethyl chloride, isatin bis (o-cresol), trimethyl trichloride, 4-
Chloroformylphthalic anhydride, benzophenone tetracarboxylic acid; 2,4,4'-trihydroxybenzophenone; 2,2 ', 4,4'-tetrahydroxybenzophenone;2,4,4'-trihydroxyphenylether; 2 , 2 ', 4,4'-Tetrahydroxyphenyl ether; 2,4,4'-trihydroxydiphenyl-2
-Propane; 2,2'-bis (2,4-dihydroxy)
Propane; 2,2 ', 4,4'-tetrahydroxydiphenylmethane;2,4,4'-trihydroxydiphenylmethane; 1- [α-methyl-α- (4'-dihydroxyphenyl) ethyl] -3- [α ', Α'-bis (4 "
-Hydroxyphenyl) ethyl] benzene; 1- [α-
Methyl-α- (4′-dihydroxyphenyl) ethyl]
-4- [α ', α'-bis (4 "-hydroxyphenyl) ethyl] benzene; α, α', α" -tris (4-
Hydroxyphenyl) -1,3,5-triisopropylbenzene; 2,6-bis (2-hydroxy-5'-methylbenzyl) -4-methylphenol; 4,6-dimethyl-2,4,6-tris ( 4'-hydroxyphenyl)
-2-heptene; 4,6-dimethyl-2,4,6-tris (4'-hydroxyphenyl) -2-heptane; 1,
3,5-Tris (4'-hydroxyphenyl) benzene; 1,1,1-tris (4-hydroxyphenyl) ethane; 2,2-bis [4,4-bis (4'-hydroxyphenyl) cyclohexyl] propane 2,6-bis (2'-hydroxy-5'-isopropylbenzyl)-
4-isopropylphenol; bis [2-hydroxy-
3- (2'-hydroxy-5'-methylbenzyl) -5
-Methylphenyl] methane; bis [2-hydroxy-3
-(2'-hydroxy-5'-isopropylbenzyl)
-5-methylphenyl] methane; tetrakis (4-hydroxyphenyl) methane; tris (4-hydroxyphenyl) phenylmethane; 2 ', 4', 7-trihydroxyflavan; 2,4,4-trimethyl-2 ', 4 ', 7
-Trihydroxyflavan; 1,3-bis (2 ', 4'
-Dihydroxyphenylisopropyl) benzene; tris (4'-hydroxyphenyl) -amyl-s-triazine and the like.

In addition, as the polycarbonate resin as the component (A), for example, a linear aliphatic divalent carboxylic acid such as adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid or decanedicarboxylic acid can be used. It is also possible to use a copolymer as a polymerization monomer.

In the present invention, the polycarbonate resin as the component (A) may be used alone or in combination of two or more kinds. From the viewpoint of mechanical strength and moldability, the polycarbonate resin preferably has a viscosity average molecular weight of 10,000 to 100,000, and particularly preferably 15,000 to 40,000.

Various aromatic polyester resins can be used as the component (B). For example,
A polyester resin obtained by polymerizing a bifunctional carboxylic acid and an alkylene glycol is particularly preferable. here,
Examples of the difunctional carboxylic acid include terephthalic acid,
Aromatic dicarboxylic acids such as isoterephthalic acid and naphthalenedicarboxylic acid. Among these, terephthalic acid is preferable, and other bifunctional carboxylic acids such as oxalic acid, malonic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and decanedicarboxylic acid are preferable as long as the effects of the present invention are not impaired. Aliphatic dicarboxylic acids such as acids and their ester-forming derivatives can also be used in combination. Generally, the mixing ratio of these other bifunctional carboxylic acids is preferably within 20 mol% with respect to the total difunctional carboxylic acids used in the polyester resin.

The alkylene glycol is not particularly limited, but for example, ethylene glycol; propylene-1,2-glycol; propylene-1,3-glycol; butylene-1,4-glycol; butylene-
2,3-glycol; hexane-1,6-diol; octane-1,8-diol; neopentyl glycol,
An aliphatic diol having 2 to 15 carbon atoms such as decane-1,10-diol, polyethylene glycol, etc. can be used. Further, two or more kinds of glycol components may be used in combination. Polyethylene terephthalate and polybutylene terephthalate are particularly preferable as the polyester resin obtained by polymerizing such a bifunctional carboxylic acid and alkylene glycol.

The aromatic polyester resin as the component (B) can be produced by a usual method in the presence or absence of a polycondensation catalyst containing titanium, germanium, antimony or the like. For example, polyethylene terephthalate is usually esterified with terephthalic acid and ethylene glycol, or transesterified with a lower alkyl ester of terephthalic acid such as dimethyl terephthalate and ethylene glycol to give a glycol ester of terephthalic acid and / or The first stage reaction to produce the low polymer and then the glycol ester and / or
Alternatively, it is produced by a second-stage reaction, which is a so-called polymerization reaction, in which the low polymer is further polymerized to obtain a polymer having a high degree of polymerization. The aromatic polyester resin as the component (B) may be used alone or in combination of two or more.

Next, as the rubber-like elastic body of the component (C),
Various ones can be used. A good example is
It is a copolymer obtained by polymerizing one or more vinyl monomers in the presence of a rubbery polymer. Examples of the vinyl-based monomer include styrene,
Examples thereof include aromatic vinyl compounds such as α-methylstyrene, acrylic acid esters such as methyl acrylate and ethyl acrylate, methacrylic acid esters such as methyl methacrylate and ethyl methacrylate, and vinyl cyanide compounds such as acrylonitrile.

Representative examples of the rubber-like elastic material include acrylic polymers and methacrylic polymers mainly containing alkyl acrylates and alkyl methacrylates, diene polymers mainly containing conjugated dienes such as butadiene and isoprene, and poly It is a copolymer of one or more silicone-based polymers mainly composed of organosiloxane, and is usually called MAS resin, MBS resin, or MABS resin. The rubber-like elastic body is, for example, Japanese Patent Publication No. Sho 48-293.
No. 08 (MAS resin), JP-B-55-9435 (MBS resin), JP-A-64-6051 (MA)
IS resins), known resins disclosed in JP-A-64-79257 and the like can be used. These rubber-like elastic bodies include, for example, Paraloid KM330 [ROHM & Haas Co., MAS resin], Metabrene C-223.
[MBS resin manufactured by Mitsubishi Rayon Co., Ltd.], METABLEN S-2001 [MAS resin manufactured by Mitsubishi Rayon Co., Ltd.]
Etc. can be easily obtained from the market.

Specific examples of rubber-like elastic bodies other than the above are, for example, butadiene rubber (BR), styrene-butadiene rubber (SBR), isobutylene-isoprene rubber (IIR), ethylene-propylene rubber (EPR), ethylene- Propylene-diene rubber (EPDM), acrylonitrile-butadiene rubber (NBR), styrene-butadiene-styrene rubber (SBS), hydride of styrene-butadiene rubber (SEBS), styrene-isoprene-styrene rubber (SIS), styrene-isoprene rubber Hydrides (SEPS) and the like.
The rubber-like elastic body as the component (C) may be used alone or in combination of two or more kinds.

The characteristics of talc as the component (D) in the resin composition of the present invention and the manufacturing method thereof are not particularly limited, but regarding the characteristics relating to the particle diameter, the average particle diameter is the light transmission type particle size distribution measurement. Measured with a measuring instrument, 0.3 to 1.0
Talc which is μm is preferred. If it exceeds 1.0 μm, there is no problem in practical use, but the surface roughness of the molded product becomes noticeable.

Further, talc can be manufactured, for example, by the following method. That is, rough stones are tube mill type crusher, impact type crusher, micron mill type crusher,
Grind with a device such as a centrifugal roller type Raymond mill.
And when fine pulverization is required, a micron mill,
It may be dry or wet finely pulverized with a jet type pulverizer, a jet-o-mizer, a micronizer, a jet pulverizer, a stirring mill (tower mill), a vibration mill, a colloid mill, or the like. Next, these crushed talc and mica are cyclone, multilon, micron separator, microplex, cyclone air separator,
Ultra Separator, Jet Cron, Craciron, Rake Classifier, Hydro Cyclone, Hydropower Classifier,
With a device such as a centrifugal classifier, physical properties such as particle size can be adjusted by repeating dry or wet classification once or multiple times.

The cause of coloring of the polycarbonate resin composition molded body by talc is the hydrolyzability of the polycarbonate or the aromatic polyester as described in the section of the prior art, but a surface treatment agent is used to prevent this. It was found that the talc surface treatment method that was used was effective.
Preferred examples of the surface treatment agent include various coupling agents, reactive silicone compounds, acidic compounds and the like.

The method of treating with these surface treatment agents is not particularly limited, and any conventionally used method such as an aqueous solution method, an organic solvent method or a spray method can be used. The surface treating agent is usually used in a proportion of 0.1 to 10% by weight with respect to talc.
If this amount is less than 0.1% by weight, the effect of suppressing the deterioration of the resin is not sufficiently exerted, and if it exceeds 10% by weight, the effect is not improved for the amount, and rather the feed during kneading is unsatisfactory. Be stable.

The polyolefin resin used as the component (E) in the resin composition of the present invention is a group consisting of polyolefin, a copolymer of polyolefin and unsaturated carboxylic acid, and a copolymer of polyolefin and unsaturated carboxylic anhydride. It is at least one kind selected from Examples of the polyolefin used here include ethylene; propylene; butene-1; isobutylene; pentene-1;
3-Methylbutene-1; 4-Methylpentene-1; Hexene-1; Homopolymers of olefins such as α-olefins such as octene, copolymers of two or more of these olefins, and 70 moles of these olefins. % Or more, preferably 80 mol% or more, and a vinyl compound, for example, vinyl ester such as vinyl acetate, vinyl halide such as vinyl chloride, unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, methyl acrylate. , And copolymers with unsaturated carboxylic acid esters such as ethyl acrylate, methyl methacrylate, and ethyl methacrylate. Specifically, low density polyethylene, linear low density polyethylene, high density polyethylene, isotactic polypropylene, atactic polypropylene, ethylene / propylene copolymer, ethylene / vinyl acetate copolymer or its saponified product, ethylene / acrylic. Examples include methyl acid copolymers, ethylene / ethyl methacrylate copolymers, ethylene / methyl methacrylate copolymers.

As a specific example of unsaturated carboxylic acid and unsaturated carboxylic acid anhydride which are copolymerization components with polyolefin, acrylic acid. Methacrylic acid, maleic acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, nadic acid (endocis-bicyclo [2.2.1] hept-5ene-2,3-dicarboxylic acid), maleic anhydride, nadic anhydride, Examples thereof include citraconic anhydride, and of these, maleic anhydride, maleic acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, nadic acid and the like are preferable.

For producing a copolymer of a polyolefin and an unsaturated carboxylic acid or a copolymer of a polyolefin and an unsaturated carboxylic acid anhydride, it is usual to modify the polyolefin with an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride. Various methods can be adopted. For example, there is a method in which a radical reaction initiator is added to polyolefin and maleic anhydride in the presence or absence of a solvent, and the mixture is heated. In this reaction, other vinyl monomers such as styrene or rubbers such as liquid rubber and thermoplastic rubber may be allowed to coexist. The content of unsaturated carboxylic acid or unsaturated carboxylic acid anhydride of the obtained copolymer is not particularly limited,
It is preferably 5.0% by weight or less. If it exceeds 5.0% by weight, the heat resistance of the polycarbonate resin composition tends to decrease, or the molded product thereof tends to yellow.

In the resin composition of the present invention, the above (A),
The composition ratio of the component (E) to the total of the components (B), (C) and (D) is 0.1 with respect to 100 parts by weight of the former.
5 to 5 parts by weight, and in the total 100% by weight of the respective components (A), (B), (C) and (D), the polycarbonate resin as the component (A) is 30 to 89% by weight, The aromatic polyester resin as the component) may be added in an amount of 10 to 50% by weight, the rubber-like elastic body as the component (C) may be added in an amount of 0 to 50% by weight, and the talc as the component (D) may be added in an amount of 1 to 30% by weight. is necessary.

When the composition ratio of the component (E) in the composition comprising the components (A) to (E) is less than 0.1 part by weight, a vehicle door molded using the composition according to the present invention. In addition to the slidability of the rotary sliding portion of the handle and the rotary shaft inserted therein being poor, the effect of improving impact resistance is also insufficient. On the other hand, if the amount exceeds 5 parts by weight, the rigidity and strength of the automobile door handle having the rotary sliding portion deteriorates, and the appearance of the molded product deteriorates. The addition amount of the component (E) is particularly preferably 0.5 to 4 parts by weight.

In the composition according to the present invention, the above (A) to
When the content of the component (A) is less than 30% by weight in the total 100% by weight of the respective components of the component (D), the original properties of the polycarbonate resin are lost, and when it exceeds 89% by weight, the blending amount of the other components is decreased. When the content of the component (B) is less than 10% by weight, the effect of improving the solvent resistance is not sufficiently exhibited, and when it exceeds 50% by weight, the composition having the desired improved physical properties is not obtained. The original properties of the polycarbonate resin cannot be fully exhibited, and the component (C) is added to improve the impact strength, but its content is 50% by weight.
When it exceeds the above range, the original properties of the polycarbonate resin cannot be fully exhibited. Further, if the content of the component (D) is less than 1% by weight, the effect of improving the rigidity is not sufficiently exhibited, and if it exceeds 30% by weight, the specific gravity of the molded product using the composition becomes large and the impact resistance is high. In addition, the appearance tends to deteriorate. However, from the viewpoint of preventing deterioration of solvent resistance, rigidity, impact resistance, appearance, etc., which are the inherent properties of polycarbonate-based resin, 50 to 85% by weight of component (A),
15-40% by weight of component (B) and 0-30 of component (C)
It is preferable to contain the component (D) in an amount of 1 to 20% by weight, and particularly the component (A) in an amount of 55 to 80% by weight,
Component (B) is 15 to 35% by weight, component (C) is 0 to 20
It is more preferable that the content of the component (D) is 1 to 15% by weight.

In the resin composition of the present invention, a phosphite-based antioxidant (hereinafter, this component is referred to as (F) as an antioxidant, if desired, in order to prevent coloration of the molded product and deterioration of strength. Is present), and is preferably blended in the range of 0.01 to 5 parts by weight with respect to 100 parts by weight in total of the components (A) to (D). If the amount is less than 0.01 parts by weight, the effect of suppressing the deterioration of the resin is not sufficiently exerted, and if it exceeds 5 parts by weight, the effect is not improved for the amount, and it is rather economically disadvantageous. . From the viewpoint of the effect of suppressing the deterioration of the resin and the economical efficiency, the more preferable compounding amount when the phosphite-based antioxidant is used is 0.0
It is in the range of 5 to 4 parts by weight, and particularly preferably in the range of 0.1 to 2 parts by weight.

There are various kinds of phosphite-based antioxidants, for example, general formula (V) (R ⁶ O) ₃ P (V) (wherein R ⁶ is a hydrogen atom and has 1 carbon atom). To an alkyl group having 20 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 30 carbon atoms or an arylalkyl group having 7 to 30 carbon atoms, and these hydrocarbon groups include a halogen atom,
An alkylthio group having 1 to 30 carbon atoms or a hydroxyl group may be introduced. The three R ^{6 s} may be the same or different, but not all of them are hydrogen atoms. ) Or a general formula (VI)

[0040]

[Chemical 6]

(In the formula, R⁷And R⁸Is hydrogen source
Child, an alkyl group having 1 to 20 carbon atoms, an alkyl group having 6 to 20 carbon atoms
Reel group, alkylaryl group having 7 to 20 carbon atoms, or charcoal
Showing an arylalkyl group having a prime number of 7 to 20
A hydrogen atom includes a halogen atom and an alkyl group having 1 to 30 carbon atoms.
A ruthio group or a hydroxyl group may be introduced.
R ⁷And R⁸May be the same or different
But neither is a hydrogen atom. Z is an ether bond
Is a tetravalent hydrocarbon residue having 1 to 20 carbon atoms which is not included.
You. The compound represented by these can be mentioned. One above
Among the phosphite compounds represented by general formula (VI), Z
Is the expression

[0042]

[Chemical 7]

A pentaerythritol type phosphite compound represented by the following formula is preferable. Examples of the phosphite compound represented by the general formula (V) include tris (mixed mono and di-nonylphenyl) phosphite, trisnonylphenyl phosphite, tris (2,4-di-t-butylphenyl). Examples include phosphite, triphenyl phosphite, diphenyl mono (2-ethylhexyl) phosphite, and the general formula (VI)
Examples of the phosphite compound represented by: bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-)
4-Methylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite and the like can be mentioned. These phosphite compounds may be used alone or in combination of two or more.

The resin composition of the present invention includes the above (A),
In addition to the components (B), (C), (D), and (E), the above phosphite-based antioxidant is added, if necessary, but various addition components within a range not impairing the object of the present invention. , Other synthetic resins, other antioxidants such as hindered phenols and amines, UV absorbers such as benzotriazoles and benzophenones, hindered amine light stabilizers, aliphatic carboxylic acid ester-based, paraffin-based ，
Internal lubricants such as silicone oil and polyethylene wax, flame retardants, flame retardant aids, antistatic agents, other inorganic fillers and organic fillers, release agents, colorants and the like can be added.

The resin composition of the present invention comprises the above (A),
It can be prepared by mixing the components (B), (C), (D) and (E) with various additive components used as necessary and kneading. For the compounding and kneading, commonly used methods such as ribbon blender, Henschel mixer, Banbury mixer, drum tumbler, single-screw extruder, twin-screw extruder, co-kneader, and multi-screw extruder are used. It can be performed by a method. The heating temperature for kneading is
It is usually selected in the range of 240 to 300 ° C. The polycarbonate resin composition thus obtained is subjected to various known molding methods such as injection molding, blow molding, extrusion molding, compression molding, calender molding, rotational molding, and various molded articles such as automobile exterior members. Can be used for manufacturing.

The present invention also provides an automobile door handle having a rotary sliding portion, which is formed by molding the above polycarbonate resin composition. The door handle for an automobile is a handle attached to open and close the door of an automobile.In the wall of the door, the handle portion of the door handle is manually rotated, and when the hand is released, it is automatically and elastically activated by a spring. Fig. 7 is a handle having a reversing rotary slide with a rotation axis and perforations with clips inserted. This rotary sliding part is required to have high sliding characteristics between the rotary shaft and the clip, that is, the amount of sliding wear, sliding friction heat, and sliding resistance are extremely low, so a material with a special material is required. However, the composition according to the present invention meets this requirement well.

FIG. 1 is a schematic view of this door handle lever, and is a perspective view seen from the side of the rotary sliding portion which is the back side of the door handle. The door handle 1 mainly includes a handle portion 2 and a rotary sliding portion 3 on the back surface thereof. The rotary sliding portion 3 has perforations 4 and 5 at the tip side thereof. It becomes the central axis of rotation of the handle. Generally, a nylon clip is attached to the perforation 5, and the perforation 5 is interlocked with an unlocking portion inside the door so that the clip rotates during operation.
Therefore, since the inner wall surfaces of the perforations 4 and 5 of the rotary sliding portion 3 always perform rotational and reverse sliding motions with respect to the rotary shaft and the outer surface of the clip, the sliding wear characteristic is an important characteristic. If the amount of dynamic wear is high, the function of the door handle will be reduced in a short period of time. Furthermore, since the door handle itself or the sliding portion is constantly subjected to tensile stress and impact stress when handling the handle of the door, high tensile strength and impact strength are required.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

【Example】

(Example 1) Polycarbonate resin and polyethylene terephthalate resin were mixed at 6 ° C at 120 ° C according to the formulation shown in Table 1.
After drying for an hour, dry blend with rubber-like elastic material, talc and low density polyethylene resin, cylinder temperature 280 ℃
Was melt-kneaded and pelletized by a twin-screw extruder with a vent. The obtained pellets were injection-molded at a cylinder temperature of 280 ° C. to prepare test pieces, and the mechanical properties such as tensile yield strength, Izod impact strength and specific wear amount were evaluated. The results are shown in the table.

Example 2 The same evaluations as in Example 1 were carried out except that the rubber-like elastic body was not used. The results are shown in the table.

Example 3 The same evaluation as in Example 1 was performed except that another rubber-like elastic body was used. The results are shown in the table.

Example 4 The same evaluations as in Example 3 were carried out except that the polyethylene terephthalate resin content was increased, the talc and low density polyethylene resin content was decreased, and the phosphite antioxidant was added. . The results are shown in the table.

Example 5 The same evaluation as in Example 4 was conducted except that the low density polyethylene resin was replaced with a maleic anhydride-modified high density polyethylene resin. The results are shown in the table.

(Example 6) The same evaluation as in Example 3 was carried out except that the polyethylene terephthalate resin was replaced with a polybutylene terephthalate resin and a phosphite antioxidant was added. The results are shown in the table.

Example 7 The same evaluation as in Example 2 was carried out except that the polyethylene terephthalate resin was replaced with a polybutylene terephthalate resin. The results are shown in the table.

Comparative Example 1 The same evaluation as in Example 3 was carried out except that the low density polyethylene resin was not used. The results are shown in the table.

Comparative Example 2 The same evaluation as in Example 4 was carried out except that the low density polyethylene resin and the phosphorus-based antioxidant were not used. The results are shown in the table.

Comparative Example 3 The same evaluation as in Example 4 was carried out except that the blending ratio of the polycarbonate resin was increased and the talc, the low density polyethylene resin and the phosphorus antioxidant were not used. The results are shown in the table.

Comparative Example 4 The same evaluation as in Example 6 was carried out except that the low density polyethylene resin and the phosphorus antioxidant were not used. The results are shown in the table.

The following components were used as the components used in Examples and Comparative Examples. In addition, (A) to (F) and (a) to (f) shown below are (A) to (F) in Table 1, respectively.
This corresponds to (F) and (a) to (f). (A) Polycarbonate resin: Polycarbonate manufactured by Idemitsu Petrochemical Co., Ltd. (trade name "Taflon A3000", viscosity average molecular weight 29,000) (B) Aromatic polyester resin: (a) Polyethylene terephthalate resin: Mitsubishi Rayon Co., Ltd. Polyethylene terephthalate (Brand name "Dianite MA-523V") (b) Polybutylene terephthalate resin: Mitsubishi Rayon Co., Ltd. polybutylene terephthalate (Brand name "Toughpet N1000") (C) Rubber-like elastic body: (c) Core shell Type Elastomer: Nippon Zeon Co., Ltd. MAIS resin (trade name "Hybrene B611") (d) Core shell type elastomer: Mitsubishi Rayon Co., Ltd.
MAS resin (trade name "Metabrene S-2001") (D) talc: talc manufactured by Asada Flour Mills (trade name "FF
R ”, average particle size 0.8 μm) (E) Polyolefin: (e) Low density polyethylene: Low density polyethylene (grade name“ 291A ”) manufactured by Tosoh Corporation (f) Maleic anhydride-modified high density polyethylene: Idemitsu Petroleum Chemical Industry Co., Ltd. maleic anhydride-modified high-density polyethylene (grade name "H6200P") (F) Phosphite-based antioxidant: Bis (2,6-di-t)
-Butyl-4-methylphenyl) pentaerythritol diphosphite

The measuring method of each characteristic shown in Table 1 is as follows. Tensile yield strength: According to JIS K-7113. Izod impact strength: Based on JIS K-7110. Specific wear amount: According to JIS K-7218 (however, method A, load 50N, mating material SUS)

[0061]

[Table 1]

Example 8 Using the polycarbonate resin composition shown in Example 3, a door handle having a shape and structure shown in FIG. 1 and having a length of about 15 cm was injection-molded and subjected to a slidability test. did. Attaching and fixing a smooth iron rotating shaft and nylon clip to the perforations 4 and 5 of the molded door handle, and applying a load of 10 kg to the door handle, a reciprocating motion of rotation and reversal of 50,000 is performed. Repeatedly, the open / close test of the door handle was performed, and the wear amount of the portion in contact with the rotating shaft and the clip was measured to evaluate the wear resistance. The amount of wear was 4 and 5 before and after the sliding test.
It was grasped by the change in the measured value of each pore size. The results are shown in Table 2.

Comparative Example 5 The same measurement as in Example 8 was carried out except that the polycarbonate resin composition shown in Comparative Example 1 was used. The results are shown in Table 2.

[0064]

[Table 2]

[0065]

INDUSTRIAL APPLICABILITY The polycarbonate resin composition of the present invention imparts not only excellent appearance, solvent resistance, impact resistance and rigidity, but also sliding wear resistance to the molded product, and the rotary sliding part. It was found that a door handle having good sliding wear resistance can be obtained by using it for an automobile door handle molded product.

[Brief description of drawings]

FIG. 1 is a perspective view of a door handle as seen from a rotary sliding portion side on the back side thereof.

[Explanation of symbols]

 1 ... Door handle 2 ... Handle part 3 ... Rotating sliding part 4 ... Perforation (rotating shaft) 5 ... Perforation (clip)

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Claims (4)

[Claims] 1. A polycarbonate resin, (B) an aromatic polyester resin, (C) a rubber-like elastic material, (D) talc and (E) a polyolefin, a copolymer of a polyolefin and an unsaturated carboxylic acid, and a polyolefin. And at least 1 selected from copolymers of unsaturated carboxylic acid anhydrides
It is a polycarbonate resin composition prepared by blending two kinds of polyolefin resins, wherein (A) is 30 to 89% by weight in the total 100% by weight of (A), (B), (C) and (D). B) is 10 to 50% by weight, (C) is 0 to 50% by weight, (D) is 1 to 30% by weight, and (A), (B),
With respect to 100 parts by weight of the total of (C) and (D), (E) is
A polycarbonate resin composition, characterized in that it is 0.1 to 5 parts by weight. 2. The polycarbonate resin composition according to claim 1, wherein the average particle size of talc (D) is 0.3 to 1.0 μm as measured by a light transmission type particle size distribution analyzer. 3. The polycarbonate resin composition according to claim 1, wherein the polyolefin (E) is polyethylene. 4. A door handle for an automobile, which has a rotary sliding portion formed by using the polycarbonate resin composition according to any one of claims 1 to 3.