JP7100565B2 - Mold - Google Patents

Description

The present invention relates to a molded product containing a thermoplastic resin.

Conventionally, molded products such as polycarbonate and ABS resin which have been hard-coated for interior and exterior parts of automobiles, ASA and ABS resin which have been painted in a jet-black tone have been used. However, the hard coat treatment (HC treatment) has problems such as defects due to the occurrence of coat spots and low productivity, and in painting, there is a problem of volatile organic compounds (VOC) contained in the paint. From the viewpoint of such problems and cost reduction, molded products without HC treatment or painting are eagerly desired, and in recent years, replacement with resin by compound has been actively studied. Here, important properties include surface appearance and scratch resistance.

In order to impart these characteristics, for example, a method of mixing (compounding) an additive with a thermoplastic resin has been used for a long time. As the thermoplastic resin, methacrylic resin is mainly used in recent years. The reason is that the methacrylic resin has excellent weather resistance and has the highest surface pencil hardness among the resins. Further, since it has high transparency, it is possible to develop a deep and good coloring in a molded product, particularly in the case of a coating substitute.

However, in applications where high required characteristics are imposed on the surface, even methacrylic resin cannot withstand various wear phenomena and is often subjected to HC treatment.

In the case of molded products, in addition to the initial high appearance, for example, assuming a vehicle member, when assembling a resin molded product to the vehicle body, the work is done while wearing work gloves, so it is resistant to hand scratches. Is required. Further, when dust or dirt adheres to the surface of the molded member during use, it is required that the surface of the molded member is not scratched when wiped with a cotton cloth, tissue paper or the like. In addition, in various cases, there is a tendency that a high degree of scratch resistance is required in practical use.

As a method for solving this problem, for example, Patent Document 1 proposes a technique for improving scratch resistance by containing a silicone and a fatty acid compound in an acrylic resin.

Further, Patent Document 2 proposes a technique for improving scratch resistance by containing a (meth) acrylic resin and an inorganic filler.

International Publication No. 2018/016473 International Publication No. 2017/200048

However, Patent Document 1 improves scratch resistance by containing a specific silicone or fatty acid compound, and although it is effective for relatively soft sliding cloth such as work gloves, it is hard such as steel wool. There is a concern that the surface appearance of the sliding cloth of the system may deteriorate.

Further, Patent Document 2 improves scratch resistance by containing silica, but the glossiness of the molded product itself tends to decrease due to the inclusion of a hard additive, and particularly in the vertical direction of the molded surface. The amount of reflection of light having an incident angle of 20 ° with respect to the above is reduced, and there is a concern that the initial surface appearance may be deteriorated.

Therefore, a molded product that has a high appearance when viewed from any direction, does not require HC treatment or coating, and has a small change in visibility after a scratch resistance test is eagerly desired for many applications.

Under the above circumstances, it is an object of the present invention to provide a molded body having a high appearance and a small change in visibility even after a scratch resistance test in view of the above-mentioned problems of the prior art. ..

As a result of diligent studies to solve the above-mentioned problems, the present inventors have found that the above-mentioned problems in the prior art can be solved by forming a molded body having a specific glossiness and maximum height on the surface. The invention was completed.

That is, the present invention is as follows.
[1] The glossiness (G20) at an incident angle of 20 °, which is molded under the conditions of (1) and (2) below and measured according to JIS Z8741, is 75% or more, and the gloss at an incident angle of 60 °. The ratio (G20 / G60) of the G20 to the degree (G60) was 0.85 to 1.0, and was measured according to ISO 1997 after a scratch resistance test (sliding 5 times under a load of 0.2 kg of steel wool). It is characterized by containing 0.01 to 10% by mass of a surface modifier (D) having a maximum height (Rz) of 1.0 μm or less, containing a thermoplastic resin (A), and having a Vickers hardness of 10 GPa or more. The molded body.
(1) Molding temperature: 140-320 ° C
(2) Mold temperature: Vicat softening temperature (VST) -70 ° C to VST-20 ° C (VST is measured at a load of 50 N and a temperature rise rate of 50 ° C / hour in accordance with ISO306 B50).
[2] The molded product according to [1], wherein the maximum height (Rz) is 0.6 μm or less.
[3] The molded product according to [1] or [2], wherein the thermoplastic resin (A) is an amorphous resin.
[4 ] The molded product according to any one of [1] to [ 3 ], which is an injection molded product.
[ 5 ] The molded product according to any one of [1] to [ 4 ], which is a housing or design material for optical use, electrical / electronic use, or vehicle use.
[ 6 ] The molded product according to [ 5 ], which is a design material for motorcycles or automobiles.
[ 7 ] The molded body according to [ 6 ], which is one of a tail lamp garnish, a rear lamp garnish, a front lamp garnish, a pillar garnish, a front grill, a rear grill, a license garnish, a wheel center cap, a license plate garnish, or a Dora mirror cover. ..

According to the present invention, it is possible to provide a molded product having a high appearance and a small change in visibility even after a scratch resistance test.

Hereinafter, embodiments for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be appropriately modified and carried out within the scope of the gist thereof.
In the present specification, the monomer component before polymerization is referred to as "-monomer", and "monomer" may be omitted. Further, the structural units constituting the polymer are referred to as "-monomer unit" and / or "-structural unit", and may be simply expressed as "-unit".

<Molded body>
The molded body of the present embodiment has a glossiness (G20) of 75% or more at an incident angle of 20 ° measured in accordance with JIS Z8741, and the ratio of the G20 to the glossiness (G60) at an incident angle of 60 °. (G20 / G60) is 0.85 to 1.0, and the maximum height (Rz) measured according to ISO 1997 after the scratch resistance test (sliding 5 times under a load of 0.2 kg of steel wool) is 1. It is a molded product having a size of 0 μm or less and containing a thermoplastic resin (A).
In the present specification, the mixture which is the raw material of the molded product of the present embodiment before molding may be referred to as a thermoplastic resin composition. The thermoplastic resin composition contains the thermoplastic resin (A), and may further contain a dye (B), a carbon black (C), a surface modifier (D), and other components described later.
Hereinafter, each component constituting the molded product of the present embodiment will be described.

[Thermoplastic resin (A)]
The thermoplastic resin (A) constituting the molded product of the present embodiment is not particularly limited, and is, for example, a methacrylic resin, a polystyrene resin, a polycarbonate resin, a syndiotactic polystyrene resin, and an ABS resin (acrylonitrile-. Butadiene-styrene copolymer), AS resin (acrylonitrile-styrene copolymer), BAAS resin (butadiene-acrylonitrile-acrylonitrile rubber-styrene copolymer, MBS resin (methyl methacrylate-butadiene-styrene copolymer) Copolymer), AAS resin (acrylonitrile-acrylonitrile rubber-styrene copolymer), biodegradable resin, polycarbonate-ABS resin alloy, modified polyphenylene ether resin, polypropylene resin, polyethylene resin, polyacetal resin , Polyester resin, polyamide resin and the like.
Among these, from the viewpoint of controlling G20 and G20 / G60 of the obtained molded product, amorphous resin is particularly preferable, and methacrylic resin, polystyrene resin, polycarbonate resin, ABS resin, and AS resin are more preferable. Of these, methacrylic resins are particularly preferable from the viewpoints of high transparency, surface hardness, and scratch resistance.
Here, the resin contains a copolymer obtained by polymerizing a plurality of types of monomers, and the copolymer contains 50% by mass of the monomer unit derived from the main monomer with respect to the total amount of the resin. The above is preferable. The main monomer mainly comprises a methacrylic acid ester monomer for a methacrylic resin, a styrene-based monomer for a polystyrene-based resin, and a carbonate-based monomer for a polycarbonate-based resin. ..
As the thermoplastic resin (A), only one type may be used alone, or two or more types may be mixed and used.

(Methacrylic resin)
Hereinafter, the details of the methacrylic resin will be described.
In the case of a methacrylic resin, it may be a copolymer composed of a structural unit derived from a methacrylic acid ester monomer (also simply referred to as “methacrylic acid ester monomer unit” in the present specification), or methacrylic acid. The ester monomer unit and the structural unit derived from another vinyl monomer copolymerizable with the methacrylic acid ester monomer (also simply referred to as "other vinyl monomer unit" in the present specification) are referred to as each other. It may be a copolymer containing. Of these, the copolymer is preferable.

（一般式（Ｉ）中、Ｒ₁は、１～１８個の炭素原子を有する炭化水素基を表し、該炭化水素基の炭素上の水素原子は水酸基やハロゲン基によって置換されていてもよい。） -Methacrylic acid ester monomer-
The methacrylic acid ester monomer forming the methacrylic acid ester monomer unit constituting the methacrylic acid resin is not particularly limited as long as it can achieve the effect of the present invention, but a preferable example is the following general formula ( Examples thereof include the monomers represented by I).

(In the general formula (I), R ₁ represents a hydrocarbon group having 1 to 18 carbon atoms, and the hydrogen atom on the carbon of the hydrocarbon group may be substituted with a hydroxyl group or a halogen group. )

The methacrylic acid ester monomer is not particularly limited, and is, for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, and methacrylic acid. (2-Ethylhexyl), methacrylic acid (t-butylcyclohexyl), benzyl methacrylate, methacrylic acid (2,2,2-trifluoroethyl) and the like can be mentioned. Among these, methyl methacrylate, ethyl methacrylate, propyl methacrylate and the like are more preferable, and methyl methacrylate is particularly preferable, from the viewpoint of easy handling and availability. The methacrylic acid ester monomer may be used alone or in combination of two or more.
When the methacrylic acid-based resin is a copolymer, the content of the methacrylic acid ester monomer unit is preferably 80 to 99.9% by mass, more preferably 88 to 9% by mass, based on the total amount of the methacrylic acid-based resin. It is 99% by mass, more preferably 90 to 98% by mass. When the content of the methacrylic acid ester monomer unit is 80% by mass or more, the heat resistance tends to be further improved. Further, when the content of the methacrylic acid ester monomer unit is 99.9% by mass or less, the fluidity tends to be further improved.

（一般式（ＩＩ）中、Ｒ₂は１～１８個の炭素原子を有する炭化水素基を表し、該炭化水素基の炭素上の水素原子は水酸基やハロゲン基によって置換されていてもよい。） -Other vinyl monomers-
The other vinyl monomer (also simply referred to as “other vinyl monomer” in the present specification) forming the above-mentioned other vinyl monomer unit constituting the methacrylic resin is not particularly limited. Preferred examples include an acrylic acid ester monomer represented by the following general formula (II).

(In the general formula (II), R ₂ represents a hydrocarbon group having 1 to 18 carbon atoms, and the hydrogen atom on the carbon of the hydrocarbon group may be substituted with a hydroxyl group or a halogen group.)

The acrylic acid ester monomer is not particularly limited, and for example, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, cyclohexyl acrylate, phenyl acrylate, and acrylic. Examples thereof include acid (2-ethylhexyl), acrylic acid (t-butylcyclohexyl), benzyl acrylate, and acrylic acid (2,2,2-trifluoroethyl). Among these, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate and the like are more preferable, and methyl acrylate is particularly preferable, from the viewpoint of easy handling and availability.

Further, the vinyl monomer other than the acrylic acid ester monomer of the general formula (II) that can be copolymerized with the methacrylic acid ester monomer is not particularly limited, but for example, acrylic acid, styrenic acid and the like. Α, β-unsaturated acids; unsaturated group-containing divalent carboxylic acids such as maleic acid, fumaric acid, itaconic acid, cinnamic acid and their alkyl esters; styrene, o-methylstyrene, m-methylstyrene, p- Methyl styrene, 2,4-dimethyl styrene, 2,5-dimethyl styrene, 3,4-dimethyl styrene, 3,5-dimethyl styrene, p-ethyl styrene, m-ethyl styrene, о-ethyl styrene, p-tert- Styrene-based monomers such as butylstyrene and isopropenylbenzene (α-methylstyrene); 1-vinylnaphthalene, 2-vinylnaphthalene, 1,1-diphenylethylene, isopropenyltoluene, isopropenylethylbenzene, isopropenylpropylbenzene, Aromatic vinyl compounds such as isopropenylbutylbenzene, isopropenylpentylbenzene, isopropenylhexylbenzene, isopropenyloctylbenzene; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; unsaturated carboxylics such as maleic anhydride and itaconic anhydride. Acid anhydrides; N-substituted maleimides such as maleimide, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, etc .; amides such as acrylamide, methacrylicamide; ethylene glycol di (meth) Ethylene glycol such as acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, or the hydroxyl groups at both ends of the oligomer are esterified with acrylic acid or methacrylic acid; neo Pentylglycol Di (meth) acrylate, di (meth) acrylate and other two alcohol hydroxyl groups esterified with acrylic acid or methacrylic acid; polyvalent alcohol derivatives such as trimethylolpropane and pentaerythritol are acrylic acid or methacrylic. Acid-esterified; Examples thereof include polyfunctional monomers such as divinylbenzene.
As the above-mentioned other vinyl monomers, only one kind may be used alone, or two or more kinds may be used in combination.

The content of the other vinyl monomer unit is preferably 0.1 to 20% by mass, more preferably 1.0 to 15% by mass, and further preferably 1 with respect to the total amount of the methacrylic resin. It is .5 to 12% by mass, and particularly preferably 2.0 to 10% by mass. When the content of the other vinyl monomer unit is 0.1% by mass or more, the fluidity and heat resistance tend to be further improved. Further, when the content of the other vinyl monomer unit is 20% by mass or less, the heat resistance tends to be further improved.

In the methacrylic resin, a vinyl monomer other than the vinyl monomer exemplified above may be appropriately added and copolymerized for the purpose of improving properties such as heat resistance and processability.

-Weight average molecular weight and molecular weight distribution of methacrylic resin-
The weight average molecular weight and the molecular weight distribution of the methacrylic resin will be described.
The weight average molecular weight (Mw) of the methacrylic resin measured by gel permeation chromatography (GPC) is preferably 50,000 to 300,000. When the weight average molecular weight of the methacrylic resin is within the above range, the fluidity, the mechanical strength, and the solvent resistance can be balanced, and good molding processability tends to be maintained. In particular, from the viewpoint of obtaining excellent mechanical strength and solvent resistance, the weight average molecular weight (Mw) of the methacrylic resin is preferably 50,000 or more, more preferably 60,000 or more, further preferably 70,000 or more, still more preferably 80,000 or more. Preferably, 90,000 or more is even more preferable. Further, from the viewpoint of showing good fluidity of the methacrylic resin, the weight average molecular weight (Mw) of the methacrylic resin is preferably 300,000 or less, more preferably 250,000 or less, further preferably 230000 or less, and further preferably 210000 or less. More preferably, it is more preferably 180,000 or less.

The molecular weight distribution (Mw / Mn) of the methacrylic resin is preferably 1.6 to 6.0, more preferably 1.7 to 5.0, and further preferably 1.8 to 5.0. be. When the molecular weight distribution of the methacrylic resin is within the above range, the balance between the molding process flow and the mechanical strength tends to be better. Here, Mw represents a weight average molecular weight, and Mn represents a number average molecular weight.
The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the methacrylic resin can be measured by GPC, and specifically, can be measured by the method described in Examples described later. Specifically, a calibration line is created from the elution time and the weight average molecular weight using a standard methacrylic resin that has a known monodisperse weight average molecular weight and is available as a reagent in advance and an analytical gel column that elutes the high molecular weight component first. Then, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the methacrylic resin to be measured can be obtained based on the subsequently obtained calibration lines. The molecular weight distribution can be calculated from the obtained weight average molecular weight (Mw) and number average molecular weight (Mn). The number average molecular weight (Mn) is a simple average of the molecular weights per molecule, and is defined by the total weight of the system / the number of molecules in the system. The weight average molecular weight (Mw) is defined as the average molecular weight by weight fraction.

-Ratio of molecular weight components of 1/5 or less of the peak top molecular weight (Mp) of methacrylic resin-
From the viewpoint of solvent resistance and fluidity, the proportion of the component having a molecular weight of 1/5 or less of the peak top molecular weight (Mp) obtained from the GPC elution curve of the methacrylic resin obtained by the GPC method is the methacrylic resin. It is preferably 6 to 50%, more preferably 7 to 45%, still more preferably 8 to 43%, still more preferably 9 to 40%, based on the total area of the GPC elution curve of the resin. Ah, even more preferably 10-38%. Since the proportion of the component having a molecular weight of 1/5 or less of the peak top molecular weight (Mp) is 6% or more, the molding fluidity tends to be further improved, the molecular orientation of the surface of the molded body is relaxed, and the scratch resistance is scratched. The sex tends to be good. Further, since the ratio of the component having a molecular weight of 1/5 or less of the peak top molecular weight (Mp) is 50% or less, the solvent resistance tends to be further improved.
Here, the "ratio (%) occupied by a component having a molecular weight of 1/5 or less of the peak top molecular weight (Mp)" is the peak top molecular weight (Mp) when the total area of the GPC elution curve is 100%. ) Is the ratio of the area area corresponding to the component having a molecular weight of 1/5 or less, and can be measured by the method described in Examples described later. The "peak top molecular weight (Mp)" refers to the weight molecular weight showing a peak in the GPC elution curve. When a plurality of peaks are present in the GPC elution curve, the molecular weight at the peak indicated by the weight molecular weight having the highest abundance is defined as the peak top molecular weight (Mp).
It should be noted that a methacrylic resin component having a weight molecular weight of 500 or less causes a foam-like appearance defect called silver at the time of molding, so it is preferable that the amount is as small as possible.

-Manufacturing method of methacrylic resin-
The methacrylic resin can be produced by any one of bulk polymerization, solution polymerization, suspension polymerization method and emulsion polymerization method. Of these, bulk polymerization, solution polymerization and suspension polymerization methods are preferable, and suspension polymerization methods are more preferable.

The polymerization temperature may be appropriately selected depending on the polymerization method, but is preferably 50 ° C. or higher and 100 ° C. or lower, and more preferably 60 ° C. or higher and 90 ° C. or lower.

When producing a methacrylic resin, a polymerization initiator may be used. The polymerization initiator is not particularly limited, but when radical polymerization is carried out, for example, di-t-butyl peroxide, lauroyl peroxide, decanoyl peroxide, stearyl peroxide, benzoyl peroxide, t-butyl peroxy. Neodecanate, t-butylperoxypivalate, dilauroyl peroxide, dicumyl peroxide, t-butylperoxy-2-ethylhexanoate, 1,1-bis (t-butylperoxy) -3, Organic radicals such as 3,5-trimethylcyclohexane, cyclohexaneperoxide, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 1,1-bis (t-butylperoxy) cyclohexane; azo; Bisisobutyronitrile, azobisisobutyronitrile, 1,1-azobis (1-cyclohexanecarbonitrile), 2,2'-azobis-4-methoxy-2,4-azobisisobutyronitrile, 2,2 Common azo-based radical polymerization initiators such as'-azobis-2,4-dimethylvaleronitrile, 2,2'-azobis-2-methylbutyronitrile, 2- (carbamoylazo) isobutyronitrile are mentioned. Be done. These may be used alone or in combination of two or more. A combination of these radical initiators and an appropriate reducing agent may be used as a redox-based initiator.

These radical polymerization initiators and / or redox-based initiators are generally used in the range of 0 to 1 part by mass with respect to 100 parts by mass of the total amount of all the monomers used in the polymerization of the methacrylic resin. It can be appropriately selected in consideration of the temperature at which the polymerization is carried out and the half-life of the polymerization initiator.

When a bulk polymerization method, a cast polymerization method, or a suspension polymerization method is selected as the polymerization method of the methacrylic resin, an organic peroxide is used as the polymerization initiator from the viewpoint of preventing the methacrylic resin from being colored. It is preferable to polymerize. Examples of such an organic peroxide include the same as those described above, and among them, lauroyl peroxide, decanoyl peroxide, t-butylperoxy-2-ethylhexanoate and the like are preferable, and lauroylper. Oxides are more preferred.

When the methacrylic resin is polymerized by the solution polymerization method at a high temperature of 90 ° C. or higher, the organic peroxide and azobis are soluble in the organic solvent used and have a 10-hour half-life temperature of 80 ° C. or higher. It is preferable to use an initiator or the like as a polymerization initiator. Examples of such organic peroxides and azobis initiators include the same as above, among which 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane and cyclohexaneper. Oxides, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 1,1-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) isobutyronitrile and the like are preferred.

When producing a methacrylic resin, the molecular weight of the methacrylic resin may be controlled, if necessary. The method for controlling the molecular weight of the methacrylic resin is not particularly limited, and examples thereof include a method of changing a polymerization method or a polymerization condition, a method of selecting a polymerization initiator, a method of adjusting the amount of a chain transfer agent, an inifata, and the like. .. As these molecular weight control methods, only one kind of method may be used, or two or more kinds of methods may be used in combination.

The inifata is not particularly limited, and examples thereof include dithiocarbamates, triphenylmethylazobenzene, and tetraphenylethane derivatives.

The chain transfer agent is not particularly limited, and examples thereof include alkyl mercaptans, dimethylacetamide, dimethylformamide, triethylamine and the like. Among these, alkyl mercaptans are preferable from the viewpoint of handleability and stability. The alkyl mercaptans are not particularly limited, but for example, n-butyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-tetradecyl mercaptan, n-octadecyl mercaptan, 2-ethylhexylthioglycol. Examples thereof include rates, ethylene glycol dithioglycolates, trimethylolpropane tris (thioglycolate), pentaerythritol tetrakis (thioglycolates) and the like.

The chain transfer agent and the inifata can be appropriately added according to the molecular weight of the target methacrylic resin, and the molecular weight can be adjusted by adjusting the addition amount of the chain transfer agent and the inifata. Generally, it is used in the range of 0.001 part by mass to 5 parts by mass with respect to 100 parts by mass of the total amount of all the monomers used in the polymerization of the methacrylic resin.

Further, as a method for producing a methacrylic resin in which the ratio of a component having a molecular weight of 1/5 or less of the peak top molecular weight (Mp) obtained from the GPC elution curve is in the range of 6 to 50%, a low molecular weight methacryl is used. Examples thereof include a method of melt-blending a based resin and a high molecular weight methacrylic resin, a method of producing by a multi-stage polymerization method, and the like. In the case of producing a methacrylic resin having a molecular weight of 1/5 or less of the above Mp and an abundance of 6 to 50%, the method is not particularly limited, but it is multistage from the viewpoint of quality stability. It is more preferable to use a polymerization method.
When the multi-stage polymerization method is used, first, in the first-stage polymerization, a polymer obtained by polymerizing a methacrylic acid ester monomer and another vinyl monomer and having a weight average molecular weight of 5000 to 50,000 measured by GPC. It is preferable to manufacture (i). Next, the inside of the polymerization system is kept at a temperature higher than the polymerization temperature of the first stage for a certain period of time. Then, in the presence of the polymer (i), the methacrylic acid ester monomer and other vinyl monomers can be further polymerized to produce a polymer (ii) having a weight average molecular weight of 60,000 to 350,000. preferable. When the methacrylic resin is a homopolymer, homopolymerization is performed in the first-stage and second-stage polymerization without using other vinyl monomers. Further, when the methacrylic resin is a mixture of a homopolymer and a copolymer, it is also possible to carry out homopolymerization in the first-stage polymerization and copolymerization in the second-stage polymerization.

From the viewpoint of improving the polymerization stability during production, the fluidity of the methacrylic resin, the mechanical strength of the resin molded product, and the relaxation of the molecular orientation of the surface of the molded product, the content of the polymer (i) is the methacrylic resin. The content of the polymer (ii) is preferably 95 to 50% by mass with respect to the total amount of the methacrylic resin. Considering the balance between polymerization stability, fluidity, mechanical strength of the molded product, and relaxation of molecular orientation on the surface of the molded product, the content ratio of the polymer (i) / polymer (ii) is more preferably 7 to 47. Mass% / 93-53% by mass, more preferably 10-45% by mass / 90-65% by mass, even more preferably 13-43% by mass / 87-57% by mass, still more preferably 15- It is 40% by mass / 85-60% by mass.

Further, the polymer (i) is preferably a polymer containing 80 to 100% by mass of a methacrylic acid ester monomer unit and 0 to 20% by mass of another vinyl monomer unit, and is preferably a methacrylic acid ester monomer. More preferably, the polymer contains 90 to 100% by mass of the unit and 0 to 10% by mass of the other vinyl monomer unit, and 95 to 100% by mass of the methacrylic acid ester monomer unit and the other vinyl monomer unit. It is more preferable that the polymer contains 0 to 5% by mass. The ratio of the monomer units constituting the polymer (i) can be adjusted by controlling the amount of the monomers added in the polymerization step of the polymer (i) of the multistage polymerization. The polymer (i) preferably has a low content of other vinyl monomers, and may not contain other vinyl monomers.

Further, from the viewpoint of suppressing defects in silver and the like during molding, polymerization stability, and fluidity, the weight flat fraction average amount of the polymer (i) is preferably 5,000 to 50,000, more preferably 10,000 to 45,000. , More preferably 18,000 to 42,000, and particularly preferably 20,000 to 40,000. As described above, the weight average molecular weight of the polymer (i) can be controlled by using a chain transfer agent or an inifata, adjusting the amounts thereof, or appropriately changing the polymerization conditions. The weight flat fraction average amount of the polymer (i) can be measured by GPC in the same manner as described above.

The polymer (ii) is preferably a polymer containing 80 to 99.9% by mass of a methacrylic acid ester monomer unit and 0.1 to 20% by mass of another vinyl monomer unit, and is a simple methacrylic acid ester. It is more preferable that the polymer contains 90 to 99.9% by mass of a weight unit and 0.1 to 10% by mass of another vinyl monomer unit, and the methacrylic acid ester monomer unit is 92.5 to 99.8. It is more preferable that the polymer contains 0.2 to 7.5% by mass and 0.2 to 7.5% by mass of other vinyl monomer units. The ratio of the monomer units constituting the polymer (ii) can be controlled by adjusting the amount of the monomers added in the polymerization step of the polymer (ii) of the multistage polymerization.

Further, from the viewpoint of solvent resistance and fluidity, the weight flat fraction average amount of the polymer (ii) is preferably 60,000 to 350,000, more preferably 100,000 to 320,000, and further preferably 130,000 to 300,000. , More preferably 150,000 to 270000. As described above, the weight average molecular weight of the polymer (ii) can be controlled by using a chain transfer agent or an inifata, adjusting these amounts, or appropriately changing the polymerization conditions. The weight flat weight averager amount of the polymer (ii) can be measured by GPC in the same manner as described above.

In the above-mentioned multi-stage polymerization method, the composition of each of the polymer (i) and the polymer (ii) can be easily controlled, the temperature rise due to the heat generation of the polymerization during the polymerization can be suppressed, and the viscosity in the system can be stabilized. In this case, the raw material composition mixture of the polymer (ii) may be partially polymerized before the polymerization of the polymer (i) is completed, but once it is cured (in this case, the inside of the system is cured. It is preferable to keep the temperature higher than the polymerization temperature) and add the raw material composition mixture of the polymer (ii) after the polymerization is completed. By curing in the first stage, not only the polymerization is completed, but also unreacted monomers, initiators, chain transfer agents, etc. can be removed or inactivated, which adversely affects the polymerization in the second stage. It will not reach. As a result, the desired weight average molecular weight can be obtained.

The polymerization temperature may be appropriately selected and produced depending on the polymerization method, but is preferably 50 ° C. or higher and 100 ° C. or lower, and more preferably 60 ° C. or higher and 90 ° C. or lower. The polymerization temperatures of the polymer (i) and the polymer (ii) may be the same or different.
The temperature for raising the temperature during curing is preferably 5 ° C. or higher, more preferably 7 ° C. or higher, and even more preferably 10 ° C. or higher than the polymerization temperature of the polymer (i). Further, the time for holding at a raised temperature during curing is preferably 10 minutes or more and 180 minutes or less, and more preferably 15 minutes or more and 150 minutes or less.

(Polystyrene resin)
Examples of the polystyrene-based resin include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,4-dimethylstyrene, and 3,5. -As a monomer unit derived from styrene-based monomers such as dimethylstyrene, p-ethylstyrene, m-ethylstyrene, о-ethylstyrene, p-tert-butylstyrene, and isopropenylbenzene (α-methylstyrene). Examples include styrene-containing resin. The polystyrene-based resin may contain a structural unit derived from the above-mentioned methacrylic acid ester monomer and other vinyl monomers (excluding the styrene-based monomer) in addition to the above-mentioned styrene-based monomer. .. Of these, polystyrene is preferable.
As the polystyrene-based resin, only one type may be used alone, or two or more types may be mixed and used.
The content of the structural unit derived from the styrene-based monomer in the polystyrene-based resin is preferably 50% by mass or more, more preferably 60% by mass or more, and further preferably 70% by mass or more.

(Polycarbonate resin)
The polycarbonate-based resin includes, for example, a resin produced by reacting a dihydric phenol-based compound with phosgen in the presence of a catalyst and a molecular weight modifier, and an ester of a carbonate precursor such as a dihydric phenol-based compound and diphenyl carbonate. Examples thereof include resins manufactured by using exchange.
As the divalent phenol compound, a bisphenol compound can be used, and 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) is preferably used. Bisphenol A may be partially or wholly converted to other divalent phenols. Examples of the dihydric phenol other than bisphenol A include hydroquinone, 4,4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) cyclohexane, and 2,2-bis ( 3,5-dimethyl-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) ketone, bis Examples thereof include (4-hydroxyphenyl) ether and halogenated bisphenol such as 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane.
As the polycarbonate-based resin, a single polymer such as bisphenol A-based polycarbonate, a copolymer of two or more kinds of divalent phenols, or a mixture thereof can be used. Examples of the polycarbonate-based resin include linear polycarbonate, branched polycarbonate, polyester carbonate copolymer, and the like.
Examples of the branched polycarbonate include those obtained by reacting a polyfunctional aromatic compound such as trimellitic acid anhydride and trimellitic acid with a dihydric phenolic compound and a carbonate precursor.
Examples of the polyester carbonate copolymer include those obtained by reacting a bifunctional carboxylic acid with a divalent phenolic compound and a carbonate precursor.
As the polycarbonate resin, only one kind may be used alone, or two or more kinds may be mixed and used.

The content of the thermoplastic resin (A) is preferably 50% by mass or more and 99.9% by mass or less with respect to the total amount of the thermoplastic resin composition from the viewpoint of further improving the surface appearance of the obtained molded body. It is more preferably 60% by mass or more and 98.5% by mass or less, and further preferably 70% by mass or more and 98% by mass or less.
The content of the methacrylic resin is preferably 50% by mass or more and 99.9% by mass or less with respect to the total amount of the thermoplastic resin composition from the viewpoint of controlling G20 / G60 and Rz of the obtained molded product. It is more preferably 60% by mass or more and 98.5% by mass or less, and further preferably 70% by mass or more and 98% by mass or less.

[Dye (B)]
The thermoplastic resin composition may contain the dye (B), assuming various uses of the molded product described later.
The dye (B) preferably contains one or more dyes selected from the group consisting of red dyes, yellow dyes, green dyes, blue dyes, and purple dyes, and preferably contains red dyes and yellow dyes. More preferably, it is one or more dyes selected from the group consisting of dyes, green dyes, blue dyes, and purple dyes.
From the viewpoint of developing a deeper jet-blackness, it is preferable to contain three or more kinds of dyes, and it is more preferable that these dyes are three or more kinds of dyes having different hues from each other, and red dyes and yellow dyes. , 3 or more kinds of dyes selected from the group consisting of green dyes, blue dyes and purple dyes are more preferable. Rather than simply combining a blue dye and a yellow dye, or a combination of a green dye and a red dye in a narrow range, a combination that evenly contains the so-called three primary colors of light expresses jet blackness. This is because it is preferable from the viewpoint of expressing a deeper jet-blackness. Such combinations include, for example, combinations of purple dyes, green dyes, yellow dyes and bluish dyes; combinations of purple dyes, yellow dyes, green dyes and red dyes; red dyes, greens. There are combinations of appropriate amounts of multiple dyes, such as combinations of dyes and blue dyes, and among these, there are already many commercially available products, and there are many types of weather-resistant dyes, which will be described later, so it is more desirable. From the viewpoint of easily realizing the jet-blackness of the above, a combination of a red dye, a green dye, a yellow dye and a blue dye is preferable.

As the red dye, for example, Solvent red 52, 111, 135, 145, 146, 149, 150, 151, 155, 179, 180, 181 , 196, 197, 207, Disperse Red 22, 60, 191 and the like. Examples of the bluish dye include Solvent Blue 35, 45, 78, 83, 94, 97, 104, 105 and the like in terms of color index. Examples of the yellow dye include Disperse Yellow 54, 160, and Solvent yellow 33 in terms of color index. Examples of the green dye include Solvent Green 3, 20, and 28 in terms of color index. Examples of the purple dye include Solvent Violet 28, 13, 31, 35, and 36 in terms of color index. These dyes are used individually for each color or in combination of two or more.

The type of dye is not particularly limited, but the dye (B) includes one or more dyes selected from the group consisting of anthraquinone dyes, heterocyclic compound dyes and perinone dyes from the viewpoint of weather resistance. It is preferable, and it is more preferable that it consists of only one or more dyes selected from the group consisting of anthraquinone dyes, heterocyclic compound dyes and perinone dyes.
Examples of the anthraquinone dye include Solvent Violet 36, Solvent Green 3, 28, Solvent Blue 94, 97, Disperse Red 22 and the like in terms of color index.
Examples of the heterocyclic compound dye include Disperse Yellow 160 and the like in terms of color index.
Examples of the perinone dye include Solvent red 179 and the like in terms of color index.
Each of these may be used alone or in combination of two or more.

The content of the dye (B) is preferably 0.01% by mass or more and 1.5% by mass or less, and more preferably 0.02% by mass or more and 1.0% by mass with respect to the total amount of the thermoplastic resin composition. % Or less, more preferably 0.03% by mass or more and 0.8% by mass or less, still more preferably 0.04% by mass or more and 0.6% by mass or less, and particularly preferably 0.05% by mass or less. It is 0.5% by mass or less. When the dye (B) is 0.01% by mass or more and 1.5% by mass or less, the G20 and G20 / G60 of the obtained molded product tend to be adjusted within a predetermined range.

[Carbon black (C)]
When the thermoplastic resin composition is toned to a black color, it is preferable to further contain carbon black (C) from the viewpoint of weather resistance. The carbon black (C) is not particularly limited, and any substance that is compatible with the thermoplastic resin (A) and does not easily affect its physical properties can be suitably used.
As the type of carbon black (C), furnace black is preferable, and it is more preferable that the arithmetic average particle size by microscopic observation is 10 to 50 nm in order to adjust G20 and G20 / G60 of the molded product within a predetermined range. ..

Further, the carbon black (C) may include a carbon black (C) whose surface is surface-coated with a coating agent. By using such carbon black (C), a deeper jet blackness can be exhibited.
The coating agent is not particularly limited, and is, for example, from zinc stearate, magnesium stearate, calcium stearate, oleic acid amide, stearic acid amide, palmitate amide, methylene bisstearyl amide, and ethylene bisstearyl amide (EBS). It is preferable to contain one or more compounds selected from the above group, and it is more preferable to contain only one or more such compounds. Of these, zinc stearate and EBS are more preferred. By using such a coating agent, there is a tendency that a deeper jet blackness can be realized. The coating agent may be used alone or in combination of two or more.
When the surface of carbon black is coated with a coating agent, the ratio (Wc / Ws) of the mass Wc of carbon black to the mass Ws of the coating agent is preferably 20/80 to 60/40, which is more preferable. Is 30/70 to 50/50. When Wc / Ws is within the above range, it tends to be possible to realize a deeper jet blackness.

As the types of carbon black before coating, more specifically, the arithmetic average diameter by microscopic observation is 10 to 40 nm, the nitrogen adsorption specific surface area specified by JIS K6217: 2001 is 50 to 400 m ² / g, and 950 ° C. A carbon black satisfying one or more of the volatile contents of 0.5 to 3% by mass when heated for 7 minutes can be preferably used.

The content of carbon black (C) is preferably 0.01% by mass or more and 1.5% by mass or less, more preferably, with respect to the total amount of the thermoplastic resin composition from the viewpoint of weather resistance and jet blackness. It is 0.02% by mass or more and 1% by mass or less, and more preferably 0.05% by mass or more and 0.5% by mass or less.

[Surface modifier (D)]
It is preferable that the thermoplastic resin composition further contains the surface modifier (D) from the viewpoint of controlling the Rz of the molded product.
The organic surface modifier (D) is not particularly limited as long as the effect of the present invention is not impaired, and is, for example, a phthalic acid ester type, a fatty acid ester type, a trimellitic acid ester type, and a phosphoric acid ester type. , Polyester-based plasticizers, higher fatty acids and salts thereof, higher fatty acid esters, higher fatty acid mono, di, or triglyceride-based release agents, polymers composed of siloxane-based skeletons, acrylic-based cross-linked beads, urethane-based cross-linked beads , Stylus-based crosslinked beads and the like.
Further, the inorganic surface modifier (D) is not particularly limited as long as the effect of the present invention is not impaired, and for example, glass fiber, carbon fiber, calcium silicate fiber, potassium titanate fiber, and fluorinated. Aluminum oxide fiber, flake-shaped glass, talc, kaolin, mica, hydrotalcite, calcium carbonate, zinc carbonate, zinc oxide, zinc dioxide, calcium monohydrogen phosphate, wollastonite, glass beads, silica, zeolite, alumina, oxidation Aluminum, boehmite, aluminum hydroxide, titanium oxide, titanium dioxide, silicic acid, silicon oxide, silicon dioxide, silicon carbide, magnesium oxide, magnesium dioxide, calcium silicate, sodium aluminosilicate, magnesium silicate, barium sulfate, brass, copper , Silver, aluminum, nickel, iron, iron oxide, graphite, carbon nanotubes, calcium fluoride, mica, montmorillonite, swellable fluorine mica, apatite, graphene and the like.
From the viewpoint of surface appearance, titanium dioxide, magnesium oxide, aluminum oxide, aluminum hydroxide, zinc dioxide, silicic acid dioxide, silicon carbide, barium sulfate, aluminum nitride, magnesium nitride, talc, kaolin, mica, calcium carbonate, wollastonite. , Glass fiber, glass beads, silica, graphite, carbon nanotube, graphene and the like are preferably contained.
As the above-mentioned surface modifier (D), only one kind may be used alone, or two or more kinds may be used in combination.

The average particle size of the surface modifier (D) is preferably 0.01 to 5 μm in order to control G20, G20 / G60, and Rz of the obtained molded product. The average particle size is more preferably 0.05 to 4 μm, further preferably 0.1 to 3 μm, even more preferably 0.2 to 2 μm, particularly preferably 0.25 to 1 μm, and 0.25 μm to 0.8 μm. More particularly preferred.
If the average particle size of the surface modifier (D) is less than 5 μm, it can be measured by a dynamic light scattering method, and if it is 5 μm or more, it can be measured by a laser diffraction method. The average particle size of the surface modifier (D) in the present specification represents the primary particle size.

Further, it is preferable that the Vickers hardness of the surface modifier (D) is 5 GPa or more in order to control the Rz of the obtained molded product. The Vickers hardness of the surface modifier (D) is more preferably 7 GPa or more, further preferably 10 GPa or more, further preferably 15 GPa or more, and particularly preferably 20 GPa or more. Further, when it is 50 GPa or less, G20 and G20 / G60 of the obtained molded product tend to improve, 40 GPa or less is more preferable, and 30 GPa or less is further preferable.
The Vickers hardness refers to a value measured at room temperature (25 ° C.) ° C. in accordance with JIS Z 2244, converted as 102 HV = 1 GPa.

Further, the surface modifier (D) may be appropriately surface-treated for the purpose of becoming more compatible with the thermoplastic resin (A).

The content of the surface modifier (D) is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.1% by mass or more and 8% by mass, based on the total amount of the thermoplastic resin composition. It is more preferably 0.1% by mass or more and 6% by mass or less, further preferably 0.1% by mass or more and 4% by mass or less, and most preferably 0.2% by mass or more and 3% by mass or less. It is particularly preferably 0.3% by mass or more and 2% by mass or less. The content of the surface modifier (D) is preferably 0.01% by mass or more in order to control Rz, and the content of the surface modifier (D) is 10% by mass or less in G20 /. It is preferable in controlling G60.

[Other ingredients]
(Additive)
Various additives may be added to the molded product of the present embodiment, if necessary.

Examples of the additive include antistatic agents such as polyether-based, polyether ester-based, polyether ester amide-based, alkyl sulphonate, and alkylbenzene sulphonate; antioxidants, ultraviolet absorbers, heat stabilizers, and the like. Stabilizers such as light stabilizers; flame retardant, flame retardant aid, curing agent, curing accelerator, conductivity-imparting agent, stress-relieving agent, crystallization accelerator, hydrolysis inhibitor, impact-imparting agent, compatibilizer, Nucleating agent, strengthening agent, reinforcing agent, flow conditioner, sensitizer, rubber polymer, thickener, anti-settling agent, anti-sagging agent, filler, defoaming agent, coupling agent, rust preventive, antibacterial -Examples include antifungal agents, antifouling agents, and conductive polymers.
In particular, it is preferable to add a heat stabilizer, an ultraviolet absorber, a flame retardant and the like for a wide range of indoor and outdoor applications. Further, in order to increase the impact strength, a rubbery copolymer may be added as a stress relaxation agent or an impact imparting agent.
The content of the additive may be 30% by mass or less with respect to the total amount of the thermoplastic resin composition.

((Heat stabilizer))
The heat stabilizer is not particularly limited, and examples thereof include antioxidants such as hindered phenol-based antioxidants and phosphorus-based processing stabilizers. Of these, hindered phenolic antioxidants are preferred. Such heat stabilizers are not particularly limited, but are, for example, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, thiodiethylenebis [3- (3,5). -Di-tert-butyl-4-hydroxyphenyl) propionate, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, N, N'-hexane-1,6-diylbis [3] -(3,5-Di-tert-butyl-4-hydroxyphenylpropionamide, 3,3', 3'', 5,5', 5''-hex-tert-butyl-a, a', a''-(Mesitylen-2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) -o-cresol, 4,6-bis (dodecylthiomethyl) -о-cresol, ethylene Bis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate, hexamethylene bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-Tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 1,3 , 5-Tris [(4-tert-butyl-3-hydroxy-2,6-xylin) methyl] -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trion, 2, 6-Di-tert-butyl-4- (4,6-bis (octylthio) -1,3,5-triazine-2-ylamine) phenol and the like can be mentioned, and pentaerythritol terakis [3- (3,5-) Di-tert-butyl-4-hydroxyphenyl) propionates are preferred. These may be used alone or in combination of two or more.

((UV absorber))
The ultraviolet absorber is not particularly limited, and is, for example, a benzotriazole-based compound, a benzotriazine-based compound, a benzoate-based compound, a benzophenone-based compound, an oxybenzophenone-based compound, a phenol-based compound, an oxazole-based compound, and a malonic acid ester-based compound. , Cyanoacrylate-based compounds, lactone-based compounds, salicylic acid ester-based compounds, benzoxadinone-based compounds and the like. Of these, benzotriazole-based compounds and benzotriazine-based compounds are preferable. These may be used alone or in combination of two or more.

The vapor pressure (P) of the ultraviolet absorber at 20 ° C. is preferably 1.0 × 10 ^-4 Pa or less, more preferably 1.0 × 10 ^-6 Pa or less, from the viewpoint of obtaining excellent molding processability. It is more preferably 1.0 × 10 ^-8 Pa or less. Here, "excellent molding processability" means, for example, that the UV absorber does not adhere to the mold surface during injection molding, and that the UV absorber adheres to the roll during film molding. means. If the UV absorber adheres to the roll, the UV absorber will eventually adhere to the surface of the target molded product, which may deteriorate the appearance and optical characteristics. Therefore, the molded product is used as an optical material. In particular, it is important that the molding processability is excellent.

The melting point (Tm) of the ultraviolet absorber is preferably 80 ° C. or higher, more preferably 100 ° C. or higher, still more preferably 130 ° C. or higher, still more preferably 160 ° C. or higher, from the viewpoint of preventing bleed-out. Is.

The mass reduction rate of the ultraviolet absorber when the temperature is raised from 23 ° C. to 260 ° C. at a rate of 20 ° C./min is preferably 50% or less, more preferably 30% or less, from the viewpoint of preventing bleed-out. , More preferably 15% or less, even more preferably 10% or less, still more preferably 5% or less.

((Flame retardants))
The flame retardant is not particularly limited, and examples thereof include a cyclic nitrogen compound, a phosphorus-based flame retardant, a silicon-based flame retardant, a cage-shaped silsesquioxane or a partially cleaved structure thereof, and a silica-based flame retardant.

Examples of the kneading method when the amorphous resin composition and various additives are mixed include the methods described in "Method for producing an amorphous resin composition" described later, and are not particularly limited. do not have.

((Rubber copolymer))
The rubber copolymer is not particularly limited, but for example, general organic rubber particles such as butadiene-based ABS rubber, acrylic-based, polyolefin-based, silicon-based, and fluororubber can be used. For example, acrylic rubber polymers disclosed in Japanese Patent Application Laid-Open No. 60-17406, Japanese Patent Application Laid-Open No. 8-245854, and Japanese Patent Application Laid-Open No. 7-68318 may be mentioned.

As the rubbery copolymer, rubber particles having a multi-layer structure of two or more layers are particularly preferable, and from the viewpoint of compatibility with the above-mentioned methacrylic resin, acrylic multi-layer rubber particles having a multi-layer structure of two or more layers are particularly preferable. More preferred. Further, by using the rubber particles having a multi-layer structure of three or more layers rather than the rubber particles having a two-layer structure, thermal deterioration during the molding process of the molded body of the present embodiment and deformation of the rubber particles due to heating are suppressed. , Maintaining heat resistance of the molded body and suppressing thermal deformation tend to be suppressed, which is particularly preferable.

The rubber particles having a multi-layer structure having a three-layer structure or more refer to rubber particles having a multi-layer structure in which a soft layer made of a rubber-like polymer and a hard layer made of a glass-like polymer are laminated, and are not particularly limited, but for example, inside. From soft-hard-soft-hard, soft-hard-hard, soft-soft-hard, hard-soft-hard, hard-hard-soft-hard, hard-soft-hard-hard, etc. Preferably, the particles have a three-layer structure formed in the order of hard layer-soft layer-hard layer from the inside, or a particle having a four-layer structure formed in the order of hard-hard-soft-hard, hard-soft-hard-hard. be.
By having the hard layer in the innermost layer and the outermost layer, the deformation of the rubber particles tends to be suppressed, and by having the soft component in the central layer, good toughness tends to be imparted.

For example, when the rubbery polymer is formed of a three-layer structure acrylic rubber, the acrylic acid ester monomer unit in the copolymer forming the innermost layer is not particularly limited, but is, for example, acrylic. Suitable examples include n-butyl acid and 2-hexyl acrylate.

When the innermost layer (bi) of the rubbery copolymer contains an aromatic vinyl compound monomer unit as a copolymer component, the aromatic vinyl compound monomer unit is used for a methacrylic resin. The same as the monomer can be used, but styrene or a derivative thereof is preferably used.

When the innermost layer (bi) of the rubbery copolymer contains a copolymerizable polyfunctional monomer unit, the copolymerizable polyfunctional monomer unit is not particularly limited, but for example, ethylene. Glycoldi (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, allyl (meth) acrylate, triallyl isocyanurate , Dialyl maleate, divinylbenzene and the like. These can be used alone or in combination of two or more.
Among the above compounds, allyl (meth) acrylate is particularly preferable.

When the rubbery copolymer is formed of three-layered acrylic rubber particles, the copolymer forming the central layer (b-ii) imparts excellent toughness to the methacrylic resin composition. Therefore, it is preferable that the copolymer exhibits soft rubber elasticity.

When the acrylic acid ester monomer unit is included as the monomer constituting the copolymer forming the central layer (b-ii), the acrylic acid ester monomer unit is not particularly limited, but is preferable. Examples thereof include methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate and the like, and one of these can be used alone or in combination of two or more.
In particular, n-butyl acrylate and 2-hexyl acrylate are more preferable.

When an aromatic vinyl compound monomer is used as the monomer copolymerized with the acrylic acid ester monomer constituting the copolymer forming the central layer (b-ii), the aromatic vinyl compound is used. As the monomer, styrene or a derivative thereof is preferable.

When the copolymer forming the central layer (b-ii) contains a copolymerizable polyfunctional monomer unit, the copolymerizable polyfunctional monomer unit is the innermost layer (b-) described above. The same copolymerizable polyfunctional monomer used in i) can be used, and the content thereof is 0.1% by mass or more and 5% by mass or less with respect to the entire central layer (b-ii). Is preferable because it has a good cross-linking effect, and the cross-linking tends to be moderate and the rubber elastic effect tends to be large.

When the rubbery copolymer is formed of acrylic rubber particles having a three-layer structure, the outermost layer (b-iii) of the acrylic rubber particles can be copolymerized with methyl methacrylate and the methyl methacrylate. It is preferable that the monomer is a copolymer with a above-mentioned monomer, and the monomer unit capable of copolymerizing with methyl methacrylate is not particularly limited, and for example, n-butyl acrylate and 2-hexyl acrylate are used. preferable.

[Manufacturing method of thermoplastic resin composition]
In the thermoplastic resin composition, for example, the thermoplastic resin (A) and the dye (B), the carbon black (C), the surface modifier (D), and other components to be blended as necessary are stirred. It can be obtained by melt-kneading (compounding) after sufficiently mixing with the above. Alternatively, a high-concentration masterbatch based on the thermoplastic resin (A) is prepared by melt-kneading using a dye (B) and / or a carbon black (C) and a surface modifier (D), and the masterbatch thereof is prepared. The batch may be diluted with another thermoplastic resin (A) and melt-kneaded.

Examples of the melt-kneading method include a method of kneading and kneading using a kneader such as an extruder, a heating roll, a kneader, a roller mixer, and a Banbury mixer. Of these, kneading with an extruder is particularly preferable from the viewpoint of productivity, and a twin-screw extruder is preferable to a single-screw extruder. The kneading temperature may follow a preferable processing temperature of the thermoplastic resin (A), preferably 140 to 320 ° C, more preferably 160 to 300 ° C, still more preferably 180 to 280 ° C. When the kneading temperature is 320 ° C or lower, the generation of residual monomers due to thermal decomposition of the thermoplastic resin can be further suppressed, the physical properties such as heat resistance are reduced due to the plasticizing effect of the residual monomers, and silver during injection molding is more effective. There is a tendency that it can be reliably prevented.
Further, the discharge amount (kg / hr) / kneading rotation speed (rpm) improves the dispersibility of the dye (B), the carbon black (C), and the surface modifier (D), and G20, G20 / G60, and In controlling Rz, it is preferably 1.4 or less, more preferably 1.2 or less, further preferably 1.0 or less, and even more preferably 0.8 or less. , 0.6 or less is particularly preferable, and 0.5 or less is most preferable.

[Characteristics of molded product]
(Glossiness at an incident angle of 20 ° (G20))
The molded product of the present embodiment has a glossiness of 75% or more at an incident angle of 20 ° measured according to JIS Z8741. G20 is preferably 76% or more, more preferably 77% or more, still more preferably 78% or more, still more preferably 79% or more, and particularly preferably 80% or more.
When G20 is 75% or more, the arithmetic mean roughness (Ra) of the molded product according to the test method described later tends to be low, and the surface appearance is good.

(Ratio of glossiness (G20) at incident angle 20 ° to glossiness (G60) at incident angle 60 ° (G20 / G60))
In the molded product of the present embodiment, the ratio (G20 / G60) of the glossiness (G20) at the incident angle of 20 ° to the glossiness (G60) at the incident angle of 60 ° measured according to JIS Z8741 is 0. It is 85 to 1.0. When G20 / G60 is in this range, the arithmetic mean roughness (Ra) of the molded product according to the test method described later tends to be low, and the molded product has an excellent glossiness even when visually recognized from any angle. G20 / G60 is preferably 0.87 to 1.0, more preferably 0.88 to 1.0, still more preferably 0.89 to 1.0, and even more preferably 0. It is 90 to 1.0, and particularly preferably 0.91 to 1.0.

The G20 indicates the glossiness when the angle of the incident light with respect to the vertical direction of the surface of the molded body is 20 °, and the G60 is the glossiness when the angle of the incident light with respect to the vertical direction of the surface of the molded body is 60 °. Indicates the degree. G20 and G60 are values measured by a gloss meter in accordance with JIS Z8741 and can be specifically measured by the method described in Examples described later.

(Arithmetic Mean Roughness (Ra))
The molded product of the present embodiment preferably has an arithmetic mean roughness (Ra) of less than 0.026 μm, more preferably less than 0.020 μm. When the arithmetic mean roughness is less than 0.026 μm, the molded product has an excellent glossy appearance no matter what angle it is visually recognized.
The arithmetic average roughness (Ra) is a value measured using a surface roughness measuring instrument in accordance with JIS-B0601, and specifically, it is measured by the method described in Examples described later. be able to.

(Maximum height (Rz) after scratch resistance test (sliding 5 times under a load of 0.2 kg of steel wool))
The molded body of the present embodiment has a maximum height (Rz) of 1.0 μm or less after a scratch resistance test (sliding 5 times under a load of 0.2 kg of steel wool). Rz is preferably 0.8 μm or less, more preferably 0.7 μm or less, still more preferably 0.6 μm or less, still more preferably 0.5 μm or less, and particularly preferably 0.4 μm or less. Is. When it is 1.0 μm or less, the amount of change in b ^* before and after the scratch resistance test in the color system b ^* , which is an index of the color difference described later, Δb ^* (Δb ^* = (b ^* after the scratch resistance test)-( B ^* before scratch resistance test
) Tends to be low, making it difficult to visually distinguish from the undamaged peripheral area, and making the scratches less noticeable.
The maximum height (Rz) is a value measured using a surface roughness measuring instrument in accordance with ISO 1997, and the evaluation curve is divided into reference lengths, and the average line is defined at each reference length. The sum of the height from the top to the highest mountain peak and the depth to the deepest valley bottom is calculated and averaged. Specifically, it can be measured by the method described in Examples described later.

(Amount of change in color system b ^* before and after scratch resistance test (Δb ^* ))
In the molded body of the present embodiment, the amount of change in b ^* on the surface of the molded body before and after the scratch resistance test with respect to the color system b ^* , which is an index of the color difference (Δb ^* = (b ^* after the scratch resistance test)-(scratch resistance test). The b ^* )) before the scratch test is preferably 0.5 or less, and more preferably 0.3 or less. Δb ^* is 0
.. When it is 5 or less, even after the scratch resistance test, there is a tendency that almost no change can be visually confirmed as compared with before the test.
Note that b ^* is a value measured by the SCE method (10 ° field of view / D65 light source) using a spectrocolorimeter based on JIS Z 8722.

(Vicat softening temperature)
The molded product of the present embodiment has a Vicat softening temperature (VST) of preferably 80 ° C. or higher, more preferably 90 ° C. or higher. In addition, there is no particular upper limit to the Vicat softening temperature.
The Vicat softening temperature is a value measured at a load of 50 N and a heating rate of 50 ° C./hour in accordance with ISO306 B50.

(Manufacturing method of molded product)
The molded product of the present embodiment can be manufactured, for example, as follows. First, if necessary, the above-mentioned thermoplastic resin composition obtained in the form of pellets is put into a mold cavity of an injection molding machine. At this time, it is preferable to use a mold having a mold cavity having a shape corresponding to the shape of the molded body and having a one-point gate as the mold. Further, the position of the gate in the mold is preferably a position in contact with a portion of the finally obtained molded product that is covered with another member and cannot be visually confirmed. Next, the thermoplastic resin composition is injection-molded by the injection molding machine under predetermined conditions. In this way, the injection molded product of the present embodiment can be obtained.

Further, the mold temperature at the time of injection molding is from the viewpoint of further enhancing the transferability of the polished mold surface when the mold surface is polished, and suppresses excessive cooling of the thermoplastic resin, and the G20 of the molded product and From the viewpoint of controlling G20 / G60, it is preferable to adjust the temperature in the range of VST-100 ° C to VST-5 ° C with respect to the Vicut softening temperature (VST) of the thermoplastic resin (A) to be molded, and more preferably. It is in the range of VST-95 ° C to VST-10 ° C, more preferably in the range of VST-90 ° C to VST-15 ° C, and even more preferably in the range of VST-70 ° C to VST-20 ° C. Particularly preferably, it is in the range of VST-60 ° C to VST-20 ° C, and most preferably it is in the range of VST-40 ° C to VST-20 ° C.
The Vicat softening temperature of the thermoplastic resin (A) is a value measured at a load of 50 N and a heating rate of 50 ° C./hour in accordance with ISO306 B50.

Further, the file count used when polishing the mold is preferably 5000 count or higher, more preferably 7000 count or higher, further preferably 8000 count or higher, and further preferably 10000 count or higher. It is even more preferable, and it is particularly preferable that the number is 12000 or higher. When the number of the mold is 5000 or more, it is preferable to control G20 and G20 / G60 of the molded product.

The molding temperature at the time of injection molding is preferably adjusted in the range of 140 to 320 ° C., more preferably in the range of 160 to 300 ° C., and further preferably 180 to 280 ° C. from the viewpoint of fluidity and thermal decomposition. Is in the range of.

(Use of molded product)
The molded product of the present embodiment has a high appearance when viewed from any angle, and can be suitably used for applications in which it is required that the change in visibility after scratch resistance is as small as that of a painted product.
Such uses are not particularly limited, but are, for example, furniture, household goods, storage / storage goods, building materials such as walls / roofs, toys / play equipment, hobby uses such as pachinko face plates, medical / welfare goods, OA. It can be used for equipment, AV equipment, battery electrical equipment, lighting equipment, ships, body parts of aircraft structures, vehicle parts, etc., especially for optical applications, electrical / electronic applications, vehicle body parts, vehicle parts, etc. It can be suitably used for the housing or the design material of.

Examples of optical applications include various lenses, touch panels, and the like, and transparent substrates used in solar cells.
In addition, in the fields of optical communication systems, optical exchange systems, and optical measurement systems, it can also be used as a waveguide, an optical fiber, a covering material for an optical fiber, an LED lens, a lens cover, a cover for EL lighting, and the like.

For electrical and electronic applications, for example, personal computers, game machines, televisions, car navigation systems, display devices such as electronic paper, printers, copy machines, scanners, fax machines, electronic notebooks and PDA, electronic desktop calculators, electronic dictionaries, cameras, and videos. Examples include cameras, mobile phones, battery packs, recording medium drives and readers, mice, ten keys, CD players, MD players, portable radio / audio players, and the like. In particular, it can be suitably used for design parts of housings such as televisions, personal computers, car navigation systems, and electronic papers.

In particular, it is preferably used as a design material for motorcycles or automobiles. Examples of the design material for automobiles include automobile exterior preparation materials and automobile interior preparation materials, but automobile exterior preparation materials are preferable from the viewpoint of more advantageously utilizing the effects of the present invention. Examples of the automobile exterior preparation material of the present embodiment include a tail lamp garnish, a rear lamp garnish, a front lamp garnish, a pillar garnish, a front grill, a rear grill, a licensed garnish, a wheel center cap, a number plate garnish, and a Dora mirror cover. , These are suitable. These uses are generally thin-walled longitudinal parts, and designability is important.

Hereinafter, the present embodiment will be specifically described with reference to Examples, but the present embodiment is not limited to the examples described later.

[Measurement and evaluation method]
<I. Molecular weight and molecular weight distribution of thermoplastic resin (A)>
The weight average molecular weight and molecular weight distribution of the thermoplastic resin (A) were measured with the following devices and conditions.
Measuring device: Tosoh gel permeation chromatography (HLC-8320GPC)
Columns: 1 TSKgel SuperH2500, 2 TSKgel SuperHM-M, 1 TSKguardcumn SuperH-H, serial connection In this column, the high molecular weight elutes quickly and the low molecular weight elutes slowly.
Detector: RI (differential refractometer) detector Detection sensitivity: 3.0 mV / min
Column temperature: 40 ° C
Sample: 0.02 g of thermoplastic resin in tetrahydrofuran 10 mL solution Injection amount: 10 μL
Developing solvent: Tetrahydrofuran, flow rate; 0.6 mL / min
As a standard sample for the calibration curve, the following 10 types of polymethylmethacrylicate Calibration Kit PL2020-0101 M-M-10 having a known monodisperse weight peak molecular weight and different molecular weights were used.
As the polymethyl methacrylate used in the standard sample for the calibration curve, the peak molecular weight of each single peak was as follows.
Peak molecular weight Standard sample 1 1,916,000
Standard sample 2 625,500
Standard sample 3 298,900
Standard sample 4 138,600
Standard sample 5 60, 150
Standard sample 6 27,600
Standard sample 7 10,290
Standard sample 8 5,000
Standard sample 9 2,810
Standard sample 10 850
Under the above conditions, the RI detection intensity with respect to the elution time of the amorphous resin was measured.
Weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), GPC peak top molecular weight (Mp) and GPC of non-crystalline resin (A) based on the area area in the GPC elution curve and the calibration line of the cubic approximation formula. The ratio (%) of the component having a molecular weight of 1/5 or less of the peak top molecular weight (Mp) was determined.

<II. Analysis of structural units of thermoplastic resin (A)>
¹ The structural unit of the thermoplastic resin (A) was identified by 1 H-NMR measurement, and its abundance (mass%) was calculated.
¹ The measurement conditions for 1 H-NMR measurement are as follows.
Equipment: JEOL-ECA500
Solvent: CDCl ₃ -d ₁ (deuterated chloroform)
Sample: 15 mg of the thermoplastic resin (A) was dissolved in 0.75 mL of CDCl ₃ -d ₁ to prepare a sample for measurement.

<III. G20 and G20 / G60>
For the flat plate-shaped evaluation samples obtained in Examples , Reference Examples and Comparative Examples, G20 (%) and G60 (%) and G60 (%) on the surface were used with a gloss meter VG7000 manufactured by Nippon Denshoku Co., Ltd. in accordance with JIS Z8741. %) Was measured, and G20 / G60 was calculated. The measurement was performed at three locations near the center of the sample surface, and the average of each measured value was calculated and used as G20 and G60.

<IV. Surface appearance ＞
As an evaluation of the surface appearance of the flat plate-shaped evaluation samples obtained in Examples , Reference Examples and Comparative Examples, the arithmetic average roughness (Ra) (μm) of the surface of the evaluation sample was measured by a surface roughness measuring instrument (SURFTEST). It was measured according to JIS-B0601 using SJ-210 (manufactured by Mitutoyo Co., Ltd.), and judged by the following evaluation criteria together with visual evaluation. The measurement was performed at three locations near the center of the sample surface, and the average of the measured values was calculated and used as Ra.
◎ (excellent): Ra is less than 0.02, and it has a high appearance from any angle.
○ (Good): Ra is 0.02 or more and less than 0.026, and the appearance is poor when viewed from some angles visually.
× (inferior): Ra is 0.026 or more, and the overall appearance is poor visually.

<V. Maximum height (Rz)>
Steel wool scratch resistance test The maximum height (Rz) was measured by the following method using the injection-molded flat plate-shaped evaluation samples obtained in Examples , Reference Examples and Comparative Examples. Steel wool (product number: TSW0000-200, count: # 0000 ultra-fine) is set on the tip of the 1 cm jig of the Gakushin type friction tester (RT-200 manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd.), and the steel wool does not shift. After fixing, the steel wool slides back and forth 5 times on the surface of the sample under the conditions of a load of 0.2 kg, a test distance of 50 mm, and a test speed of 100 mm / s in a direction perpendicular to the flow direction of the resin. I let you. After that, in order to measure the maximum height (Rz) (μm) of the sliding portion, the Rz in the direction perpendicular to the sliding direction (direction perpendicular to the surface of the sample) is measured by the surface roughness measuring instrument (SURFTEST SJ-). 210, manufactured by Mitutoyo Co., Ltd.) and measured in accordance with ISO 1997.
The maximum height (Rz) is defined by dividing the evaluation curve into reference lengths and finding the sum of the height from the average line to the highest peak and the depth to the deepest valley bottom at each reference length. It is an average value.

<VI. Amount of change in color system b ^* (Δb ^* )>
In addition, the above V. As a visibility evaluation after the scratch resistance test, the color system b ^* on the sample surface before and after the test was measured using a spectrocolorimeter (Konica Minolta Japan Co., Ltd., "CM-700d") compliant with JIS Z 8722. Measured by SCE method (10 ° field of view / D65 light source), Δb
^* (Δb ^* = (b ^* after scratch resistance test)-(b ^* before scratch resistance test)) was calculated. Judgment was made based on the following evaluation criteria as well as visual evaluation.
◎ (excellent): Δb ^* is 0.3 or less, and there is almost no visual change before and after the scratch resistance test.
◯ (Good): Δb ^* is more than 0.3 and 0.5 or less, and the visual change before and after the scratch resistance test is slight.

× (inferior): Δb ^* is more than 0.5, and there is a clear visual change before and after the scratch resistance test.

<VII. Heat resistance>
As an evaluation of heat resistance, the thermoplastic resin (A) of Examples , Reference Examples and Comparative Examples and the Bicut softening temperature (VST) (° C.) of the flat plate-shaped evaluation sample were used in an HDT test apparatus (heat distortion tester) (Toyo Seiki). It was measured according to ISO306 B50 using (manufactured by Mfg. Co., Ltd.). The load was 50 N, and the heating rate was 50 ° C./hour.

<Comprehensive evaluation>
Comprehensive evaluation was carried out according to the following criteria.
◎ (excellent): The visual evaluation of the surface appearance is ◎, and the visual evaluation after the scratch resistance test is ◎.
○ (Slightly excellent): The visual evaluation of the surface appearance is ◎ and the visual evaluation after the scratch resistance test is ○, or the visual evaluation of the surface appearance is ○ and the visual evaluation after the scratch resistance test is ◎.
Δ (Good): The visual evaluation of the surface appearance is ○, and the visual evaluation after the scratch resistance test is ○.
× (inferior): Either or both of the visual evaluation of the surface appearance and the visual evaluation after the scratch resistance test are ×.

[Thermoplastic resin composition]
Regarding the thermoplastic resin (A), the dye (B), the carbon black (C), and the surface modifier (D) used for producing the thermoplastic resin composition in Examples , Reference Examples, and Comparative Examples described later. Described below.

[Raw materials used in Examples , Reference Examples and Comparative Examples]
(Thermoplastic resin (A))
The commercially available products used as the thermoplastic resin (A) and the raw materials used for producing the thermoplastic resin (A) are as follows.
-Polycarbonate Mitsubishi Engineering Grade name: H-3000
Weight average molecular weight: 38,000, molecular weight distribution: 2.3, Vicat softening temperature: 140 ° C
-Polystyrene PS Japan grade name: G9305
Weight average molecular weight: 250,000, molecular weight distribution: 2.3, Vicat softening temperature: 102 ° C.
The structural unit was St: 100% by mass.
-Methacrylic resin As the methacrylic resin, the methacrylic resins of (A-1) to (A-3) produced by the following Production Examples A1 to A3 were used.

Methyl methacrylate (MMA), a raw material for methacrylic resin : manufactured by Asahi Kasei Chemicals (2,4-dimethyl-6-t-butylphenol (2,4-di-methyl-6-tert-butylphenyl) manufactured by Chugai Trading Co., Ltd. as a polymerization inhibitor) 2.5 ppm added)
-Methyl acrylate (MA): manufactured by Mitsubishi Chemical Corporation (14 ppm of 4-methoxyphenol manufactured by Kawaguchi Chemical Industry Co., Ltd. is added as a polymerization inhibitor)
・ N-Phenylmaleimide (PMI): manufactured by Nippon Catalyst ・ Styrene (St): manufactured by Asahi Kasei ・ n-octylmercaptan: manufactured by Alchema ・ 2-ethylhexyl thioglycolate: manufactured by Alchema ・Lauroyl peroxide: manufactured by Nippon Oil & Fats, calcium phosphate: manufactured by Nippon Kagaku Kogyo, used as a suspending agent, calcium carbonate (calcium carbononate), manufactured by Shiraishi Kogyo, used as a suspending agent, lauryl sulfate. Sodium (sodium lauryl sulfate): manufactured by Wako Pure Chemical Industries, Ltd., used as a suspension aid

<Manufacturing Example A1 (Manufacturing of methacrylic resin (A-1))>
Ion-exchanged water: 2 kg, tricalcium phosphate: 65 g, calcium carbonate: 39 g, and sodium lauryl sulfate: 0.39 g were put into a container having a stirrer to obtain a mixed solution (a).
Next, 26 kg of ion-exchanged water was added to a 60 L reactor and the temperature was raised to 80 ° C., and the mixture (a), methyl methacrylate: 21.2 kg, methyl acrylate: 0.43 kg, lauroyl peroxide: 27 g and n-octyl mercaptan: 58 g were added.
Then, suspension polymerization was carried out at about 80 ° C., and after observing an exothermic peak, the temperature was raised to 92 ° C. at a rate of 1 ° C./min and aged for 60 minutes to substantially complete the polymerization reaction.
Then, in order to cool to 50 ° C. and dissolve the suspending agent, 20% by mass sulfuric acid was added, and then the polymerization reaction solution was sieved through a 1.68 mm mesh to remove aggregates, and the obtained beaded polymer was obtained. The polymer fine particles were obtained by washing, dehydrating and drying.
The obtained polymer fine particles were melt-kneaded by a twin-screw extruder having a diameter of 30 mm set at 240 ° C., and the strands were cooled and cut to obtain a resin pellet [methacrylic resin (A-1)].
The weight average molecular weight of the obtained resin pellets was 102,000, the peak top molecular weight (Mp) was 109,000, and the molecular weight distribution (Mw / Mn) was 1.85. Further, the abundance (%) of the molecular weight component having a molecular weight of 1/5 or less of the Mp value was 4.5%. The structural unit was MMA / MA = 98/2 (mass%), and the Vicat softening temperature was 110 ° C.

<Manufacturing Example A2 (Manufacturing of methacrylic resin (A-2))>
(1st stage)
Ion-exchanged water: 2 kg, tricalcium phosphate: 65 g, calcium carbonate: 39 g, and sodium lauryl sulfate: 0.39 g were put into a container having a stirrer to obtain a mixed solution (b).
Next, 23 kg of ion-exchanged water was added to a 60 L reactor and the temperature was raised to 80 ° C., and the mixture (b), methyl methacrylate: 5.5 kg, lauroyl peroxide: 40 g, and 2-ethylhexylthioglycolate were added. Rate: 90 g was added. Then, suspension polymerization was carried out at about 80 ° C. An exothermic peak was observed 80 minutes after the raw material was added.
(2nd stage)
Then, the temperature was raised to 92 ° C. at a rate of 1 ° C./min, and then the temperature was maintained at 92 ° C. to 94 ° C. for 30 minutes. Then, after lowering the temperature to 80 ° C. at a rate of 1 ° C./min, methyl methacrylate: 16.2 kg, methyl acrylate: 0.75 kg, lauroyl peroxide: 21 g, n-octyl mercaptan: 17.5 g were added. Then, suspension polymerization was continuously carried out at about 80 ° C. An exothermic peak was observed 105 minutes after the raw material was added. Then, the temperature was raised to 92 ° C. at a rate of 1 ° C./min and then aged for 60 minutes to substantially complete the polymerization reaction.
Next, in order to cool to 50 ° C. and dissolve the suspending agent, 20% by mass sulfuric acid was added, and then the polymerization reaction solution was sieved through a 1.68 mm mesh to remove aggregates, and the obtained beaded polymer was obtained. Was washed, dehydrated and dried to obtain polymer fine particles. The obtained polymer fine particles were melt-kneaded by a twin-screw extruder having a diameter of 30 mm set at 240 ° C., and the strands were cooled and cut to obtain a resin pellet [methacrylic resin (A-2)].
The weight average molecular weight of the obtained resin pellets was 172,000, the peak top molecular weight (Mp) was 197,000, and the molecular weight distribution (Mw / Mn) was 3.65. Further, the abundance (%) of the molecular weight component having a molecular weight of 1/5 or less of the Mp value was 24.5%. The structural unit was MMA / MA = 96.5 / 3.5 (mass%), and the Vicat softening temperature was 107 ° C.

<Manufacturing Example A3 (Manufacturing of methacrylic resin (A-3))>
Ion-exchanged water: 2 kg, tricalcium phosphate: 65 g, calcium carbonate: 39 g, and sodium lauryl sulfate: 0.39 g were put into a container having a stirrer to obtain a mixed solution (d).
Next, 26 kg of ion-exchanged water was added to a 60 L reactor and the temperature was raised to 75 ° C., and the mixture (d), methyl methacrylate: 16.8 kg, phenylmaleimide: 2.93 kg, styrene: 1.04 kg. , Lauroyl peroxide: 27 g, and n-octyl mercaptan: 43 g were added. Then, suspension polymerization was carried out at about 75 ° C., and after observing an exothermic peak, the temperature was raised to 92 ° C. at a rate of 1 ° C./min and aged for 60 minutes to substantially complete the polymerization reaction.
Then, in order to cool to 50 ° C. and dissolve the suspending agent, 20% by mass sulfuric acid was added, and then the polymerization reaction solution was sieved through a 1.68 mm mesh to remove aggregates, and the obtained beaded polymer was obtained. The polymer fine particles were obtained by washing, dehydrating and drying.
The obtained polymer fine particles were melt-kneaded by a twin-screw extruder having a diameter of 30 mm set at 240 ° C., and the strands were cooled and cut to obtain a resin pellet [methacrylic resin (A-4)].
The weight average molecular weight of the obtained resin pellets was 123,000, the peak top molecular weight (Mp) was 109,000, and the molecular weight distribution (Mw / Mn) was 1.83. Further, the abundance (%) of the molecular weight component having a molecular weight of 1/5 or less of the Mp value was 4.0%. The structural unit was MMA / PMI / St = 81/14/5 (mass%), and the Vicat softening temperature was 125 ° C.

(Dye (B))
As the dyes, the commercially available products shown in Table 1 were used, and they were used as compound raw materials. The respective compounding amounts are shown in Table 3-1 and Table 3-2.

(Carbon black (C))
For C-1, the carbon black C-0 shown in Table 2 was surface-coated with a coating agent. Specifically, first, a coating agent having a mass 1.5 times that of carbon black C-0 is weighed, heated to 160 ° C., which is above the melting point, and melted, and then a predetermined amount of carbon black is added. It was poured into the melt and stirred. The melting point of zinc stearate is about 140 ° C. After stirring and dispersing sufficiently, the mixture was cooled to obtain a carbon black having a coated surface.

(Surface modifier (D))
The following commercially available surface modifier was used.
D-1: Amorphous silica (average particle size 0.5 μm) (Admafine SC2500-SMJ, methacrylic surface treatment, manufactured by Admatex Co., Ltd., Vickers hardness: 9 GPa)
D-2: Amorphous silica (average particle size 1.5 μm) (Admafine S0-C5, manufactured by Admatex Co., Ltd., Vickers hardness: 9 GPa)
D-3: Aluminum oxide (average particle size 0.6 μm) (A2-SM-C5, methacrylic surface treatment, manufactured by Admatex Co., Ltd., Vickers hardness: 15 GPa)
D-4: SiC (average particle size 0.57 μm) (Sintec 15C / manufactured by Saint-Gobain Co., Ltd., Vickers hardness: 24 GPa)
D-5: SiC (average particle size 2.3 μm) (UNIKILIN FCP07 / manufactured by Saint-Gobain Co., Ltd., Vickers hardness: 24 GPa)
D-6: Polysiloxane compound having a polyester group (TEGOMER® H-Si 6440P, manufactured by Evonik, Vickers hardness: 1 GPa or less)
D-7: Erucic acid amide (Diamid L-200, manufactured by Mitsubishi Chemical Corporation, Vickers hardness: 1 GPa or less)

[Examples 2 to 4, 6 to 21] [Reference Examples 1, 5] [Comparative Examples 1 to 4]
After weighing the thermoplastic resin (A), the dye (B), the carbon black (C), and the surface modifier (D) so as to have the blending ratios shown in Tables 3-1 and 3-2, respectively. It was mixed and dispersed by dry blending. After sufficient mixing, the mixed raw material is put into a φ48 mm twin-screw extruder, melt-kneaded (compounded) to form strands, the strands are cooled in a water bath, and then cut with a pelletizer to cut pellets. Obtained. At the time of compounding, a vacuum line was connected to the vent portion of the extruder to remove volatile components such as water and monomer components. In this way, a thermoplastic resin composition was obtained. The kneading temperature and discharge amount (kg / hr) / rotation speed (rpm) of the thermoplastic resin composition at the time of compounding are shown in Tables 3-1 and 3-2.

[Sample for flat plate evaluation (molded body)]
(injection molding)
The pellets of the obtained thermoplastic resin composition were put into an injection molding machine and molded into a flat plate (100 mm × 100 mm × t3 mm) to prepare a sample for evaluation. As the mold, a mold whose surface (inner surface of the mold cavity) was polished with a polishing count of 4000, 8000, or 12000 was used. Then, the surface to which the surface of the mold on the side polished by the polishing count was transferred was used as the test surface of this evaluation sample.
The molding conditions of this evaluation sample were set as shown in Table 3-1 and Table 3-2.
The components contained in the obtained evaluation sample and the mass ratio of each component were the same as those of the thermoplastic resin composition.

In Reference Example 1, amorphous silica was blended as polycarbonate, dye (B), carbon black (C), and surface modifier (D), and kneading conditions and molding conditions were appropriate, so molding was performed. The maximum height Rz of the body G20, G20 / G60, and steel wool after the scratch resistance test could be controlled, and the initial surface appearance Ra and Δb ^* were at practically good levels. Further, by using polycarbonate, it was a molded product having high heat resistance.
In Example 2, polystyrene, dye (B), carbon black (C), and aluminum oxide were blended as the surface modifier (D), and since the kneading conditions and molding conditions were appropriate, the initial surface appearance Ra, At Δb ^* , it was at a practically good level.
Since SiC was used as the surface modifier (D) in Examples 3 and 4, the maximum height of the molded product after the scratch resistance test of G20, G20 / G60 and steel wool was higher than that of Reference Example 1 and Example 2. Rz can be controlled, and the initial surface appearance Ra and Δb ^* are at a slightly excellent level in practical use.
In Reference Example 5, when 1 part by mass of amorphous silica was blended with 100 parts by mass of polystyrene, the maximum height Rz after the scratch resistance test of steel wool became slightly larger than that of other examples, and it became Δb ^* . Although it had an effect, it was at a practically good level.
In Example 6, since 1 part by mass of aluminum oxide was blended with 100 parts by mass of polystyrene, the maximum height Rz after the scratch resistance test of steel wool was smaller than that of Reference Example 5, and Δb ^* tended to improve. there were.
In Example 7, a methacrylic resin, a dye (B), a carbon black (C), and aluminum oxide (3 parts by mass with respect to 100 parts by mass of the methacrylic resin) are blended as a surface modifier (D). Furthermore, since the kneading conditions and the molding conditions were appropriate, the G20, G20 / G60 of the molded body, and the maximum height Rz after the steel wool scratch resistance test could be controlled, and the initial surface appearance Ra, Δb ^* was practically excellent. It was on the level.
In Example 8, since a methacrylic resin was used and SiC was used as the surface modifier (D), the G20, G20 / G60 of the molded product, and the maximum height Rz after the steel wool scratch resistance test were controlled particularly well. It was possible, and the initial surface appearance Ra and Δb ^* were at an excellent level for practical use.
Further, in Example 9, the proportion of the component having a molecular weight of 1/5 or less of the peak top molecular weight (Mp) obtained from the GPC elution curve in the methacrylic resin is the total area of the GPC elution curve of the methacrylic resin. On the other hand, since it was in a preferable range, it was at a practically excellent level in the initial surface appearance Ra and Δb ^* .
In Examples 10 and 11, 0.5 part by mass of SiC was blended with 100 parts by mass of the methacrylic resin, but the amount was slightly smaller than that of Example 9, so the maximum height Rz after the steel wool scratch resistance test was used. Slightly increased and affected Δb ^* , but it was at an excellent level for practical use.
In Example 12, since 1 part by mass of the polysiloxane compound was further added as the surface modifier (D) to Example 9, the maximum height Rz after the steel wool scratch resistance test was slightly reduced, and Δb ^* was increased. There was a slight improvement trend.
In Example 13, since a methacrylic resin (A-3), which is a heat-resistant acrylic resin, was used, it was a molded product having not only excellent initial surface appearance Ra and Δb ^* but also high heat resistance.
In Example 14, since the discharge amount / rotation speed, which is the kneading condition, was the most preferable condition, the maximum height Rz after the scratch resistance test of G20, G20 / G60, and steel wool was higher than that of Example 8. It became a preferable value, and a molded body having a small initial surface appearance Ra and Δb ^* of the molded body was obtained.
Further, in Example 15, since the polishing of the mold, which is a molding condition, was particularly preferable, G20 and G20 / G60 became more preferable values as compared with Example 8, and the initial surface appearance Ra of the molded product was improved. A slightly smaller molded product was obtained.
In Example 16, since the molds that were not preferably polished, which are the molding conditions, were used, G20 and G20 / G60 were slightly inferior to those of Example 8, and the initial surface appearance Ra and Δb ^* of the molded product were slightly inferior. Although it became a slightly large molded body, it was at a slightly excellent level in practical use.
In Example 17, since the average particle size of the surface modifier (D) was out of the more preferable range, control of the maximum height Rz after the scratch resistance test of G20, G20 / G60, and steel wool was carried out. Although it was more difficult than in Example 8, it was a practically good level in the initial surface appearance Ra and Δb ^* .
In Example 18, since the discharge amount / rotation speed, which is the kneading condition, deviates from the preferable conditions, it is more difficult to control the maximum height Rz after the scratch resistance test of G20, G20 / G60, and steel wool as compared with Example 8. However, the initial surface appearance Ra and Δb ^* were at a slightly excellent level in practical use.
In Examples 19 and 20, since the mold temperature at the time of molding was set in the most preferable range, G20 and G20 / G60 were improved as compared with Examples 8 and 9, and the initial surface appearance Ra was at a practically excellent level. Met.
In Example 21, in the methacrylic resin, the proportion of the component having a molecular weight of 1/5 or less of the peak top molecular weight (Mp) obtained from the GPC elution curve is the ratio of the total area of the GPC elution curve of the methacrylic resin. Since SiC was used as the surface modifier (D) in a preferable range, the kneading conditions of the discharge amount / rotation speed, the molding conditions of polishing the mold, and the mold temperature were also the most preferable conditions. The surface appearance Ra and Δb ^* were at very excellent levels.
On the other hand, in Comparative Example 1, a methacrylic resin was used, but the maximum height Rz after the steel wool scratch resistance test was high, and Δb ^* was insufficient.
In Comparative Example 2, a polysiloxane compound and an erucic acid amide were used as the surface modifier (D), but the maximum height Rz after the steel wool scratch resistance test was increased and Δb ^* was increased as in Comparative Example 1. It was inadequate.
In Comparative Example 3, amorphous silica was used as the surface modifier (D), but G20 and G20 / G60 deviated from the lower limit, and the initial surface appearance Ra was insufficient.
In Comparative Example 4, polycarbonate was used, and amorphous silica (3 parts by mass with respect to 100 parts by mass of polycarbonate) was used as the surface modifier (D), but a mold polishing count of 4000, which is a molding condition, was used. However, since the discharge amount / rotation speed, which is the kneading condition, deviated from the preferable conditions, G20 and G20 / G60 deviated from the lower limit values, and the initial surface appearance Ra and Δb ^* were insufficient.

Regarding the use of the molded product of the present embodiment, it has a high appearance from any angle, and is generally used for applications where a small visual change is required even after a ni scratch resistance test similar to that of a painted product or an HC-treated product. It is industrially available.

Claims (7)

Molded under the conditions of (1) and (2) below,
The glossiness (G20) at an incident angle of 20 ° measured according to JIS Z8741 is 75% or more, and the ratio of G20 (G20 / G60) to the glossiness (G60) at an incident angle of 60 ° is 0. It is 85 to 1.0, and the maximum height (Rz) measured according to ISO 1997 after the scratch resistance test (sliding 5 times under a load of 0.2 kg of steel wool) is 1.0 μm or less.
A molded product containing the thermoplastic resin (A) and containing 0.01 to 10% by mass of the surface modifier (D) having a Vickers hardness of 10 GPa or more .
(1) Molding temperature: 140-320 ° C
(2) Mold temperature: Vicat softening temperature (VST) -70 ° C to VST-20 ° C (VST is measured at a load of 50 N and a temperature rise rate of 50 ° C / hour in accordance with ISO306 B50). The molded product according to claim 1, wherein the maximum height (Rz) is 0.6 μm or less. The molded product according to claim 1 or 2, wherein the thermoplastic resin (A) is an amorphous resin. The molded product according to any one of claims 1 to 3 , which is an injection molded product. The molded product according to any one of claims 1 to 4 , which is a housing or design material for optical use, electrical / electronic use, or vehicle use. The molded product according to claim 5 , which is a design material for motorcycles or automobiles. The molded body according to claim 6 , which is either a tail lamp garnish, a rear lamp garnish, a front lamp garnish, a pillar garnish, a front grill, a rear grill, a license garnish, a wheel center cap, a license plate garnish, or a Dora mirror cover.