JP2005314461A - Resin composition for direct vapor deposition and molding using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a thermoplastic resin composition for direct vapor deposition, which has excellent weather resistance, causes a few fisheyes in deep coloring and provides a beautiful and brilliant appearance after direct vapor deposition. <P>SOLUTION: The thermoplastic resin composition for direct vapor deposition is obtained by mixing 1-100 parts by mass of a graft copolymer (A) obtained by grafting a vinyl-based polymer onto a compound rubber-like polymer (G) composed of a polyorganosiloxane and a (meth) acrylic acid ester-based polymer with 99-0 parts by mass of another thermoplastic resin (B) (the total of the components (A) and (B) is 100 parts by mass) and 0.1-10 parts by mass of carbon black (C) having ≥20 nm primary particle diameter. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a thermoplastic resin composition suitable for a so-called direct vapor deposition method, which is not subjected to an undercoat treatment, and a molded article thereof.

A metal layer of copper, chromium, nickel, etc. is formed on the surface of automotive resin parts such as lamp housings for vehicles and thermoplastic resin molded products for various electrical equipment casings in order to enhance design and other functions. There is a case where a plating surface treatment or a metallization treatment for forming a metal layer (thickness of several tens to several hundreds of nanometers) such as aluminum or chromium by a vacuum deposition method, a sputtering method, or the like is performed.
In the latter metallization treatment, in order to smooth the surface of the molded article and obtain glitter, an undercoat treatment layer was formed in advance by coating or plasma polymerization treatment before metallization treatment, and further obtained by metallization treatment. In order to protect the metal layer, it is common to form a silicon-based topcoat layer. As described above, the conventional metallization treatment requires a large number of steps, dedicated equipment, and a high-cost treatment agent. The “direct vapor deposition method” has been adopted. Since the design of molded products obtained by the direct vapor deposition method is likely to vary depending on the type of resin material and the surface condition of the molded product, it is one of the important issues to stably obtain a beautiful brilliant appearance without surface fogging. Met.
In order to solve the problem, a resin composition for direct vapor deposition containing a graft rubber copolymer obtained by grafting a vinyl monomer to a rubber polymer having a specific particle size distribution has been proposed (for example, Patent Documents 1 to 3).

By the way, in general, molded products that are subjected to metallization by the direct vapor deposition method are very often colored in dark colors such as black or gray. Therefore, various black pigments are contained in the resin composition. And dyes were often added as colorants. However, when a pigment is added, a so-called fish eye may occur on the surface of the molded product due to a resin component having poor pigment dispersion or poor melting. When fish eyes are generated on the surface of a molded product, the design of the molded product subjected to the metallization process by the direct vapor deposition method is lowered, so that a material that does not easily generate fish eyes is strongly demanded.
Thus, as a method for improving the surface smoothness during pigmentation and suppressing the generation of fish eyes, a method using carbon black of a specific volatile content has been disclosed (see Patent Document 4).
JP 2001-002869 A JP 2002-133916 A JP 2003-128868 A Japanese Patent Laid-Open No. 11-228764

However, Patent Documents 1 and 2 do not mention any means for improving the weather resistance of a molded product, which is a requirement necessary for applications such as a lamp housing for a vehicle, and fish generated when pigments are colored. There is no mention of how to improve the eye. Therefore, the weather resistance and the bright appearance after direct vapor deposition were insufficient.
Although the thermoplastic resin composition described in Patent Document 3 is excellent in weather resistance and glitter after direct vapor deposition, there is no mention of a method for improving fish eyes generated during pigment coloring. Therefore, the bright appearance after direct vapor deposition was insufficient.
Furthermore, in the thermoplastic resin composition disclosed in Patent Document 4, a method for improving the surface smoothness during black coloring with carbon black is shown, but no mention is made of the glitter in direct vapor deposition. Not. In addition, none of the resin compositions described in the Examples sufficiently satisfy the high required level in the field in terms of the amount of fish eye generated, and the glitter appearance after direct vapor deposition was insufficient.
The present invention has been made in view of such circumstances, and is a thermoplastic resin composition for direct vapor deposition that is excellent in weather resistance, has little generation of fish eyes when colored deeply, and provides a beautiful glitter appearance after direct vapor deposition. And it aims at providing the molded article using the resin composition.

The thermoplastic resin composition for direct vapor deposition of the present invention comprises a graft copolymer (A) in which a vinyl polymer is grafted to a composite rubber-like polymer (G) comprising a polyorganosiloxane and a (meth) acrylic acid ester polymer. 1-100 parts by mass;
99 to 0 parts by mass of other thermoplastic resin (B) (provided that the total of components (A) and (B) is 100 parts by mass);
It is characterized by blending 0.1 to 10 parts by mass of carbon black (C) having a primary particle size of 20 nm or more.
In the thermoplastic resin composition for direct vapor deposition of the present invention, the proportion of the rubbery polymer having a particle diameter of 500 nm or more in the composite rubbery polymer (G) is preferably less than 3% by mass.
In the thermoplastic resin composition for direct vapor deposition of the present invention, the other thermoplastic resin (B) is polymethyl methacrylate, acrylonitrile-styrene copolymer, acrylonitrile-α-methylstyrene copolymer, styrene-maleic anhydride. Copolymer, acrylonitrile-styrene-N-substituted maleimide terpolymer, styrene-maleic anhydride-N-substituted maleimide terpolymer, polycarbonate resin, polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polychlorinated It is preferably at least one selected from the group consisting of vinyl, polystyrene, methyl methacrylate-styrene copolymer, acrylonitrile-styrene-methyl methacrylate copolymer, modified polyphenylene ether, and polyamide.
The molded product of the present invention is formed by molding the above-described thermoplastic resin composition for direct vapor deposition.
The molded product of the present invention may be subjected to metallization treatment by direct vapor deposition on the surface.

  The thermoplastic resin composition and molded product for direct vapor deposition of the present invention are excellent in weather resistance, have little generation of fish eyes during coloring, have excellent surface smoothness, and have a beautiful glitter appearance after direct vapor deposition. In particular, the balance between the weather resistance and the surface smoothness during black coloring is very superior to the conventionally known rubber-modified resin compositions, and the thermoplastic resin composition for direct vapor deposition and molded products of the present invention are used in various industries. The utility value as a material for use is extremely high. Specifically, it is particularly suitable for a vehicle lamp housing.

Hereinafter, the present invention will be described in detail.
The thermoplastic resin composition for direct vapor deposition of the present invention (hereinafter abbreviated as a thermoplastic resin composition) is obtained by adding a vinyl rubber to a composite rubber-like polymer (G) comprising a polyorganosiloxane and a (meth) acrylic acid ester polymer. A graft copolymer (A) grafted with a polymer, carbon black (C), and, if necessary, other thermoplastic resin (B) are blended.

<Graft copolymer (A)>
The graft copolymer (A) used in the present invention is obtained by grafting a vinyl polymer onto a composite rubber-like polymer (G) comprising a polyorganosiloxane and a (meth) acrylic acid ester polymer. For example, the composite rubber-like polymer (G) can be obtained by emulsion graft polymerization of at least one vinyl monomer.
<Composite rubbery polymer (G)>
The composite rubber-like polymer (G) used to obtain the graft copolymer (A) consists of a polyorganosiloxane and a (meth) acrylic acid ester polymer, and exhibits excellent glitter after direct vapor deposition of a molded product. It is a component to be made.

Although it does not specifically limit as polyorganosiloxane which comprises a composite rubber-like polymer (G), The vinyl polymerizable functional group containing polyorganosiloxane which contains a vinyl polymerizable functional group containing siloxane unit as a structural component is preferable.
In the vinyl polymerizable functional group-containing polyorganosiloxane, the content of the vinyl polymerizable functional group-containing siloxane unit is not particularly limited, but is preferably 0.3 to 3 mol%, and preferably 0.5 to 2 mol%. It is more preferable, and it is especially preferable that it is 0.5-1 mol%. If the content of the vinyl polymerizable functional group-containing siloxane unit is within such a range, the polyorganosiloxane and the (meth) acrylate rubber can be sufficiently combined, and the polyorgano can be formed on the surface of the resulting molded product. Siloxane hardly bleeds out. Therefore, the brightness of the molded product after direct vapor deposition is particularly good, and the impact resistance is also excellent.

  The vinyl polymerizable functional group-containing siloxane is not particularly limited as long as it contains a vinyl polymerizable functional group and can be bonded to dimethylsiloxane through a siloxane bond, but considering the reactivity with dimethylsiloxane. Various alkoxysilane compounds containing a vinyl polymerizable functional group are suitable. Specifically, β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylethoxydiethylsilane, γ-methacryloyloxypropyldiethoxymethylsilane, methacryloyloxysiloxane such as δ-methacryloyloxybutyldiethoxymethylsilane, vinylsiloxane such as tetramethyltetravinylcyclotetrasiloxane, p-vinylphenyldimethoxymethylsilane, and γ-mercaptopropyl And mercaptosiloxanes such as dimethoxymethylsilane and γ-mercaptopropyltrimethoxysilane. These can be used alone or in combination of two or more.

  Examples of the siloxane other than the vinyl polymerizable functional group-containing siloxane unit in the polyorganosiloxane include dimethylsiloxane. As the dimethylsiloxane, a dimethylsiloxane-based cyclic body having a 3-membered ring or more is preferable, and a 3- to 7-membered ring is particularly preferable. Specific examples include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane. These can be used alone or in combination of two or more.

Further, as the polyorganosiloxane, it is particularly preferable that the silicon atom having three or more siloxane bonds is 1 mol% or less with respect to all silicon atoms in the polyorganosiloxane, and is 0 to 0.8 mol%. Is particularly preferred. By setting it as this structure, the brightness after direct vapor deposition of the molded article obtained becomes especially excellent.
That is, as a preferable embodiment of polyorganosiloxane, for example, it is composed of 0.3 to 3 mol% of vinyl polymerizable functional group-containing siloxane units and 99.7 to 97 mol% of dimethylsiloxane units, and 3 or more siloxane bonds. Examples thereof include those having a silicon atom of 1 mol% or less based on the total silicon atoms in the polyorganosiloxane.

  The particle diameter of the polyorganosiloxane is not particularly limited, but the mass average particle diameter is preferably 600 nm or less, and more preferably 200 nm or less, for the purpose of improving the glitter after direct vapor deposition of the obtained molded product.

The polyorganosiloxane is produced, for example, as follows.
An emulsifier and water are added and emulsified in a siloxane mixture obtained by mixing dimethylsiloxane and vinyl polymerizable functional group-containing siloxane to obtain a latex. Next, the latex is made into fine particles using a homomixer that makes fine particles by a shearing force generated by high-speed rotation, a homogenizer that makes fine particles by a jet output from a high-pressure generator, or the like. Here, it is preferable to use a high-pressure emulsifier such as a homogenizer because the particle size distribution of the polyorganosiloxane latex becomes small.
And the polyorganosiloxane latex can be obtained by putting the latex after the micronization into an acid aqueous solution containing an acid catalyst and polymerizing at a high temperature. The polymerization can be stopped by cooling the reaction solution and further neutralizing with an alkaline substance such as caustic soda, caustic potash or sodium carbonate.

  As the emulsifier used for the polymerization, anionic emulsifiers such as sodium alkylbenzene sulfonate and sodium polyoxyethylene nonylphenyl ether sulfate are preferable, and among them, sulfonic acid-based emulsifiers such as sodium alkylbenzene sulfonate and sodium lauryl sulfonate are preferable. . These emulsifiers can be used alone or in combination of two or more. Usually, the amount of the emulsifier used is preferably 0.05 parts by mass or more with respect to 100 parts by mass of the siloxane mixture because the dispersion state is stable and an emulsified state having a fine particle diameter can be maintained. Moreover, since the coloring of the molded product due to the color of the emulsifier itself and the color change of the molded product due to the deterioration of the emulsifier accompanying the deterioration of the thermoplastic resin composition can be suppressed, the amount may be 5 parts by mass or less with respect to 100 parts by mass of the siloxane mixture. preferable.

Examples of the acid catalyst include sulfonic acids such as aliphatic sulfonic acid, aliphatic substituted benzenesulfonic acid, and aliphatic substituted naphthalenesulfonic acid, and mineral acids such as sulfuric acid, hydrochloric acid, and nitric acid. These acid catalysts can be used alone or in combination of two or more. Among the above-described compounds, aliphatic substituted benzenesulfonic acid is preferable and n-dodecylbenzenesulfonic acid is particularly preferable because it is excellent in stabilizing action of the polyorganosiloxane latex. Further, when n-dodecylbenzenesulfonic acid and a mineral acid such as sulfuric acid are used in combination, coloring of the molded product by the emulsifier used in the polyorganosiloxane latex can be suppressed. Although the addition amount of an acid catalyst should just be determined suitably, it is about 0.1-20 mass parts normally with respect to 100 mass parts of siloxane mixtures.
As a method for adding an acid catalyst, a method of mixing an acid catalyst together with a siloxane mixture, an emulsifier and water in advance may be adopted. You may employ | adopt the method of dripping. Among these, the latter method is preferably employed because the particle diameter of the resulting polyorganosiloxane can be easily controlled.
The polymerization time is not limited, but when the acid catalyst is mixed with a siloxane mixture, an emulsifier and water to form a fine particle for polymerization, it is preferably 2 hours or longer, particularly 5 hours or longer. In the method in which the latex in which the siloxane mixture is atomized is dropped into the aqueous solution of the acid catalyst, it is preferable to hold the latex for about 1 hour after the end of the dropping of the latex.
The polymerization temperature is preferably 50 ° C. or higher, particularly 80 ° C. or higher. The upper limit of the polymerization temperature is not particularly defined, but is usually about 95 ° C.

The (meth) acrylic acid ester polymer constituting the composite rubber-like polymer (G) contains at least one (meth) acrylic acid alkyl ester monomer or (meth) acrylic acid alkyl ester monomer. It is obtained by polymerizing a monomer mixture. In addition, monomer units other than the (meth) acrylic acid alkyl ester monomer may be contained in the (meth) acrylic acid ester polymer.
Examples of the (meth) acrylic acid alkyl ester monomer include acrylic acid alkyl esters such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and methacrylic acid. Examples include methacrylic acid alkyl esters such as hexyl, 2-ethylhexyl methacrylate, and n-lauryl methacrylate. These can be used alone or in combination of two or more. Among the above, n-butyl acrylate is preferred because the resulting thermoplastic resin composition is excellent in impact resistance.
It does not specifically limit as a manufacturing method of a (meth) acrylic-ester type polymer, A well-known method is employable.

The method for producing the composite rubber-like polymer (G) constituting the graft polymer (A) used in the present invention is, for example, heteroaggregating a plurality of latexes each containing a polyorganosiloxane and a (meth) acrylate polymer. Or a method of co-hypertrophy; in the presence of a latex containing one or both of a polyorganosiloxane and a (meth) acrylic acid ester polymer, of the polyorganosiloxane and the (meth) acrylic acid ester polymer It may be carried out by a known method such as a method of forming a polymer not contained in the latex and making it complex;
In particular, since the resulting molded article is more excellent in impact resistance and brightness after direct vapor deposition, radical polymerization of (meth) acrylic acid ester monomers (including mixtures) is carried out in the presence of latex polyorganosiloxane. The method is preferred. At that time, the method of adding the (meth) acrylic acid ester monomer (including the mixture) to the latex polyorganosiloxane may be added all at once or continuously or intermittently. You may do it.

  In the polymerization, a graft crossing agent and a crosslinking agent can be used as necessary. Examples of the grafting agent and the crosslinking agent include allyl methacrylate, triallyl cyanurate, triallyl isocyanurate, divinylbenzene, diethylene methacrylate ethylene glycol diester, dimethacrylic acid propylene glycol diester, and dimethacrylic acid 1,3-butylene glycol diester. And 1,4-butylene glycol diester of dimethacrylic acid. These can be used alone or in combination of two or more.

The content ratio of the polyorganosiloxane and the (meth) acrylic acid ester polymer in the composite rubber-like polymer (G) is such that the impact resistance of the obtained molded product and the glitter after direct vapor deposition are more excellent. Therefore, the polyorganosiloxane content is preferably 1 to 90% by mass, and the (meth) acrylic acid ester polymer content is preferably 99 to 10% by mass. The polyorganosiloxane content is more preferably 2 to 50% by mass, and particularly preferably 3 to 10% by mass.
The mass average particle diameter of the composite rubber-like polymer (G) is not particularly limited, but is preferably less than 400 nm, particularly preferably 300 nm or less, because the resulting molded article is more excellent in glitter appearance after direct vapor deposition. The lower limit of the mass average particle diameter of the composite rubbery polymer (G) is not particularly limited, but is preferably about 30 nm.

In addition, since a molded article exhibiting a glittering appearance after direct vapor deposition at a high level can be obtained, the ratio of the composite rubber-like polymer having a particle diameter of 500 nm or more in the composite rubber-like polymer (G) is 3 mass. % (Including 0% by mass), more preferably 2% by mass or less, and particularly preferably 1% by mass or less.
For the same reason, the degree of swelling of the composite rubber-like polymer (G) measured in a toluene solvent is preferably more than 0 and less than 20, and more preferably more than 0 and less than 10. The degree of swelling under a toluene solvent can be controlled by changing the type and amount of the crosslinking agent and graft crossing agent used when producing the composite rubber-like polymer (G), for example. That is, to reduce the swelling degree of the composite rubber-like polymer (G), the crosslinking agent or graft crossing agent may be increased, and to increase the swelling degree, these may be reduced. In order to control the degree of swelling within the above range, for example, about 0.3 to 6 parts by mass of a crosslinking agent or graft crossing agent is added to 100 parts by mass of (meth) acrylic acid ester monomer (including a mixture). It ’s fine.

<Vinyl monomer>
Although it does not specifically limit as a vinyl-type monomer grafted to a composite rubber-like polymer (G), Since the characteristic of this invention can fully be expressed, an aromatic alkenyl compound, (meth) acrylic-acid alkylester, A vinyl cyanide compound and the like are preferable.
Examples of the aromatic alkenyl compound include styrene, α-methylstyrene, vinyltoluene and the like. Examples of the (meth) acrylic acid alkyl ester include methyl methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate, methyl acrylate, ethyl acrylate, and butyl acrylate. Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile. Among these, it is preferable to use styrene and acrylonitrile in combination because the resulting thermoplastic resin composition or molded article is excellent in impact resistance.

The content ratio of the composite rubber-like polymer (G) used to obtain the graft copolymer (A) used in the present invention and the vinyl polymer is not particularly limited.
Among them, the content ratio (mass ratio) between the composite rubber-like polymer (G) and the vinyl monomer is as follows: composite rubber-like polymer (G) / vinyl monomer = 10-80 / 90-20 ( (Unit: mass%) is preferred, and 30-70 mass% / 70-30 (unit: mass%) is particularly preferred.
When the graft copolymer (A) obtained by graft-polymerizing a vinyl polymer to the composite rubber-like polymer (G) at such a content ratio is used, the resulting thermoplastic resin composition has impact resistance and fluidity. In addition, it has excellent brightness after direct vapor deposition of the molded product.
Although it does not specifically limit as an emulsifier used when manufacturing a graft copolymer (A), Since it is excellent in the latex stability at the time of emulsion polymerization and a polymerization rate is raised, sodium sarcosinate, fatty acid potassium, fatty acid sodium, alkenyl succinic acid Anionic emulsifiers such as various carboxylates such as dipotassium acid and rosin acid soap, alkyl sulfates, sodium alkylbenzene sulfonate and sodium polyoxyethylene nonylphenyl ether sulfate are preferred. These are properly used according to the purpose.
In addition, an emulsifier is not added at the time of emulsion graft polymerization, and the emulsifier used in the production of the polyorganosiloxane or the composite rubber-like polymer (G) can be used as it is. In that case, it is preferable to use the emulsifier mentioned above in manufacture of a polyorganosiloxane or composite rubber-like polymer (G).

Examples of the radical polymerization initiator used for the graft polymerization include a peroxide, an azo initiator, a redox initiator combined with an oxidizing agent / reducing agent, and the like. Among these, a redox initiator is preferable. The redox initiator is preferably a combination of ferrous sulfate, sodium pyrophosphate, glucose, hydroperoxide, ferrous sulfate, ethylenediaminetetraacetic acid disodium salt, longalite, hydroperoxide. In addition, the radical polymerization initiator quoted here is suitable also for superposition | polymerization of a (meth) acrylic acid ester type polymer.
In order to control the graft ratio and the molecular weight of the graft component, various chain transfer agents such as mercaptan compounds, terpene compounds, and α-methylstyrene dimers may be added to the vinyl monomers. it can.
The polymerization conditions are not particularly limited, and can be appropriately set as necessary.

As a method of recovering the graft copolymer (A) from the graft copolymer (A) latex obtained by a method such as emulsion graft polymerization, for example, the graft copolymer (A) latex is dissolved in a coagulant. Wet recovery method that coagulates in a slurry state by throwing it into hot water or semi-directly recovers the graft copolymer (A) by spraying the graft copolymer (A) latex in a heated atmosphere And spray drying method.
Examples of the coagulant used in the wet recovery method include inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid and nitric acid, and metal salts such as calcium chloride, calcium acetate and aluminum sulfate, which are selected according to the emulsifier used in the polymerization. Is done. For example, when only a carboxylic acid soap such as fatty acid soap or rosin acid soap is used as an emulsifier, the graft copolymer (A) can be recovered by using any coagulant, but an acid such as sodium alkylbenzene sulfonate can be recovered. When an emulsifier exhibiting stable emulsifying power is contained even in the region, the above-mentioned inorganic acid is insufficient, and it is necessary to use a metal salt as a coagulant.
As a method for obtaining a dry graft copolymer (A) from the slurry-like graft copolymer (A) obtained by the wet recovery method, first, the remaining emulsifier residue is eluted in water and washed, Examples include a method in which the slurry is dehydrated with a centrifugal or press dehydrator and then dried with an air dryer or the like, and a method in which dehydration and drying are simultaneously performed with a press dehydrator or an extruder. By this method, a powder or particulate dry graft copolymer (A) is obtained. The graft copolymer (A) discharged from the press dehydrator or the extruder can be recovered and directly sent to an extruder or a molding machine for producing the thermoplastic resin composition to obtain a molded product. is there.

<Other thermoplastic resin (B)>
The thermoplastic resin composition of the present invention can contain other thermoplastic resin (B) as required.
Other thermoplastic resins (B) are not particularly limited, but polymethyl methacrylate, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-α-methylstyrene copolymer (αSAN resin), styrene-maleic anhydride copolymer Polymer, acrylonitrile-styrene-N-substituted maleimide terpolymer, styrene-maleic anhydride-N-substituted maleimide terpolymer, polycarbonate resin, polybutylene terephthalate (PBT resin), polyethylene terephthalate (PET resin) , Polyethylene naphthalate (PEN resin), polyvinyl chloride, polystyrene, methyl methacrylate-styrene copolymer (MS resin), acrylonitrile-styrene-methyl methacrylate copolymer, modified polyphenylene ether (modified PPE resin), polyethylene Liamide and the like are preferably used.
In addition, polyolefins such as polyethylene and polypropylene, styrene elastomers such as styrene-butadiene-styrene (SBS), styrene-butadiene (SBR), hydrogenated SBS, styrene-isoprene-styrene (SIS), various olefin elastomers, and various polyesters. A series elastomer, polyacetal resin, ethylene-vinyl acetate copolymer, PPS resin, PES resin, PEEK resin, polyarylate, liquid crystal polyester resin, and the like can also be used.
These other thermoplastic resins (B) can be used singly or in combination of two or more.

<Carbon black (C)>
Carbon black (C) used in the present invention does not generate fish eyes of the resulting thermoplastic resin composition and is excellent in jet blackness, and therefore has a primary particle diameter of 20 nm or more.
Among these, it is preferable that the lower limit exceeds 20 nm. The upper limit is preferably 100 nm or less, more preferably 50 nm or less, and particularly preferably 35 nm or less.
When the primary particle diameter of the carbon black (C) is less than 20 nm, a lot of fish eyes tend to be generated on the surface of the obtained molded product, and when it exceeds 100 nm, the jetness tends to be lowered. .
In addition, the primary particle diameter of carbon black (C) here is a value calculated | required by the measurement based on JIS-K-6221.

The thermoplastic resin composition of the present invention is a composition comprising the aforementioned graft copolymer (A) and carbon black (C), and further blending with other thermoplastic resin (B) as required. . Specifically, carbon black (C) 0.1 with respect to 100 parts by mass of the total amount of graft copolymer (A) 1 to 100 parts by mass and other thermoplastic resin (B) 99 to 0 parts by mass. -10 mass parts is mix | blended.
Among them, since the glitter appearance after direct vapor deposition tends to be more excellent, the blending ratio of the graft copolymer (A) and the other thermoplastic resin (B) is the graft copolymer (A) / others. The thermoplastic resin (B) is preferably 5 to 80/95 to 20 (mass ratio), and the graft copolymer (A) / other thermoplastic resin (B) = 10 to 50/90 to 50 (mass). Ratio).
Carbon black (C) is blended in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the total amount of the graft copolymer (A) and the other thermoplastic resin (B). Fish eyes do not occur in the obtained molded product, and jet blackness can be imparted. Among these, it is preferable that it is the range of 0.2-8 mass parts, and it is more preferable that it is 0.3-5 mass parts.

If the amount of carbon black (C) added is less than 0.1 parts by mass, the jet blackness of the resulting thermoplastic resin composition will be low, and if it exceeds 10 parts by mass, many fish eyes will be generated.
Although the volatile matter in carbon black (C) is not particularly limited, it is preferably 0.1% by mass or more and less than 10% by mass because fish eyes of the resulting thermoplastic resin composition are reduced. Moreover, the pH value of carbon black (C) is not specifically limited.
As such carbon black (C), for example, MA7, MA8, MA11, MA100, MA220, MA230, # 4000, # 4010, # 5, # 10, # 15, # 20, #, manufactured by Mitsubishi Chemical Corporation Generally available materials such as 25, # 30, # 32, # 33, # 40, # 44, # 45, # 47, # 50, # 52, # 95, # 260 can be used.

  In the thermoplastic resin composition of the present invention, in addition to the graft copolymer (A), other thermoplastic resin (B), carbon black (C), if necessary, a stabilizer, a reinforcing agent, a filler, Additives such as flame retardants, foaming agents, lubricants, plasticizers, antistatic agents, weathering agents and UV absorbers may be blended.

  Although it does not specifically limit as a manufacturing method of a thermoplastic resin composition, A graft copolymer (A) and carbon black (C), and other thermoplastic resin (B) and various additives as needed, V-type blender Or a Henschel mixer or the like, and the mixture can be melt-kneaded using an extruder, a Banbury mixer, a kneader such as a pressure kneader, or a roll.

The molded article of the present invention is formed by molding the above-described thermoplastic resin composition. The molding method is not particularly limited, and various known molding methods such as an injection molding method, an extrusion molding method, a blow molding method, a compression molding method, a calendar molding method, and an inflation molding method can be employed.
Molded products that have undergone primary processing by the various molding methods described above are metallized by direct vapor deposition, such as vacuum vapor deposition or sputtering, on the surface without special pretreatment such as formation of an undercoat treatment layer. Processing can be performed. The metallized glitter surface may be left as it is, but in order to further protect against the generation of scratches due to dust or the like, a top coat treatment such as painting may be applied to form a silicon-based film.
It is desirable that the number of fish eyes generated on the surface of the molded product is as small as possible, and if it is less than 100 per 1 mm ² , it is preferable because a beautiful brilliant appearance can be obtained after direct vapor deposition, and further less than 50 per 1 mm ^2. If it exists, it is especially preferable from the fact that the bright appearance is more excellent.
Such a molded article is suitably used for vehicle parts, in particular, vehicle lamp housings such as tail lamps, stop lamps, and head lamps, home appliance parts such as lighting equipment housings, OA equipment housings, interior members, and the like.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to these. “%” And “parts” in the following examples and comparative examples are based on mass unless otherwise specified.
In the production examples, the mass average particle size and particle size distribution of the polymer in the latex were measured using a “submicron particle size distribution analyzer CHDF-2000” manufactured by MATEC APPLIED SCIENCES.

Production Example 1 Production of Polyorganosiloxane (L-1) Latex 98 parts of octamethylcyclotetrasiloxane and 2 parts of γ-methacryloyloxypropyldimethoxymethylsilane were mixed to obtain 100 parts of a siloxane-based mixture. To this was added an aqueous solution consisting of 0.67 parts of sodium dodecylbenzenesulfonate and 300 parts of deionized water, stirred for 2 minutes at 10000 rpm with a homomixer, and then passed once through the homogenizer at a pressure of 20 MPa. A premixed organosiloxane latex was obtained.
Further, 10 parts of dodecylbenzenesulfonic acid and 90 parts of deionized water were charged into a reactor equipped with a reagent injection container, a cooling tube, a jacket heater, and a stirring device to prepare a 10% aqueous solution of dodecylbenzenesulfonic acid. . While this aqueous solution was heated to 85 ° C., the premixed organosiloxane latex was added dropwise over 4 hours. After the completion of the addition, the temperature was maintained for 1 hour, and then cooled to 40 ° C. or lower. Next, this reaction product was neutralized to pH 7 with an aqueous caustic soda solution to complete the polymerization to obtain a polyorganosiloxane (L-1) latex.
The polyorganosiloxane (L-1) latex was dried at 170 ° C. for 30 minutes and the solid content was determined to be 17.7%. The mass average particle diameter of the polyorganosiloxane (L-1) in the latex was 50 nm, and the ratio of the rubber-like polymer having a particle diameter of 500 nm or more was almost 0%. Further, the content of the vinyl polymerizable functional group-containing siloxane unit in the polyorganosiloxane is 0.65 mol%, and the silicon atoms having 3 or more siloxane bonds are 0 mol% with respect to the total silicon atoms in the polyorganosiloxane. there were.

(Production Example 2) Production of polyorganosiloxane (L-2) latex 95.5 parts of octamethylcyclotetrasiloxane, 0.5 part of γ-methacryloyloxypropyldimethoxymethylsilane and 4 parts of tetraethoxysilane were mixed to form a siloxane system. 100 parts of a mixture were obtained. To this was added an aqueous solution consisting of 1 part of dodecylbenzenesulfonic acid, 1 part of sodium dodecylbenzenesulfonate, and 200 parts of deionized water. After stirring for 2 minutes with a homomixer at 10,000 rpm, the homogenizer was charged with a pressure of 20 MPa. A stable premixed organosiloxane latex was obtained through one pass.
This premixed organosiloxane latex is put into a reactor equipped with a cooling tube, a jacket heater and a stirrer, heated at 80 ° C. for 5 hours with stirring and mixing, then cooled to about 20 ° C. and left as it is for 48 hours. did. Next, this reaction product was neutralized to pH 7.0 with an aqueous caustic soda solution, and the polymerization was completed to obtain a polyorganosiloxane (L-2) latex.
When the solid content of the polyorganosiloxane (L-2) latex was determined in the same manner as in Production Example 1, it was 36.5%. The mass average particle diameter of the polyorganosiloxane (L-2) in the latex was 160 nm, and the ratio of the rubber-like polymer having a particle diameter of 500 nm or more was 0%. Further, the content of the vinyl polymerizable functional group-containing siloxane unit in the polyorganosiloxane is 0.3 mol%, and the silicon atoms having 3 or more siloxane bonds are 1.5 mol with respect to the total silicon atoms in the polyorganosiloxane. %Met.

(Production Example 3) Production of Graft Copolymer (A-1) In a reactor equipped with a reagent injection container, a cooling tube, a jacket heater and a stirrer, the polyorganosiloxane (L-1) obtained in Production Example 1 was used. ) Latex 2 parts (based on solid content), Latemul ASK (dipotassium alkenyl succinate; manufactured by Kao Corporation) 0.7 part, and deionized water 148.5 parts were charged and mixed. Thereafter, a mixture consisting of 45.7 parts of n-butyl acrylate (BA), 2.3 parts of allyl methacrylate (AMA), and 0.11 part of t-butyl hydroperoxide was added.
A nitrogen stream was passed through the reactor to replace the atmosphere with nitrogen, and the internal temperature was raised to 60 ° C. At that time, 0.000075 parts of ferrous sulfate heptahydrate, ethylenediaminetetraacetic acid disodium salt 0 An aqueous solution consisting of .000225 parts, Rongalite 0.2 parts and deionized water 10 parts was added to initiate radical polymerization. The liquid temperature rose to 78 ° C. by polymerization of the acrylate component. This state was maintained for 1 hour to complete the polymerization of the acrylate component to obtain a latex of a composite rubber-like polymer (G-1) of polyorganosiloxane (L-1) and n-butyl acrylate rubber.
The mass average particle diameter of the composite rubber-like polymer (G-1) is 140 nm, and in 100% of this composite rubber-like polymer (based on solid content), the proportion of rubber-like polymers having a particle diameter of 500 nm or more is almost the same. 0%. Further, a solid product of this composite rubber polymer was obtained, extracted with toluene at 90 ° C. for 12 hours, and measured for gel content (GC). As a result, it was 94.3% and the degree of swelling was 1.9. Table 1 shows the properties of the composite rubber-like polymer (G-1).

Further, after the temperature of the liquid inside the reactor was lowered to 70 ° C., an aqueous solution consisting of 0.25 parts of Rongalite and 10 parts of deionized water was added to this composite rubber-like polymer (G-1) latex, As an eye, a mixture of 2.5 parts of acrylonitrile, 7.5 parts of styrene, and 0.05 parts of t-butyl hydroperoxide was added dropwise over 2 hours for polymerization. After completion of dropping, the temperature was kept at 60 ° C. for 1 hour, and then 0.001 part of ferrous sulfate heptahydrate, 0.003 part of disodium ethylenediaminetetraacetate, 0.2 part of Rongalite, Latemu ASK (Kao ( Co., Ltd.) 0.2) and an aqueous solution consisting of 10 parts of deionized water were added. Then, as the second stage, 2 parts of a mixture consisting of 10 parts of acrylonitrile, 30 parts of styrene and 0.2 part of t-butyl hydroperoxide were added. Dropped over time and polymerized. After completion of the dropwise addition, the state at a temperature of 60 ° C. was maintained for 0.5 hours, 0.05 parts of cumene hydroperoxide was added, and the state at a temperature of 60 ° C. was maintained for 0.5 hours, followed by cooling. In this way, a graft copolymer (G-1) grafted with a copolymer of acrylonitrile and styrene on a composite rubber-like polymer (G-1) composed of polyorganosiloxane (L-1) and n-butyl acrylate rubber ( A latex of A-1) was obtained.
Subsequently, 150 parts of a 1% calcium acetate aqueous solution was heated to 60 ° C., and 100 parts of the graft copolymer (A-1) latex was gradually dropped into the solution to solidify. Then, the precipitate was dehydrated, washed, and dried to obtain a white powder graft copolymer (A-1).

(Production Examples 4 to 6) Production of Graft Copolymers (A-2) to (A-4) As shown in Table 1, the types and amounts of polyorganosiloxane, n-butyl acrylate, and allyl methacrylate are listed. Except having changed, it carried out similarly to manufacture example 3, and obtained composite rubber-like polymer (G-2)-(G-4). Table 1 shows the characteristics of each composite rubber-like polymer.
Furthermore, using each of the obtained composite rubber-like polymers (G-2) to (G-4), polymerization and recovery from the latex were performed in the same manner as in Production Example 3, and the graft copolymer (A-2 ) To (A-4) were obtained.

(Production Example 7) Production of thermoplastic resin (B-1) Acrylonitrile comprising 29 parts of acrylonitrile and 71 parts of styrene and having a reduced viscosity of N, N-dimethylformamide solution measured at 25 ° C. of 0.60 dl / g A styrene copolymer (B-1) was produced by a known suspension polymerization.

(Production Example 8) Production of thermoplastic resin (B-2) Composed of 19 parts of acrylonitrile, 53 parts of styrene and 28 parts of N-phenylmaleimide, the reduced viscosity of the N, N-dimethylformamide solution measured at 25 ° C. was 0.00. An acrylonitrile-styrene-N-phenylmaleimide terpolymer (B-2) of 65 dl / g was produced by a known continuous solution polymerization.

(Production Example 9) Production of thermoplastic resin (B-3) Composed of 25 parts of acrylonitrile and 75 parts of α-methylstyrene, the reduced viscosity of the N, N-dimethylformamide solution measured at 25 ° C is 0.50 dl / g. Acrylonitrile-α methylstyrene copolymer (B-3) was produced by known emulsion polymerization.

(Commercially available thermoplastic resin)
In addition to the thermoplastic resins produced in Production Examples 7 to 9, the following commercially available thermoplastic resins were also used.
Thermoplastic resin (B-4)
Polycarbonate (product name: Iupilon S2000F, manufactured by Mitsubishi Engineering Plastics)
Thermoplastic resin (B-5)
Polyester (Mitsubishi Rayon Co., Ltd., trade name: Toughpet N1300)

(Carbon black)
A carbon black pigment manufactured by Mitsubishi Chemical Corporation having the following primary particle size was used.
(C-1) # 2600 Primary particle size; 13 nm
(C-2) # 960 Primary particle size; 16 nm
(C-3) # 1000 Primary particle size: 18 nm
(C-4) MA100 primary particle size; 22 nm
(C-5) # 44 Primary particle size; 24 nm
(C-6) # 25 Primary particle size; 40 nm

(Examples 1-12 and Comparative Examples 1-5) Production of Thermoplastic Resin Composition The above graft copolymer and thermoplastic resin were blended in the composition shown in Table 2 or Table 3, and ethylene bisstearylamide was further added. After adding 0.4 parts with respect to 100 parts of these resin components in total, the mixture was mixed using a Henschel mixer, and this mixture was heated to a barrel temperature of 260 ° C. (TEX manufactured by Nippon Steel Works) -30) and kneaded to obtain pellets. In Tables 2 and 3, the unit of the blending amount is “part”.

(Evaluation)
The obtained thermoplastic resin composition is evaluated by the following method.
(1) Weather resistance 100 mm x 100 mm x 3 mm black plate test piece under the conditions of cylinder setting temperature 230 ° C, mold temperature 70 ° C, injection speed 99%, using an injection molding machine "IS80FP" manufactured by Toshiba Machine Co., Ltd. Is molded.
The obtained black test piece was subjected to an exposure treatment of 500 hours using a sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd.) at a black panel temperature of 63 ° C. and a cycle condition of 60 minutes (rainfall: 12 minutes). Apply. Then, the gloss of the test piece before and after the test is measured using a digital variable angle gloss meter “UGV-5D” manufactured by Suga Test Instruments Co., Ltd., and the gloss retention (%) represented by the following formula is obtained.
Gloss retention (%) = (Gloss of specimen after exposure test) / (Gloss of specimen before exposure test) × 100

(2) Brightness after direct vapor deposition Using an injection molding machine “IS80FP” manufactured by Toshiba Machine Co., Ltd., with a cylinder set temperature of 230 ° C., a mold temperature of 70 ° C., and an injection speed of 99%, 100 mm × 100 mm × 3 mm Mold into a plate. Next, an aluminum vapor deposition film having a film thickness of about 50 nm is formed on the surface of the obtained molded article by a vacuum vapor deposition method under the conditions of a vacuum degree of 1 × 10 ⁻⁶ Torr, a current value of 400 mA, and a film formation speed of 1.5 nm / second. Is deposited. Then, a top coat layer made of SiO _{2 is} further vacuum-deposited on the aluminum deposition film.
About the molded article which performed direct vapor deposition as mentioned above, a regular reflectance (%) and diffuse reflectance (%) are measured with a reflectometer (Murakami Color Research Laboratory "HR-100"). Then, the brightness is evaluated.

(3) Number of fish eyes on the molded plate 100 mm x 100 mm x 3 mm under conditions of cylinder set temperature 230 ° C, mold temperature 70 ° C, injection speed 60%, using an injection molding machine "IS80FP" manufactured by Toshiba Machine Co., Ltd. A black plate test piece was molded.
The surface of the obtained black test piece is visually measured with an optical microscope (manufactured by Nikon Corporation) for the number of fish eyes per 1 mm ² to determine surface smoothness.

(result)
The evaluation results are shown in Tables 2 and 3.
As shown in Tables 2 and 3, a graft copolymer (A) in which a vinyl polymer is grafted to a composite rubber-like polymer (G) composed of a polyorganosiloxane and a (meth) acrylic acid ester polymer, and In Examples 1 to 12 containing carbon black having a primary particle diameter of 20 nm or more, all of the obtained molded articles exhibited high gloss values after the weather resistance test. Furthermore, the number of projecting fish eyes was small, the diffuse reflectance after direct vapor deposition was low, and the luster was excellent, as well as jetness.
On the other hand, in Comparative Examples 1 to 3 containing carbon black having a primary particle diameter of less than 20 nm and Comparative Example 5 in which the amount of carbon black exceeds 10 parts by mass, the surface smoothness was low. In Comparative Example 4 where the amount of carbon black was less than 0.1 parts by mass, the jetness was low.

Further, when the proportion of the rubber-like polymer having a mass average particle diameter of 500 nm or more is less than 3% by mass in the total composite rubber-like polymer (G) (Example 8), the glitter after direct vapor deposition is high. It became clear by comparison with Example 1 that it tends to be higher.
Furthermore, it turned out that various things can be used from the result of Examples 1-12 as another thermoplastic resin (B) mix | blended with a graft copolymer (A).

Claims (5)

1 to 100 parts by mass of a graft copolymer (A) obtained by grafting a vinyl polymer on a composite rubber-like polymer (G) comprising a polyorganosiloxane and a (meth) acrylic acid ester polymer;
99 to 0 parts by mass of other thermoplastic resin (B) (provided that the total of components (A) and (B) is 100 parts by mass);
A thermoplastic resin composition for direct vapor deposition, comprising 0.1 to 10 parts by mass of carbon black (C) having a primary particle size of 20 nm or more.   The thermoplastic resin composition for direct vapor deposition according to claim 1, wherein the ratio of the rubber-like polymer having a particle diameter of 500 nm or more in the composite rubber-like polymer (G) is less than 3% by mass.   Other thermoplastic resins (B) are polymethyl methacrylate, acrylonitrile-styrene copolymer, acrylonitrile-α methylstyrene copolymer, styrene-maleic anhydride copolymer, acrylonitrile-styrene-N-substituted maleimide ternary. Copolymer, styrene-maleic anhydride-N-substituted maleimide terpolymer, polycarbonate resin, polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polyvinyl chloride, polystyrene, methyl methacrylate-styrene copolymer, acrylonitrile The thermoplastic resin composition for direct vapor deposition according to claim 1 or 2, wherein the thermoplastic resin composition is at least one selected from the group consisting of a styrene-methyl methacrylate copolymer, a modified polyphenylene ether, and a polyamide.   A molded article obtained by molding the thermoplastic resin composition for direct vapor deposition according to any one of claims 1 to 3.   The molded article according to claim 4, wherein the surface is subjected to metallization treatment by a direct vapor deposition method.