JP6006976B2 - Compact - Google Patents

Description

  The present invention relates to a molded article obtained by molding a polycarbonate resin composition. More specifically, the present invention relates to a molded body obtained by molding a polycarbonate resin composition useful as an automobile part or as an electronic device or an information device.

Some automotive parts, particularly automobile interior parts, electronic devices, information devices, etc., must be painted on the surface of the product from the viewpoint of design and prevention of scratches. The main design features include a glossy appearance and an appearance (weld appearance) in a weld portion formed by the joining of resins during molding.
However, if the gloss and scratch resistance can be improved by the material itself, there is a possibility that a part satisfying the required characteristics can be obtained without using the mold technique and the molding technique.
Many automotive parts have filler-filled polypropylene as the main component, but because the surface hardness is low, scratch resistance is insufficient, and the interface between the filler and polypropylene is destroyed, There is a problem that the damaged part is whitened. On the other hand, in order to improve the scratch resistance, a method of increasing the surface hardness and a method of sliding the surface have been developed. According to the study of the present inventor, even if these methods are used, filler-filled polypropylene is used. When the main component is used, it has been found that the surface hardness of the product is limited, and the scratch resistance is not sufficient.
Also, when polycarbonate (hereinafter may be abbreviated as “PC”) alone, ABS (acrylonitrile-butadiene-styrene copolymer) alone, and PC / ABS alloy are the main components, filler-filled polypropylene is the main component. Compared to the above, it has excellent mechanical properties such as surface hardness and improved scratch resistance, but it is highly glossy and causes light reflection, so it has a particularly low gloss appearance. It is difficult to use for the product for.
From the above, from the viewpoint of achieving both low gloss and scratch resistance, it has been difficult to unpaint automobile parts.

  By the way, the alloy of PC and polyolefin (PO), especially PC and polypropylene (PP) or polyethylene, has been hitherto to obtain a molded article excellent in impact resistance, bending strength, chemical resistance and fluidity. The polycarbonate resin composition which has an alloy with (PE) as a main component is developed (for example, refer patent documents 1-3).

JP 2009-275131 A JP 2009-298993 A JP 2010-024368 A

In Patent Documents 1 to 3, there is a description that a molded body excellent in impact resistance, bending strength, chemical resistance, fluidity, and the like can be obtained, but there is a problem with the degree of gloss and scratch resistance of the molded product. Therefore, there is no description thereof, and there has been a demand for the development of a molded body that achieves both low gloss and scratch resistance.
SUMMARY OF THE INVENTION An object of the present invention is to provide a molded article having both low gloss and scratch resistance, and an automobile part, an electronic device and an information device obtained using the molded article.

  As a result of intensive studies, the inventor obtained by molding a polycarbonate resin composition containing a specific PC, an olefin polymer containing an epoxy group or a glycidyl group, and an unmodified polyolefin in a specific ratio. It has been found that the molded article has low gloss and is excellent in the transferability of the embossed shape (texture transferability) during molding using a mold having an embossed shape. And, since it has a low gloss and is excellent in the texture transfer property, even if the molded product obtained by applying the texture to the composition is scratched, the scratch is not noticeable (appears to be scratched) In the present invention, the fact that scratches are not noticeable is synonymous with high scratch resistance. The present invention has been completed based on such findings.

That is, the present invention relates to the following [1] to [6].
[1] (A) 50 to 94% by mass of an aromatic polycarbonate resin having a viscosity average molecular weight of 10,000 to 35,000,
(B) 1-30% by mass of an olefin polymer containing an epoxy group or a glycidyl group,
(C) 1 to 30% by mass of unmodified polyolefin, and (D) From the following (D1) to (D5) with respect to 100 parts by mass of the mixture comprising the components (A) to (C) as an anti-scratch agent. At least one selected,
A molded article having a textured shape obtained by molding an aromatic polycarbonate resin composition comprising
[(D) Scratch prevention agent]
(D1) Silicone / acrylic composite rubber 5-20 parts by weight.
(D2) polysiloxane 2-10 parts by weight.
(D3) 10 to 40 parts by mass of polymethyl methacrylate.
(D4) 0.5-5 parts by mass of wax ester.
(D5) Talc 10-30 parts by weight.
[2] The molded article according to the above [1], wherein the component (B) is a polyethylene containing an epoxy group or a glycidyl group.
[3] The molded article according to the above [1] or [2], wherein the component (C) is unmodified polyethylene or unmodified polypropylene.
[4] An automobile part obtained by using the molded article according to any one of [1] to [3].
[5] An electronic device obtained using the molded article according to any one of [1] to [3].
[6] An information device obtained using the molded article according to any one of [1] to [3].

The molded product of the present invention has a low gloss, and the textured shape of the mold is well transferred and has a textured shape with large irregularities, so even if the molded product is scratched, it is attached. The wound is inconspicuous. Therefore, it also has scratch resistance. In other words, since the molded article of the present invention has both low gloss and scratch resistance, it can be used as an unpainted automobile part and as a housing for electronic equipment and information equipment. Secondary processing costs such as can be reduced.
In the aromatic polycarbonate resin composition, as component (D), that is, as an anti-scratch agent, (D1) silicone / acrylic composite rubber, (D2) polysiloxane, (D3) polymethyl methacrylate, (D4) wax ester and (D5) By containing at least one selected from the group consisting of talc, the scratch resistance of the molded body is further improved.

The molded body of the present invention is
(A) Aromatic polycarbonate resin having a viscosity average molecular weight of 10,000 to 35,000, 50 to 94% by mass,
(B) 1-30% by mass of an olefin polymer containing an epoxy group or glycidyl group, and (C) 1-30% by mass of an unmodified polyolefin.
A molded article having a textured shape obtained by molding an aromatic polycarbonate resin composition containing a mixture of
Hereafter, each component which the said aromatic polycarbonate resin composition contains is demonstrated in order, and the manufacturing method of a molded object is demonstrated after that.

[(A) aromatic polycarbonate resin]
The aromatic polycarbonate resin (A) is an aromatic polycarbonate resin having a viscosity average molecular weight of 10,000 to 35,000. When the viscosity average molecular weight is less than 10,000, mechanical properties such as impact resistance are low, and when it exceeds 35,000, fluidity is lowered. From the same viewpoint, the viscosity average molecular weight is preferably 13,000 to 35,000, more preferably 13,000 to 30,000, still more preferably 17,000 to 30,000, and particularly preferably 20,000 to 30. , 000.
The viscosity average molecular weight of the aromatic polycarbonate resin is the following specific viscosity (η _sp ) measured using an Ubbelohde viscometer with a solution of about 0.7 g of the aromatic polycarbonate resin dissolved in 100 cm ³ of methylene chloride at 20 ° C. It is obtained by inserting into the formula.
(Η _sp ) / C = [η] + 0.45 × [η] ² C
[Η] = 1.23 × 10 ⁻⁵ M ^0.83
([Η] is the intrinsic viscosity, C is the polymer concentration, and M is the viscosity average molecular weight.)

The aromatic polycarbonate resin includes those having a hydroxy group as a molecular chain end group. When it has a hydroxy group as a molecular chain end group, the content of the hydroxy group with respect to all the end groups is preferably 1 mol% or more, more preferably 2 mol% or more, and further preferably 3 mol% or more. In addition, the content of the hydroxy group with respect to all terminal groups is usually preferably 80 mol% or less, and an aromatic polycarbonate resin that is 50 mol% or less, or further an aromatic polycarbonate resin that is 30 mol% or less. It may be used. In particular, when using an aromatic polycarbonate resin having a low hydroxy group content with respect to all terminal groups (for example, 10 mol% or less), “aliphatic amine salt, aromatic amine salt, ammonium hydroxide and hydroxylamine, which will be described later, are used. It is preferable to contain “at least one selected from the group consisting of salts”. When the content of hydroxy groups with respect to all terminal groups is within this range, the hydrolyzability, heat resistance and the like are good.
As the component (A), various aromatic polycarbonate resins produced by a reaction between a dihydric phenol compound and a carbonate precursor can be used.

A known aromatic dihydric phenol compound can be used as the dihydric phenol compound. Examples of aromatic dihydric phenol compounds include 4,4′-dihydroxydiphenyl; 1,1-bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, and 2,2-bis ( Bis (hydroxyphenyl) alkane such as 4-hydroxyphenyl) propane [so-called bisphenol A]; bis (4-hydroxyphenyl) cycloalkane; bis (4-hydroxyphenyl) oxide; bis (4-hydroxyphenyl) sulfide; (4-hydroxyphenyl) sulfone; bis (4-hydroxyphenyl) sulfoxide; bis (4-hydroxyphenyl) ketone and the like. A dihydric phenol type compound may be used individually by 1 type, and may use 2 or more types together.
Among these, bis (hydroxyphenyl) alkane is preferable, and bisphenol A or bisphenol A as a main raw material is more preferable.

  Examples of the carbonate precursor include carbonyl halide, haloformate, carbonate ester and the like. More specifically, examples of the carbonyl halide include phosgene, examples of the haloformate include dihaloformates of aromatic dihydric phenols, and examples of the carbonic acid ester include diphenyl carbonate, dimethyl carbonate, and diethyl carbonate. Of these, phosgene is preferable.

  The aromatic polycarbonate resin as component (A) may have a branched structure. In order to introduce a branched structure into the aromatic polycarbonate resin, a branching agent may be used in the production of the aromatic polycarbonate resin. Examples of the branching agent include 1,1,1-tris (4-hydroxyphenyl) ethane, α, α ′, α ″ -tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene, 1- [α-Methyl-α- (4′-hydroxyphenyl) ethyl] -4- [α ′, α′-bis (4 ″ -hydroxyphenyl) ethyl] benzene, phloroglucin, trimellitic acid, isatin bis (o A compound having three or more functional groups such as (-cresol) can be used.

In addition, when manufacturing the aromatic polycarbonate which has a hydroxyl group as a molecular chain terminal group, the following method is mentioned preferably as a method of adjusting the content rate of the hydroxyl group with respect to all the terminal groups. That is, when an aromatic polycarbonate resin is produced by reacting a dihydric phenol compound with a carbonate precursor, a monohydric phenol conventionally used as a terminal stopper and an alcoholic hydroxy group-containing phenol are used. It can be carried out by controlling the use ratio and the use ratio relative to the dihydric phenol compound.
Examples of monohydric phenols include phenol, p-cresol, p-tert-butylphenol, p-tert-octylphenol, p-cumylphenol, p-nonylphenol and p-tert-amylphenol. Monovalent phenols may be used alone or in combination of two or more.
Examples of the alcoholic hydroxy group-containing phenols include 2-hydroxybenzyl alcohol, 3-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, 2- (4-hydroxyphenyl) ethyl alcohol and 2,6-dihydroxy-4-methylphenol. Etc.

  Content of (A) component in an aromatic polycarbonate resin composition is 50-94 mass% in the mixture which consists of (A)-(C) component. When the content of the component (A) is less than 50% by mass in the mixture consisting of the components (A) to (C), the mechanical properties such as tensile strength are deteriorated. It becomes sufficient, and the scratches on the molded body tend to be noticeable, and it tends to become high gloss. From the same viewpoint, the content of the component (A) is preferably 55 to 94% by mass, more preferably 60 to 90% by mass, and further preferably 75 to 90% in the mixture composed of the components (A) to (C). % By mass.

[(B) Olefin polymer containing epoxy group or glycidyl group]
Component (B) is, for example, (b-1) an olefin homopolymer having an epoxy group or glycidyl group, (b-2) a copolymer of an olefin and an unsaturated monomer having an epoxy group or glycidyl group, (B-3) Any of those obtained by copolymerizing an olefin polymer with an unsaturated monomer having an epoxy group or a glycidyl group. The copolymer may be any of a graft copolymer, a random copolymer, and a block copolymer.
(B) A component may be used individually by 1 type and may use 2 or more types together.

  Further, for example, the terminal of the olefin polymer, or the unsaturated bond present in the copolymer of olefin and other unsaturated monomer and the composite thereof, hydrogen peroxide, perbenzoic acid, performic acid In addition, an epoxy group may be introduced by oxidation with an organic peracid such as peracetic acid. That is, there is no particular limitation as long as an epoxy group or a glycidyl group is introduced into the olefin polymer.

The component (B) may be a polyolefin resin or a polyolefin elastomer.
The polyolefin elastomer is a low crystalline or amorphous olefin copolymer containing an epoxy group or a glycidyl group and having a crystallinity measured by an X-ray diffraction method of 50% or less.

Examples of the olefin as a raw material include ethylene, propylene, 1-butene, isobutylene, 2-butene, cyclobutene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-butene, 4- Examples thereof include methyl-1-butene, cyclopentene, 1-hexene, cyclohexene, 1-octene, 1-decene and 1-dodecene. These may be used alone or in combination of two or more.
Of these, ethylene and propylene are preferable, and ethylene is more preferable.

Examples of the unsaturated monomer having an epoxy group or glycidyl group include glycidyl acrylate, glycidyl methacrylate, vinyl glycidyl ether, allyl glycidyl ether, methacryl glycidyl ether, 2-methylpropenyl glycidyl ether, styrene-p-glycidyl ether, glycidyl cinna Mate, itaconic acid glycidyl ester, N- [4- (2,3-epoxypropoxy) -3,5-dimethylbenzyl] methacrylamide and the like. These may be used alone or in combination of two or more.
Of these, glycidyl acrylate and glycidyl methacrylate are preferable, and glycidyl methacrylate is more preferable.
Furthermore, together with these unsaturated monomers having an epoxy group or glycidyl group, an unsaturated monomer having no epoxy group or glycidyl group such as alkyl acrylate or alkyl methacrylate was copolymerized. What contains groups, such as an acrylate ester and a methacrylate ester in addition to the glycidyl group, can also be used as the component (B).

  Content of (B) component in an aromatic polycarbonate resin composition is 1-30 mass% in the mixture which consists of (A)-(C) component. When the content of the component (B) is less than 1% by mass in the mixture composed of the components (A) to (C), mechanical properties such as tensile strength are reduced due to a decrease in compatibility, and 30% by mass. If it exceeds, self-crosslinking may occur, and mechanical properties such as impact resistance tend to be lowered. From the same viewpoint, the content of the component (B) is preferably 1 to 15% by mass, more preferably 2 to 10% by mass in the mixture composed of the components (A) to (C).

  Moreover, it is preferable that the weight average molecular weight of (B) component is about 50,000 to 500,000. Within this range, good impact resistance can be obtained, and fluidity can be improved. In addition, a weight average molecular weight is calculated | required in standard polystyrene conversion by the gel permeation chromatography (GPC) method.

In the present invention, as the component (B), one or more polyolefin resins having an epoxy group or glycidyl group may be used, or one or more polyolefin elastomers having an epoxy group or glycidyl group may be used. Also, one or more polyolefin resins and one or more polyolefin elastomers may be used in combination.
Among these, as the polyolefin resin, a polyethylene resin is preferable, and as the polyolefin elastomer, a polyethylene elastomer is preferable.

[(C) Unmodified polyolefin]
The component (C) is an unmodified polyolefin that does not have an epoxy group or a glycidyl group like the component (B).
The melt index (MI) of the unmodified polyolefin is preferably 35 g / 10 min or less, more preferably 0.01 to 20 g / 10 min, more preferably 0.01 to 10 g / min, from the viewpoint of impact resistance and fluidity. 10 minutes, more preferably 0.01 to 5 g / 10 minutes.
In this specification, MI is measured in accordance with ASTM D 1238 at a resin temperature of 230 ° C. and a load of 21.18 N.

As the component (C), one olefin alone may be polymerized, or two or more olefins may be copolymerized. As olefin, the same thing as the exemplary compound in the said (B) component is mentioned. Of these, ethylene and propylene are preferable as the olefin.
Specific examples of the component (C) include polyethylene such as high density polyethylene, medium density polyethylene, low density polyethylene, and linear low density polyethylene; ethylene-α-olefin copolymer; ethylene-ethyl acrylate copolymer, ethylene -Copolymers mainly composed of ethylene such as methacrylate copolymers; polypropylenes such as isotactic propylene homopolymers and syndiotactic propylene homopolymers. Examples of the ethylene-α-olefin copolymer include a copolymer of ethylene and propylene.
The copolymer may be any of a graft copolymer, a random copolymer, or a block copolymer.
The component (C) is preferably polyethylene or polypropylene, that is, unmodified polyethylene or unmodified polypropylene.
(C) A component may be used individually by 1 type and may use 2 or more types together.

  Content of (C) component in an aromatic polycarbonate resin composition is 1-30 mass% in the mixture which consists of (A)-(C) component. When the content of the component (C) is less than 1% by mass in the mixture consisting of the components (A) to (C), mechanical properties such as tensile strength are reduced due to a decrease in compatibility, and 30% by mass is reduced. If it exceeds the upper limit, mechanical properties such as impact resistance tend to be lowered, and scratches on the molded body are easily noticeable. From the same viewpoint, the content of the component (C) is preferably 1 to 25% by mass, more preferably 5 to 25% by mass, and further preferably 5 to 20% in the mixture composed of the components (A) to (C). % By mass.

[(D) Scratch prevention agent]
It is preferable that the aromatic polycarbonate resin composition further contains at least one selected from the group consisting of the following (D1) to (D5) as the component (D) because scratches are difficult to be attached. In addition, since it exists in the tendency for the impact resistance of a molded object to fall, so that (D) component is put, it is preferable to use it moderately within the range mentioned later.
(D1): Silicone / acrylic composite rubber (D2): Polysiloxane (D3): Polymethyl methacrylate (D4): Wax ester (D5): Talc

((D1) Silicone / acrylic composite rubber)
The silicone / acrylic composite rubber refers to a rubbery polymer containing a polyorganosiloxane rubber and a polyalkyl (meth) acrylate rubber.
Examples of the polyalkyl (meth) acrylate rubber include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, ethoxyethoxyethyl acrylate, methoxytripropylene glycol acrylate, 4-hydroxybutyl acrylate, Examples thereof include those obtained by copolymerizing alkyl (meth) acrylates such as lauryl methacrylate and stearyl methacrylate. These may be used individually by 1 type and may use 2 or more types together.
The polyalkyl (meth) acrylate rubber is preferably a copolymer having two or more glass transition temperatures.
The alkyl (meth) acrylate monomer includes aromatic vinyl compounds such as styrene and α-methylstyrene; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; methacrylic acid-modified silicones and fluorine-containing vinyl compounds. The vinyl monomer may be contained as a copolymerization component in an amount of preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably about 10% by mass or less.

As said polyorganosiloxane rubber, what copolymerized organosiloxane can be used. Examples of the organosiloxane include various reduced products having three or more members, preferably hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrimethyl. Examples thereof include siloxane, tetramethyltetraphenylcyclotetrasiloxane, and octaphenylcyclotetrasiloxane. And these may be used individually by 1 type and may use 2 or more types together. The amount of these organosiloxanes used is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more in the polyorganosiloxane rubber component.
Commercially available silicone / acrylic composite rubber such as Methbrene SRK-200, Methbrene SRK-200A, Methbrene SX-005, Methbrene S-2030, Methbrene S-2006, Methbrene S-2001 (manufactured by Mitsubishi Rayon Co., Ltd.). Product can be used.
When the component (D1) is contained in the aromatic polycarbonate resin composition, the content thereof is based on 100 parts by mass of the mixture composed of the components (A) to (C) from the viewpoints of scratch resistance and impact resistance. The amount is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, and still more preferably 0.5 to 10 parts by mass.

（式中、Ｒ¹〜Ｒ³は、それぞれ独立して、水素原子、炭素数１〜１０のアルキル基、炭素数６〜１２のアリール基又は炭素数７〜２０のアラルキル基を表す。Ｒ⁴及びＲ⁵は、それぞれ独立して、炭素数１〜１０のアルキル基を表す。Ｒ⁶及びＲ⁷は、それぞれ独立して、炭素数１〜１０のアルキル基、炭素数６〜１２のアリール基又は炭素数７〜２０のアラルキル基を表す。ｍ及びｎは平均繰り返し単位数を表し、ｍは５０〜２，０００、ｎは１０〜２００である。） ((D2): polysiloxane)
A known polyorganosiloxane can be used as the polysiloxane. Especially, what is represented by the following general formula (I) or (II) can be used preferably.

(In the formula, R ^{1 to} R ³ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. R ⁴ And R ⁵ each independently represents an alkyl group having 1 to 10 carbon atoms, and R ⁶ and R ⁷ each independently represent an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms. Or an aralkyl group having 7 to 20 carbon atoms, m and n represent the average number of repeating units, m is 50 to 2,000, and n is 10 to 200.)

Examples of the alkyl group having 1 to 10 carbon atoms represented by R ^{1 to} R ⁷ include, for example, a methyl group, an ethyl group, and various propyl groups (“various” means linear and all branched ones). The same shall apply hereinafter.), Various butyl groups, various hexyl groups, various octyl groups, and various decyl groups. Especially, a C1-C5 alkyl group is preferable and a C1-C3 alkyl group is more preferable.
Examples of the aryl group having 6 to 12 carbon atoms represented by R ^{1 to} R ³ , R ⁶ and R ⁷ include a phenyl group and a naphthyl group. Of these, a phenyl group is preferred.
Examples of the aralkyl group having 7 to 20 carbon atoms represented by R ^{1 to} R ³ , R ⁶ and R ⁷ include benzyl group, phenethyl group, dimethylphenylethyl group (2,2-dimethyl-2-phenylethyl group) and the like. It is done. Of these, a dimethylphenylethyl group (2,2-dimethyl-2-phenylethyl group) is preferable.
R ^{1 to} R ⁵ are preferably alkyl groups having 1 to 10 carbon atoms, and more preferably as described above.
R ⁶ and R ⁷ are preferably an alkyl group having 1 to 10 carbon atoms or an aralkyl group having 7 to 20 carbon atoms.
m is 50 to 2,000, preferably 50 to 1,500. n is 10 to 200, preferably 10 to 150.
The polysiloxane is preferably dimethylphenylethyl polysiloxane or polysiloxane having an alkyl group.
When the component (D2) is contained in the aromatic polycarbonate resin composition, the content thereof is from 100 parts by weight of the mixture composed of the components (A) to (C) from the viewpoint of scratch prevention effect and impact resistance. And preferably 0.1 to 10 parts by mass, more preferably 0.5 to 10 parts by mass, and more preferably 0.5 to 7 parts by mass.

((D3): polymethyl methacrylate)
A well-known thing can be used for polymethyl methacrylate (PMMA). Usually, polymethyl methacrylate is produced by bulk polymerization of a methyl methacrylate monomer in the presence of a peroxide or an azo polymerization initiator.
The molecular weight of polymethyl methacrylate is preferably about 1,000 to 200,000, more preferably 10,000 to 180,000, still more preferably 70, from the viewpoint of compatibility with the aromatic polycarbonate resin of component (A). 000 to 150,000.
The melt index (MI) of polymethyl methacrylate is preferably 0.01 to 20 g / 10 minutes, more preferably 0.1 to 20 g / 10 minutes, more preferably 0.1 to 10 g / 10 minutes, Preferably it is 0.5-6 g / 10min.
When the component (D3) is contained in the aromatic polycarbonate resin composition, the content thereof is from 100 parts by weight of the mixture composed of the components (A) to (C) from the viewpoint of the scratch prevention effect and impact resistance. The amount is preferably 1 to 40 parts by mass, more preferably 1 to 35 parts by mass, more preferably 1 to 25 parts by mass, and still more preferably 1 to 15 parts by mass.

((D4): wax ester)
The wax ester is an ester in which a higher fatty acid and a higher monohydric alcohol are bonded one-to-one. The total carbon number of the wax ester is preferably 20 to 100, more preferably 30 to 80, and still more preferably 30 to 50.
Examples of wax esters include plant-derived waxes such as carnauba wax, urushi wax, hydrogenated jojoba wax, rice wax, and candelilla wax; and waxes derived from animals such as beeswax, white beeswax, and whale wax.
The wax ester is solid at normal temperature (25 ° C.) and has a melting point of 100 ° C. or less.
When the component (D4) is contained in the aromatic polycarbonate resin composition, the content thereof is based on 100 parts by mass of the mixture composed of the components (A) to (C), from the viewpoint of scratch resistance and impact resistance. The amount is preferably 0.1 to 5 parts by mass, more preferably 0.1 to 3 parts by mass.

((D5): Talc)
As talc, what is marketed as an additive of a thermoplastic resin can be used arbitrarily.
Talc is a hydrous silicate of magnesium, and may contain trace amounts of aluminum oxide, calcium oxide, and iron oxide in addition to the main components of silicic acid and magnesium oxide. The talc used in the present invention may also contain these.
Moreover, the average particle diameter of talc is preferably 0.5 to 50 μm, more preferably 1 to 20 μm, and still more preferably 2 to 8 μm. The aspect ratio is preferably 2-20.
The average particle size and aspect ratio are determined by comprehensively considering other components depending on the fluidity at the time of molding, the impact resistance required for the molded product, the rigidity, and the like.
Moreover, as talc, the thing surface-treated with the fatty acid etc., the talc etc. which were grind | pulverized in presence of a fatty acid etc. can be used.
When the component (D5) is contained in the aromatic polycarbonate resin composition, the content thereof is based on 100 parts by mass of the mixture composed of the components (A) to (C) from the viewpoints of scratch resistance and impact resistance. The amount is preferably 1 to 30 parts by mass, more preferably 1 to 25 parts by mass, and still more preferably 1 to 20 parts by mass.

((E): aliphatic amine salt, aromatic amine salt, ammonium hydroxide, hydroxylamine salt)
Furthermore, as component (E), by containing at least one selected from the group consisting of aliphatic amine salts, aromatic amine salts, ammonium hydroxide and hydroxylamine salts, (A) component and (B) component The reactivity with can be increased. In particular, a great effect can be expected when the content of the terminal hydroxy group of the component (A) is 10 mol% or less.
(Aliphatic amine salt, aromatic amine salt)
The aliphatic amine salt and an aromatic amine salt is not particularly limited, may be used, for example the general formula R ¹¹ R ¹² R ¹³ is represented by N · ¹ / nA 1 compound. In the formula, R ^{11 to} R ¹³ each independently represent a hydrogen atom, an aliphatic group or an aromatic group (however, all of R ^{11 to} R ¹³ do not represent a hydrogen atom at the same time). Specifically, in the case of an aliphatic amine salt, R ^{11 to} R ¹³ each independently represent a hydrogen atom or an aliphatic group (however, all of R ^{11 to} R ¹³ do not represent a hydrogen atom at the same time). ). In the case of an aromatic amine salt, R ^{11 to} R ¹³ each independently represent a hydrogen atom, an aliphatic group or an aromatic group (provided that at least one of R ^{11 to} R ¹³ represents an aromatic group). . A ¹ represents an acid, and examples thereof include hydrochloric acid, sulfuric acid, nitric acid, chloric acid, perchloric acid, acetic acid, monoalkyl sulfuric acid, and sulfonic acid compounds. n is the valence of the anion acid A ^1, for example, in the case of hydrochloric acid n = 1, in the case of sulfuric acid it is n = 2.

(Ammonium hydroxide)
Although it does not specifically limit as ammonium hydroxide, For example, the compound represented by general formula R ^{< 14 >} R ^{< 15 >} R ^{< 16 >} R ^{< 17 >} N ^<+> OH ^{< - >} can be used. In the formula, each of R ^{14 to} R ¹⁷ independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms (provided that all of R ^{14 to} R ¹⁷ simultaneously represent a hydrogen atom. Nothing.)
Specific examples of ammonium hydroxide include tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, tetra-n-propylammonium hydroxide, tetraisopropylammonium hydroxide, and the like.

(Hydroxylamine salt)
The hydroxylamine salt is not particularly limited, may be used, for example the general formula ^{R 18 R 19 NOH · 1 /} mA represented by ² compound. In the formula, each of R ¹⁸ and R ¹⁹ independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms (provided that R ¹⁸ and R ¹⁹ represent a hydrogen atom at the same time). No.) A ² represents an acid, and m is the valence of the anion of acid A ² .
Specific examples of the hydroxylamine salt include methylhydroxylamine hydrochloride, ethylhydroxylamine hydrochloride, n-propylhydroxylamine hydrochloride, isopropylhydroxylamine hydrochloride, dimethylhydroxylamine hydrochloride, diethylhydroxylamine hydrochloride and the like. Moreover, the hydroxylamine salt etc. which substituted the hydrochloric acid in these hydroxylamine salts with other acids, for example, a sulfuric acid, nitric acid, an acetic acid, a monoalkyl sulfuric acid, a sulfonic acid compound, etc. can be mentioned.

  When the aromatic polycarbonate resin composition contains the component (E), the content is preferably 0.001 to 1 part by mass with respect to 100 parts by mass of the mixture composed of the components (A) to (C). More preferably, it is 0.002-0.8 mass part, More preferably, it is 0.003-0.5 mass part. If it is 1 mass part or less, there is no worry that impact resistance will fall.

[Other ingredients]
The aromatic polycarbonate resin composition can appropriately contain other components as long as the effects of the present invention are not significantly impaired.
Other components include, for example, antioxidants, flame retardants, flame retardant aids, antistatic agents, benzotriazole and benzophenone UV absorbers, hindered amine light stabilizers (weathering agents), antibacterial agents, Examples include solubilizers, colorants (dyes and pigments), additives such as mold release agents, and other thermoplastic resins.
When these other components are contained, the content thereof is preferably 30 parts by mass or less, more preferably 10 parts by mass or less, and more preferably 10 parts by mass or less with respect to 100 parts by mass of the mixture composed of the components (A) to (C). Preferably it is 5 mass parts or less.

Examples of the antioxidant include phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, vitamin antioxidants, lactone antioxidants, and amine antioxidants.
Examples of phenolic antioxidants include Irganox 1010 (Irganox 1010), Irganox 1076 (Irganox 1076), Irganox 1330 (Irganox 1330), Irganox 3114 (Irganox 3114), Irganox 3125 (Irganox 3125), Irganox 3125 As described above, Ciba Specialty Chemicals Co., Ltd., Irganox: registered trademark], BHT (2,6-di-t-butyl-4-methylphenol), Cyanox 1790 (Cyanox 1790, manufactured by Cyanamid Co., Ltd.), Sumilyzer GA- Commercial products such as 80 (Sumilizer GA-80, manufactured by Sumitomo Chemical Co., Ltd., Sumilyzer: registered trademark) can be mentioned.

Examples of phosphorus-based antioxidants include Irgafos 168 (Irgafos 168), Irgafos 12 (Irgafos 12), Irgafos 38 (Irgafos 38), and Ciba Specialty Chemicals Co., Ltd., Irgafos: registered trademark, ADK STAB 329K (ADKSTAB 329K) ADK STAB PEP36 (ADKSTAP PEP36), ADK STAB PEP-8 (ADKSTAB PEP-8) [above, manufactured by ADEKA, ADK STAB: registered trademark], Sardstab P-EPQ (manufactured by Clariant), Weston 618 (Weston 618), Commercial products such as Weston 619G (Weston 619G) and Weston-624 (Weston-624) [manufactured by GE Corporation] can be mentioned.
Examples of the sulfur-based antioxidant include DSTP (Yoshitomi), DLTP (Yoshitomi), DMTP (Yoshitomi) [above, manufactured by Yoshitomi Pharmaceutical Co., Ltd.], Seenox (registered trademark) 412S (manufactured by Sipro Kasei Co., Ltd.), Commercial products such as Cyanox 1212 (manufactured by Cyanamid Co., Ltd.) can be mentioned.

Examples of vitamin antioxidants include tocopherol, Irganox (registered trademark) E201 (Irganox E201, manufactured by Ciba Specialty Chemicals, Inc., compound name; 2,5,7,8-tetramethyl-2 (4 ′, 8 There are commercially available products such as', 12'-trimethyltridecyl) coumarone-6-ol).
As the lactone antioxidant, those described in JP-A-7-233160 and JP-A-7-247278 can be used. Further, HP-136 (manufactured by Ciba Specialty Chemicals Co., Ltd., compound name; 5,7-di-t-butyl-3- (3,4-dimethylphenyl) -3H-benzofuran-2-one), etc. A commercial item can be mentioned.
Examples of amine-based antioxidants include commercially available products such as Irgastab (registered trademark) FS042 (manufactured by Ciba Specialty Chemicals Co., Ltd.) and GENOX EP (manufactured by Crompton, compound name; dialkyl-N-methylamine oxide). be able to.
When the antioxidant is contained, the content of the antioxidant in the aromatic polycarbonate resin composition is usually preferably 0.01 to 100 parts by mass of the mixture composed of the components (A) to (C). About 5 mass parts, More preferably, it is 0.02-3 mass parts, More preferably, it is 0.02-2 mass parts.
An antioxidant may be used individually by 1 type and can also use 2 or more types together.

Examples of the flame retardant include halogen flame retardant, nitrogen flame retardant, metal hydroxide, phosphorus flame retardant, organic alkali metal salt, organic alkaline earth metal salt, silicone flame retardant, and expandable graphite. A flame retardant may be used individually by 1 type and can also use 2 or more types together.
Other thermoplastic resins include, for example, polystyrene resins such as ABS (acrylonitrile / butadiene / styrene copolymer), polystyrene, high impact polystyrene (HIPS); polyethylene terephthalate (PET), polybutylene terephthalate (PBT), etc. And polyester resin. Another thermoplastic resin may be used individually by 1 type, and can also use 2 or more types together.

<Aromatic polycarbonate resin composition, method for producing molded article>
First, the aromatics used in the production of the molded body by mixing the components (A) to (C) and, if necessary, the (D) component, the (E) component, and other components in a predetermined amount and melt-kneading them. A pellet of the polycarbonate resin composition can be obtained.
Examples of the melt kneader include a Banbury mixer, a single screw extruder, a twin screw extruder, a kneader, and a multi screw extruder. The heating temperature in melt kneading is usually suitably 220 to 300 ° C.
Next, the obtained pellet is injection-molded at a mold temperature of 40 to 120 ° C. and a resin temperature (cylinder temperature) of 250 to 310 ° C. using a mold having a crimped shape, preferably a mold having a textured texture. By this, the molded article of the present invention is obtained.
Although the mold temperature is as described above, it is preferably 80 to 100 ° C. from the viewpoint of emboss transferability. Moreover, although resin temperature is as above-mentioned, Preferably it is 260-300 degreeC from a fluid viewpoint.
Further, since the molded body is also low glossy, there is an effect that even if the molded body is scratched, the scratches on the molded body are very inconspicuous due to the fine reproduction of the embossed shape.

Hereinafter, the present invention will be described more specifically based on examples. However, the present invention is not limited to these examples.
In the following, GMA represents glycidyl methacrylate. MI represents a melt index (measurement conditions: resin temperature 230 ° C., load 21.18 N).

Each component used in Examples , Reference Examples and Comparative Examples is shown below.
(A) Aromatic polycarbonate resin A1: Viscosity average molecular weight (Mv) 26,000, terminal hydroxyl group content 5 mol% or less; “Taflon (registered trademark) FN-2600A” [trade name, manufactured by Idemitsu Kosan Co., Ltd.]
A2: Viscosity average molecular weight (Mv) 15,000, terminal hydroxyl group content 5 mol% or less; “Taflon (registered trademark) FN-1500A” [trade name, manufactured by Idemitsu Kosan Co., Ltd.]
A3: Viscosity average molecular weight (Mv) 22,000, terminal hydroxyl group content 5 mol% or less; “Taflon (registered trademark) FN-2200A” [trade name, manufactured by Idemitsu Kosan Co., Ltd.]

(B) Polyolefin B1 containing an epoxy group or glycidyl group: ethylene-GMA copolymer [GMA content: 12% by mass (5.46% by mass as a glycidyl group)], “Bond First (registered trademark) E” [ (Sumitomo Chemical Co., Ltd.)

(C) Polyethylene resin C1: Polypropylene, MI: 0.3 g / 10 min; E-185G [trade name, manufactured by Prime Polymer Co., Ltd.]
C2: Polypropylene, MI: 30 g / 10 min; J-3054HP [trade name, manufactured by Prime Polymer Co., Ltd.]
C3: high density polyethylene, MI: 1.1 g / 10 min; 3300F [trade name, manufactured by Prime Polymer Co., Ltd.]

ABS: acrylonitrile / butadiene / styrene copolymer, “Santac (registered trademark) AT-05” (manufactured by Nippon A & L Co., Ltd.)

(D) Scratch prevention agent D1: Using any of silicone / acrylic composite rubber, “Metablene (registered trademark) SX-005” (manufactured by Mitsubishi Rayon Co., Ltd.) and “SRK200A” (manufactured by Mitsubishi Rayon Co., Ltd.) The evaluation results were the same.
D2: The evaluation results were the same regardless of whether the polysiloxane, “TEGOMER® M-Si 2650” (Evonik Industries) or “TEGOMER® ANTISCRATCH L” (Evonik Industries) was used. It was.
D3: Polymethyl methacrylate, “Acrypet VH” (MI = 3.0 g / 10 min, molecular weight = 129,000) [trade name, manufactured by Mitsubishi Rayon Co., Ltd.]
D4: wax ester, golden brand Sarashi beeswax [trade name, manufactured by Miki Chemical Industry Co., Ltd.]
D5: Talc, average particle size 4.96 μm; TP-A25 [trade name, manufactured by Fuji Talc Co., Ltd.]

(E) Ammonium hydroxide E1: Tetramethylammonium hydroxide 2.38% aqueous solution [manufactured by Tama Chemical Co., Ltd.]
(Other ingredients)
Antioxidant 1: “ADK STAB (registered trademark) PEP-8” (manufactured by ADEKA Corporation)
Antioxidant 2: “Irgaphos (registered trademark) 168” (manufactured by Ciba Specialty Chemicals)
Colorant: Pigmo Color 1603S04 [trade name, manufactured by Daito Kasei Kogyo Co., Ltd.]

Examples 5 to 9, 11 to 15 , 17 to 29, Reference Examples 1 to 4, 10, 16 and Comparative Examples 1 to 11
After dry blending each component according to the blending ratios shown in Tables 1 and 2, using a twin-screw kneader (TEX-44, manufactured by Nippon Steel Works Co., Ltd.), a set temperature of 250 ° C., a rotation speed of 300 rpm, and a discharge amount are set. Melt kneading was performed while controlling at 100 kg / hr to obtain pellets.
After drying the obtained pellets at 120 ° C. for 5 hours or more, using a mold having a satin texture (80 mm × 80 mm × 2 mm thickness), a mold temperature of 80 ° C. and a cylinder temperature (resin temperature) of 280 ° C. A predetermined embossed test piece (molded body) was produced under the conditions where the filling speed and the resin filling amount were 38 cm ³ / sec. The surface roughness of the embossed surface of the mold is in the range of 10.4 to 12.6 by Ra measurement using a laser microscope “Lasertec H1200”.
Using the obtained test pieces, the degree of gloss and the ease of noticeable scratches were evaluated.
The obtained results are shown in Tables 1 and 2.

<Evaluation method>
(1) Gloss measurement It measured by the 60 degree reflection method (incident angle 60 degrees and reflection angle 60 degrees) in the center part of the test piece. A smaller value is preferable because of low gloss.
(2) Less noticeable scratches (scratch resistance)
The test piece was scratched under the following test conditions, the appearance of the scratch was visually confirmed, and evaluated according to the following evaluation criteria.
(Test conditions)
Wound needle: 0.5R
Load: 200g (one way in a certain direction)
Speed: 200 mm / min (evaluation criteria)
0: Scratches are not visible at all angles 1: Slightly scratches are visible when carefully checked, but scratches are not visible depending on the angle 2: Slightly scratches are visible when carefully checked, but scratches are visible depending on the angle Cannot be seen 3: Slightly scratched from any angle 4: Slightly scratched from any angle 5: Clearly scratched from any angle 6: Scratched site has been peeled off and whitened Have

From Table 1 and Table 2, it can be seen that the molded product of the present invention is a material that has low gloss and is hardly noticeable even if scratched.
On the other hand, as in Comparative Examples 1 to 3, it can be seen that the molded body using only the component (A) or the alloy of the component (A) and ABS is highly glossy and scratches are easily noticeable.
As in Comparative Example 4, in the case of a molded article composed of the component (C) and the component (D) which is an anti-scratch agent, the gloss is low, but it can be seen that the scratches are very conspicuous.
Furthermore, as in Comparative Examples 5 to 11, molded articles obtained by blending the component (D) with the component (A) alone are still highly glossy. Furthermore, Examples 5 to 7 (contrast with Comparative Example 5), Examples 8 to 9 (contrast with Comparative Example 6), Examples 11 to 13 (Comparative Example 7 and the same) are blended with the same component (D). Comparison), Examples 14 to 15 (Comparison with Comparative Example 8), Examples 21 to 22 (Comparison with Comparative Example 9), Examples 23 and 26 (Contrast with Comparative Example 10), Example 27 and 28 (contrast with Comparative Example 11), it can be seen that in Comparative Examples 5 to 11, the scratches are easily noticeable.

  Since the molded article of the present invention has both low gloss and scratch resistance, it can be suitably used as automobile parts, electronic equipment, information equipment (particularly housing), etc. that require these characteristics.

Claims (6)

(A) Aromatic polycarbonate resin having a viscosity average molecular weight of 10,000 to 35,000, 50 to 94% by mass,
(B) 1-30% by mass of an olefin polymer containing an epoxy group or a glycidyl group,
(C) 1 to 30% by mass of unmodified polyolefin, and (D) From the following (D1) to (D5) with respect to 100 parts by mass of the mixture comprising the components (A) to (C) as an anti-scratch agent. At least one selected,
A molded article having a textured shape obtained by molding an aromatic polycarbonate resin composition comprising
[(D) Scratch prevention agent]
(D1) Silicone / acrylic composite rubber 5-20 parts by weight.
(D2) polysiloxane 2-10 parts by weight.
(D3) 10 to 40 parts by mass of polymethyl methacrylate.
(D4) 0.5-5 parts by mass of wax ester.
(D5) Talc 10-30 parts by weight.   The molded article according to claim 1, wherein the component (B) is polyethylene containing an epoxy group or a glycidyl group.   The molded article according to claim 1 or 2, wherein the component (C) is unmodified polyethylene or unmodified polypropylene.   An automobile part obtained by using the molded body according to claim 1.   The electronic device obtained using the molded object in any one of Claims 1-3.   An information device obtained using the molded body according to claim 1.