JP7123715B2 - molding - Google Patents

Description

TECHNICAL FIELD The present invention relates to a molded article containing an amorphous resin.

BACKGROUND ART Conventionally, molded articles such as hard-coated polycarbonate and ABS resin, and jet-black painted ASA and ABS resin have been used for interior and exterior parts of automobiles. However, the hard coat treatment (HC treatment) has problems such as defects due to the occurrence of coat spots and low productivity. Against the background of these problems, from the viewpoint of cost reduction, moldings that do not require HC treatment or painting have been desired, and the use of compounds to replace resins has been actively studied in recent years. Here, the important properties are the scratch resistance and jet-blackness of the surface.

In order to impart these properties, for example, a method of mixing (compounding) an additive with a thermoplastic resin has been used for a long time. In recent years, methacrylic resins are mainly used as thermoplastic resins. The reason for this is that methacrylic resins are excellent in weather resistance and have the highest surface pencil hardness and scratch resistance among resins. In addition, because of its high transparency, it is possible to develop deep and good coloring in molded articles, particularly in the case of paint substitutes.

However, in applications where high requirements are imposed on the surface, even methacrylic resins cannot withstand various wear phenomena and are often subjected to HC treatment. As a method for solving this problem, for example, Patent Document 1 proposes a technique for improving scratch resistance by incorporating an acrylic resin and a scratch-resistant agent.
In addition, Patent Document 2 introduces a technique for expressing high jet-blackness.

International Publication No. 2016/158564 JP 2016-37518 A

In Patent Document 1, the scratch resistance is improved by containing a specific anti-scratch agent, but the inclusion of the additive makes it impossible to maintain the blackness of the molded product itself. There is a concern that it will be colored black with a whitish tinge, which is called "", and it is not suitable for applications that require a particularly high degree of jet-blackness. Moreover, it cannot be said that the scratch resistance is sufficient.

In Patent Document 2, high jet blackness is expressed by controlling a certain amount of CB and surface roughness, but the scratch resistance is insufficient and does not meet market requirements.
In addition, by making it black, the scratches are more noticeable than the transparent molded body, and the higher the jet blackness and the smaller the surface roughness, the ΔL ^* (change rate of lightness) after scratching.
tends to increase. Therefore, it has become important to design a molded article with a moderately low initial L ^* before scratching and a small ΔL ^* after scratching, which is not subjected to HC treatment or painting, has an adjusted initial jet-blackness, and is durable. Abrasive moldings are desired for many applications.

Under such circumstances, in view of the above-mentioned problems of the prior art, the present invention provides a molded article that has high jet-blackness even when reflecting external light and has high scratch resistance comparable to that of painted products. The purpose is to

As a result of intensive studies to solve the above problems, the present inventors found that the above-described problems in the prior art can be solved by using a molded article having specific parameters in a molded article containing a dye. Completed.

（式（Ｉ）中、Ｒは、各々独立して、１～１１個の炭素原子を有するアルキル基であり、Ｒ_１は、各々独立して、１～１１個の炭素原子を有するアルキル基又はポリエステル基であり、Ｒ_２は、各々独立して、ポリエステル基又は１２～３６個の炭素原子を有する炭化水素基であり、ｎ、ｍ、及びｐは、各々独立して、０～５８であり、かつ、Ｎ＝ｎ＋ｍ＋ｐ＋２は、１５～７５を満たし、ｍ及びｐが０である場合、全てのＲ_１はポリエステル基である。）
〔６〕
上記染料（Ｂ）が、赤系染料、黄系染料、緑系染料、青系染料、及び紫系染料からなる群より選ばれる１種以上の染料を含む、〔１〕～〔５〕のいずれかに記載の成形体。
〔７〕
上記染料（Ｂ）が、アントラキノン系染料、複素環式化合物系染料、及びペリノン系染料からなる群より選ばれる１種以上の染料を含む、〔１〕～〔６〕のいずれかに記載の成形体。
〔８〕
ゲルパーミエーションクロマトグラフィー（ＧＰＣ）で測定した、上記メタクリル系樹脂の重量平均分子量が、５００００～３０００００であり、かつ、
上記メタクリル系樹脂のＧＰＣ溶出曲線から得られるピークトップ分子量（Ｍｐ）の１／５以下の分子量を有する成分の割合が、上記メタクリル系樹脂の上記ＧＰＣ溶出曲線の総面積に対して、６～５０％である、〔１〕～〔７〕のいずれかに記載の成形体。
〔９〕
射出成形体である、〔１〕～〔８〕のいずれかに記載の成形体。
〔１０〕
前記成形体の厚さｔ（単位：ｍｍ）と流動長Ｌ（単位：ｍｍ）とが下記式（ＩＩ）の関係を満たし、かつ、１つのゲート部を有する、〔１〕～〔９〕のいずれかに記載の成形体。
Ｌ／ｔ＜１５０ ・・・（ＩＩ）
〔１１〕
上記成形体の厚さｔ（単位：ｍｍ）が、０．５以上３．０以下である、〔１〕～〔１０〕のいずれかに記載の成形体。
〔１２〕
テールランプガーニッシュ、リアランプガーニッシュ、フロントランプガーニッシュ、ピラーガーニッシュ、フロントグリル、リアグリル、及びナンバープレートガーニッシュのいずれかである、〔１〕～〔１１〕のいずれかに記載の成形体。
〔１３〕
前記メタクリル系樹脂の重量平均分子量が５００００～３０００００であり、
前記メタクリル系樹脂が、メタクリル酸エステル単量体単位の含有量が前記メタクリル系樹脂の総量に対して８０～９９．９質量％であり、前記メタクリル系樹脂を構成するメタクリル酸エステル単量体に共重合可能な他のビニル単量体単位の含有量が前記メタクリル系樹脂の総量に対して０．１～２０質量％である、〔１〕～〔１２〕のいずれかに記載の成形体。 That is, the present invention is as follows.
[1]
comprising an amorphous resin (A) and a dye (B), having a lightness (L ^* ) measured by SCE of 0.3 or more and 1.6 or less , wherein the amorphous resin (A) is a methacrylic For automobile exterior, characterized in that it is a resin, and the content of the amorphous resin (A) in the molded body is 60% by mass or more and 99.9% by mass or less with respect to the total amount of the molded body. A molded product that is a design material .
[2]
The molded article according to [1], further comprising carbon black (C).
[3]
The carbon black (C) is carbon black surface-coated with a coating agent, and the coating agent is zinc stearate, magnesium stearate, calcium stearate, oleic acid amide, stearic acid amide, palmitic acid amide, methylene bis. The molded article according to [2], containing one or more selected from the group consisting of stearylamide and ethylenebisstearylamide.
[4]
The molded article according to any one of [1] to [3], further comprising a sliding agent (D).
[5]
The molded article according to [4], wherein the sliding agent (D) contains a siloxane compound represented by the following formula (I).

(In formula (I), each R is independently an alkyl group having 1 to 11 carbon atoms, and each R ₁ is independently an alkyl group having 1 to 11 carbon atoms, or a polyester group, R ₂ is each independently a polyester group or a hydrocarbon group having 12 to 36 carbon atoms, and n, m, and p are each independently 0 to 58; and N=n+m+p+2 satisfies 15 to 75, and all R ₁ are polyester groups when m and p are 0.)
[6]
Any of [1] to [5], wherein the dye (B) contains one or more dyes selected from the group consisting of red dyes, yellow dyes, green dyes, blue dyes, and purple dyes. The molded article described in k.
[7]
The molding according to any one of [1] to [6], wherein the dye (B) contains one or more dyes selected from the group consisting of anthraquinone dyes, heterocyclic compound dyes, and perinone dyes. body.
[8]
The weight average molecular weight of the methacrylic resin measured by gel permeation chromatography (GPC) is 50000 to 300000, and
The ratio of components 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 is 6 to 50 with respect to the total area of the GPC elution curve of the methacrylic resin. %, the molded article according to any one of [1] to [7] .
[9]
The molded article according to any one of [1] to [8] , which is an injection molded article.
[ 10 ]
[1] to [9] , wherein the thickness t (unit: mm) and the flow length L (unit: mm) of the molded body satisfy the relationship of the following formula (II) and have one gate portion. A molded article according to any one of the above.
L/t<150 (II)
[ 11 ]
The molded article according to any one of [1] to [ 10 ], wherein the molded article has a thickness t (unit: mm) of 0.5 or more and 3.0 or less.
[ 12 ]
The molded article according to any one of [1] to [ 11 ], which is any one of tail lamp garnish, rear lamp garnish, front lamp garnish, pillar garnish, front grille, rear grille and license plate garnish.
[13]
The methacrylic resin has a weight average molecular weight of 50,000 to 300,000,
The methacrylic resin has a methacrylic acid ester monomer unit content of 80 to 99.9% by mass with respect to the total amount of the methacrylic resin, and the methacrylic acid ester monomer constituting the methacrylic resin The molded article according to any one of [1] to [12], wherein the content of other copolymerizable vinyl monomer units is 0.1 to 20% by mass relative to the total amount of the methacrylic resin.

ADVANTAGE OF THE INVENTION According to this invention, the molded object which has high jet-blackness comparable to a painted or HC-processed article, and high abrasion resistance can be provided.

It is a figure which shows typically the abrasion resistance test in an Example.

EMBODIMENT OF THE INVENTION Hereinafter, the form (henceforth "this embodiment") for implementing this invention is demonstrated 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 modified appropriately within the scope of its gist.
In this specification, a monomer component before polymerization is referred to as "monomer" and may be abbreviated as "monomer". Further, a structural unit constituting a polymer is referred to as "-monomer unit", and sometimes simply written as "-unit".

The molded article of this embodiment contains an amorphous resin (A) and a dye (B). The molded article of this embodiment may further contain carbon black (C), a sliding agent (D), and other components.
In this specification, the mixture which is the raw material of the molded article of the present embodiment before molding may be referred to as an amorphous resin composition. The amorphous resin composition contains an amorphous resin (A) and a dye (B), and may further contain carbon black (C), a sliding agent (D), and other components.
Each component constituting the molded article of the present embodiment will be described below.

[Amorphous resin (A)]
The amorphous resin (A) is not particularly limited, but examples include methacrylic resins, polystyrene resins, polycarbonate resins, syndiotactic polystyrene resins, and ABS resins (acrylonitrile-butadiene-styrene copolymers). , AS resin (acrylonitrile-styrene copolymer), BAAS resin (butadiene-acrylonitrile-acrylonitrile rubber-styrene copolymer), MBS resin (methyl methacrylate-butadiene-styrene copolymer), AAS resin Resin (acrylonitrile-acrylonitrile rubber-styrene copolymer), biodegradable resin, polycarbonate-ABS resin alloy, modified polyphenylene ether resin and the like. Among these, methacrylic resins, polystyrene resins, polycarbonate resins, and ABS resins are preferable from the viewpoint of jet-blackness and scratch resistance. Resins are particularly preferred.
Here, the resin includes a copolymer obtained by polymerizing a plurality of types of monomers, and in the copolymer, the content of monomer units derived from the main monomer is 50% by mass with respect to the total amount of the resin. It is preferable that it is above. The main monomer is a main monomer that mainly constitutes each resin, such as a methacrylic acid ester monomer for methacrylic resin, a styrene monomer for polystyrene resin, and a carbonate monomer for polycarbonate resin. .
The amorphous resin (A) may be used singly or in combination of two or more.

(methacrylic resin)
Details of the methacrylic resin are described below.
In the case of a methacrylic resin, it may be a homopolymer consisting of structural units derived from methacrylic acid ester monomers (herein, simply referred to as "methacrylic acid ester monomer units"), or methacrylic acid An ester monomer unit and a structural unit derived from another vinyl monomer copolymerizable with a methacrylic acid ester monomer (herein, simply referred to as "another vinyl monomer unit") It may be a copolymer containing Among these, copolymers are preferred.

（一般式（ＩＩＩ）中、Ｒ₃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。） -Methacrylate ester monomer-
The methacrylic acid ester monomer that forms the methacrylic acid ester monomer unit that constitutes the methacrylic resin is not particularly limited as long as it can achieve the effects of the present invention. Examples thereof include the monomers represented by III).

(In general formula (III), R ₃ represents a hydrocarbon group having 1 to 18 carbon atoms, and the hydrogen atoms on the carbon atoms of the hydrocarbon group may be substituted with a hydroxyl group or a halogen group. )

The methacrylate monomer is not particularly limited, but examples include methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, and methacryl. acid (2-ethylhexyl), methacrylic acid (t-butylcyclohexyl), benzyl methacrylate, methacrylic acid (2,2,2-trifluoroethyl) and the like. Among these, methyl methacrylate, ethyl methacrylate, propyl methacrylate, and the like are more preferable, and methyl methacrylate is particularly preferable, from the viewpoint of ease of handling and availability. The methacrylic acid ester monomers may be used singly or in combination of two or more.

When the methacrylic 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 99.9% by mass, based on the total amount of the methacrylic resin. It is 99% by mass, more preferably 90 to 98% by mass. When the content of the methacrylic acid ester monomer units 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（ＩＶ）中、Ｒ₄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-
Other vinyl monomers that form other vinyl monomer units that can be copolymerized with the methacrylic acid ester monomer that constitutes the methacrylic resin (in this specification, simply referred to as "other vinyl monomers" ) is not particularly limited, but preferable examples thereof include acrylic acid ester monomers represented by the following general formula (IV).

(In general formula (IV), R ₄ represents a hydrocarbon group having 1 to 18 carbon atoms, and the hydrogen atoms on the carbon atoms of the hydrocarbon group may be substituted with a hydroxyl group or a halogen group.)

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

In addition, the vinyl monomer other than the acrylic acid ester monomer represented by the general formula (IV), which can be copolymerized with the methacrylic acid ester monomer, is not particularly limited, but examples include acrylic acid and α,β-unsaturated acids such as methacrylic acid; unsaturated group-containing divalent carboxylic acids such as maleic acid, fumaric acid, itaconic acid and cinnamic acid, and their alkyl esters; styrene, o-methylstyrene, m-methylstyrene , p-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethylstyrene, p-ethylstyrene, m-ethylstyrene, o-ethylstyrene, p -Styrenic monomers such as tert-butylstyrene and isopropenylbenzene (α-methylstyrene); 1-vinylnaphthalene, 2-vinylnaphthalene, 1,1-diphenylethylene, isopropenyltoluene, isopropenylethylbenzene, isopropenyl Aromatic vinyl compounds such as propylbenzene, isopropenylbutylbenzene, isopropenylpentylbenzene, isopropenylhexylbenzene, isopropenyloctylbenzene; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; maleic anhydride, itaconic anhydride, etc. Unsaturated carboxylic acid anhydrides; maleimide, N-substituted maleimide such as N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide; amides such as acrylamide and methacrylamide; Both terminal hydroxyl groups of ethylene glycol such as (meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate or oligomer thereof are esterified with acrylic acid or methacrylic acid. Those obtained by esterifying the hydroxyl groups of two alcohols such as neopentyl glycol di(meth)acrylate and di(meth)acrylate with acrylic acid or methacrylic acid; Polyhydric alcohol derivatives such as trimethylolpropane and pentaerythritol Those esterified with acid or methacrylic acid; polyfunctional monomers such as divinylbenzene; and the like.
The other vinyl monomers may be used singly or in combination of two or more.

The content of the other vinyl monomer unit is preferably 0.1 to 20% by mass, more preferably 1.0 to 15% by mass, more preferably 1.0 to 15% by mass, based on the total amount of the methacrylic resin. 1.5 to 12% by mass, particularly preferably 2.0 to 10% by mass. When the content of other vinyl monomer units is 0.1% by mass or more, fluidity and heat resistance tend to be further improved. Moreover, when the content of other vinyl monomer units is 20% by mass or less, the heat resistance tends to be further improved.

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

-Weight average molecular weight and molecular weight distribution of methacrylic resin-
The weight average molecular weight and 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, it is possible to achieve a balance between fluidity, mechanical strength, and solvent resistance, and tends to maintain good moldability. 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, even more preferably 70,000 or more, and even more preferably 80,000 or more. Preferably, 90,000 or more is even more preferable. Further, from the viewpoint that the methacrylic resin exhibits good fluidity, the weight average molecular weight (Mw) of the methacrylic resin is preferably 300,000 or less, more preferably 250,000 or less, even more preferably 230,000 or less, and further preferably 210,000 or less. More preferably, 180,000 or less is even more preferable.

The molecular weight distribution (Mw/Mn) of the methacrylic resin is preferably 1.6 to 6.0, more preferably 1.7 to 5.0, still more preferably 1.8 to 5.0. be. When the molecular weight distribution of the methacrylic resin is within the above range, there is a tendency that the balance between molding flow and mechanical strength is more excellent. Here, Mw represents the weight average molecular weight and Mn represents the number average molecular weight.
The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the methacrylic resin can be measured by GPC, and specifically, by the method described in Examples below. Specifically, a standard methacrylic resin that has a known monodisperse weight-average molecular weight and is available as a reagent, and an analytical gel column that first elutes high-molecular-weight components are used to create a calibration curve from the elution time and weight-average molecular weight. Subsequently, based on the calibration curve obtained, the weight average molecular weight (Mw) and number average molecular weight (Mn) of the methacrylic resin to be measured can be obtained. A 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 the average molecular weight per simple molecule and is defined as the total weight of the system/number of molecules in the system. Weight average molecular weight (Mw) is defined as the average molecular weight by weight fraction.

-Proportion of molecular weight component of 1/5 or less of peak top molecular weight (Mp) of methacrylic resin-
From the viewpoint of solvent resistance and fluidity, the ratio of components 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 It is preferably 6 to 50%, more preferably 7 to 45%, still more preferably 8 to 43%, still more preferably 9 to 40%, relative to the total area of the GPC elution curve of the resin. Oh, and more preferably 10 to 38%. When the ratio 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, and the molecular orientation on the surface of the molded body is relaxed, resulting in abrasion resistance. tend to be better. Moreover, 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 "proportion (%) of components having a molecular weight of 1/5 or less of the peak top molecular weight (Mp)" is the peak top molecular weight (Mp ), and can be measured by the method described in Examples below. In addition, "peak top molecular weight (Mp)" refers to the weight molecular weight showing a peak in the GPC elution curve. When there are multiple peaks in the GPC elution curve, the molecular weight at the peak indicated by the weight molecular weight with the highest abundance is defined as the peak top molecular weight (Mp).
A methacrylic resin component having a weight molecular weight of 500 or less causes a foam-like appearance defect called silver during molding, so the amount is preferably as small as possible.

- Method for producing methacrylic resin -
The methacrylic resin can be produced by bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization. Among these, bulk polymerization, solution polymerization and suspension polymerization are preferred, and suspension polymerization is more preferred.

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

A polymerization initiator may be used when producing the methacrylic resin. The polymerization initiator is not particularly limited, but when performing radical polymerization, for example, di-t-butyl peroxide, lauroyl peroxide, decanoyl peroxide, stearyl peroxide, benzoyl peroxide, t-butyl peroxide neodecanate, t-butyl peroxypivalate, dilauroyl peroxide, dicumyl peroxide, t-butyl peroxy-2-ethylhexanoate, 1,1-bis(t-butylperoxy)-3, Organic peroxides such as 3,5-trimethylcyclohexane, cyclohexane peroxide, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, 1,1-bis(t-butylperoxy)cyclohexane; azo bisisobutyronitrile, azobisisovaleronitrile, 1,1-azobis(1-cyclohexanecarbonitrile), 2,2'-azobis-4-methoxy-2,4-azobisisobutyronitrile, 2,2 '-azobis-2,4-dimethylvaleronitrile, 2,2'-azobis-2-methylbutyronitrile, 2-(carbamoyl azo) isobutyronitrile and other general azo radical polymerization initiators. be done. These may be used singly or in combination of two or more. A combination of these radical initiators and a suitable reducing agent may be used as a redox initiator.

These radical polymerization initiators and/or redox 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 monomers used in the polymerization of the methacrylic resin. It can be appropriately selected in consideration of the polymerization temperature 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 for the methacrylic resin, an organic peroxide is used as a polymerization initiator from the viewpoint of preventing coloring of the methacrylic resin. Polymerization is preferred. Examples of such organic peroxides include those mentioned above. Among these, lauroyl peroxide, decanoyl peroxide, and t-butylperoxy-2-ethylhexanoate are preferred. Oxide is more preferred.

Further, when a methacrylic resin is polymerized by a solution polymerization method at a high temperature of 90 ° C. or higher, an organic peroxide and azobis that have a 10-hour half-life temperature of 80 ° C. or higher and are soluble in the organic solvent used It is preferable to use an initiator or the like as the polymerization initiator. Examples of such organic peroxides and azobis initiators include those mentioned above. Among them, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, Oxide, 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 as necessary. A method for controlling the molecular weight of the methacrylic resin is not particularly limited, but examples thereof include a method of changing the polymerization method or polymerization conditions, a method of selecting a polymerization initiator, a method of adjusting the amount of a chain transfer agent, an iniferter, and the like. . As for these molecular weight control methods, only one method may be used, or two or more methods may be used in combination.

Examples of iniferters include, but are not limited to, dithiocarbamates, triphenylmethylazobenzene, tetraphenylethane derivatives and the like.

Examples of chain transfer agents include, but are not limited to, alkylmercaptans, 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 examples include n-butyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-tetradecyl mercaptan, n-octadecyl mercaptan, 2-ethylhexyl thioglyco ethylene glycol dithioglycolate, trimethylolpropane tris (thioglycolate), pentaerythritol tetrakis (thioglycolate) and the like.

The chain transfer agent and iniferter can be appropriately added according to the desired molecular weight of the methacrylic resin, and the molecular weight can be adjusted by adjusting the amounts of the chain transfer agent and iniferter added. Generally, it is used in the range of 0.001 to 5 parts by weight per 100 parts by weight of the total amount of all monomers used in the polymerization of the methacrylic resin.

In addition, as a method for producing a methacrylic resin in which the ratio of components 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%, low molecular weight methacrylic Examples include a method of melt-blending a system resin and a high-molecular-weight methacrylic resin, and a method of manufacturing by a multistage polymerization method. When producing a methacrylic resin in which the abundance of a component having a molecular weight of 1/5 or less of Mp is 6 to 50%, the method is not particularly limited, but from the viewpoint of quality stability, multistage More preferably, a polymerization method is used.
When using a multistage polymerization method, first, in the first stage polymerization, a methacrylic acid ester monomer and another vinyl monomer are polymerized, and a polymer having a weight average molecular weight measured by GPC of 5000 to 50000 is obtained. It is preferred to produce (i). Next, the inside of the polymerization system is held at a temperature higher than the polymerization temperature in the first stage for a certain period of time. Thereafter, a methacrylic acid ester monomer and another vinyl monomer are further polymerized in the presence of polymer (i) to produce 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 and second stages of polymerization without using other vinyl monomers. Moreover, when the methacrylic resin is a mixture of a homopolymer and a copolymer, homopolymerization can be performed in the first stage polymerization, and copolymerization can be performed 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 on the surface of the molded product, the content of the polymer (i) is The content of the polymer (ii) is preferably 95 to 50% by mass based on the total amount of the methacrylic resin. Considering the balance between polymerization stability, fluidity, mechanical strength of the molded article, and relaxation of molecular orientation on the surface of the molded article, the content ratio of polymer (i)/polymer (ii) is more preferably 7 to 47. % by mass/93 to 53% by mass, more preferably 10 to 45% by mass/90 to 65% by mass, still more preferably 13 to 43% by mass/87 to 57% by mass, still more preferably 15 to 40% by mass/85 to 60% by mass.

Furthermore, the polymer (i) is preferably a polymer containing 80 to 100% by mass of methacrylic acid ester monomer units and 0 to 20% by mass of other vinyl monomer units. It is more preferably a polymer containing 90 to 100% by mass of units and 0 to 10% by mass of other vinyl monomer units, and 95 to 100% by mass of methacrylic acid ester monomer units and other vinyl monomer units. More preferably, 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) in the multistage polymerization. Polymer (i) preferably has a lower content of other vinyl monomers, and does not have to contain other vinyl monomers.

In addition, from the viewpoint of suppression of defects such as silver during molding, polymerization stability, and fluidity, the weight average molecular weight 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 polymer (i) can be controlled by using a chain transfer agent or iniferter, adjusting the amounts thereof, or appropriately changing the polymerization conditions. The weight average molecular weight of polymer (i) can be measured by GPC in the same manner as described above.

Polymer (ii) is preferably a polymer containing 80 to 99.9% by mass of methacrylic acid ester monomer units and 0.1 to 20% by mass of other vinyl monomer units. More preferably, it is a polymer containing 90 to 99.9% by mass of monomer units and 0.1 to 10% by mass of other vinyl monomer units, and 92.5 to 99.8% by mass of methacrylic acid ester monomer units. More preferably, it is a polymer containing 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) in the multistage polymerization.

From the viewpoint of solvent resistance and fluidity, the weight average molecular weight of polymer (ii) is preferably 60,000 to 350,000, more preferably 100,000 to 320,000, and still more preferably 130,000 to 300,000. , and more preferably 150,000 to 270,000. As described above, the weight average molecular weight of polymer (ii) can be controlled by using a chain transfer agent or iniferter, adjusting the amounts thereof, or appropriately changing the polymerization conditions. The weight average molecular weight of polymer (ii) can be measured by GPC in the same manner as described above.

The multi-stage polymerization method makes it easy to control the respective compositions of the polymer (i) and the polymer (ii), suppresses temperature rise due to heat generated by polymerization during polymerization, and stabilizes the viscosity in the system. 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. (maintaining a temperature higher than the polymerization temperature) and adding the raw material composition mixture of the polymer (ii) after completing the polymerization. Curing in the first stage not only completes the polymerization, but also removes or deactivates unreacted monomers, initiators, chain transfer agents, etc., which adversely affects the second stage polymerization. no longer affect. As a result, the target weight average molecular weight can be obtained.

The polymerization temperature may be appropriately selected according to the polymerization method, and is preferably 50° C. or higher and 100° C. or lower, more preferably 60° C. or higher and 90° C. or lower. The polymerization temperatures of polymer (i) and polymer (ii) may be the same or different.
The temperature to be raised during curing is preferably 5° C. or higher, more preferably 7° C. or higher, still more preferably 10° C. or higher than the polymerization temperature of the polymer (i). Furthermore, the time for holding at the elevated temperature during curing is preferably 10 minutes or more and 180 minutes or less, more preferably 15 minutes or more and 150 minutes or less.

(polystyrene resin)
Examples of the polystyrene resin include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,4-dimethylstyrene, 3,5 -As a monomer unit derived from a styrenic monomer such as dimethylstyrene, p-ethylstyrene, m-ethylstyrene, о-ethylstyrene, p-tert-butylstyrene, isopropenylbenzene (α-methylstyrene), etc. resin containing. The polystyrene-based resin, in addition to the styrene-based monomer, may contain structural units derived from the above-described methacrylic acid ester monomers and other vinyl monomers (excluding styrene-based monomers). . Among them, polystyrene is preferred.
The above polystyrene-based resins may be used singly or in combination of two or more.
The content of structural units derived from styrene-based monomers in the polystyrene-based resin is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 70% by mass or more.

(polycarbonate resin)
Examples of the polycarbonate-based resin include, for example, a resin produced by reacting a dihydric phenol-based compound with phosgene in the presence of a catalyst and a molecular weight modifier, an ester of a dihydric phenol-based compound and a carbonate precursor such as diphenyl carbonate. Examples thereof include resins manufactured using exchange.
As the dihydric 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 types of dihydric phenols. Examples of dihydric phenols other than bisphenol A include hydroquinone, 4,4'-dihydroxydiphenyl, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 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 include (4-hydroxyphenyl)ether and halogenated bisphenols such as 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane.
As the polycarbonate-based resin, a homopolymer such as a bisphenol A-based polycarbonate, a copolymer of two or more dihydric phenols, or a mixture thereof can be used. Examples of the polycarbonate-based resins include linear polycarbonates, branched polycarbonates, polyester carbonate copolymers, and the like.
Examples of the branched polycarbonate include those obtained by reacting polyfunctional aromatic compounds such as trimellitic anhydride and trimellitic acid with dihydric phenol compounds and carbonate precursors.
Examples of the polyester carbonate copolymer include those obtained by reacting a bifunctional carboxylic acid with a dihydric phenol-based compound and a carbonate precursor.
The above polycarbonate-based resins may be used alone or in combination of two or more.

The content of the amorphous resin (A) is preferably 50% by mass or more and 99.9% by mass or less with respect to the total amount of the amorphous resin composition, from the viewpoint of further improving the jet-blackness of the resulting molded product. more preferably 60% by mass or more and 98.5% by mass or less, and still more preferably 70% by mass or more and 98% by mass or less.
In addition, the content of the methacrylic resin is preferably 50% by mass or more and 99% by mass based on the total amount of the amorphous resin composition, from the viewpoint of more excellent jet-blackness, surface hardness, and scratch resistance of the resulting molded product. 9 mass % or less, more preferably 60 mass % or more and 98.5 mass % or less, and still more preferably 70 mass % or more and 98 mass % or less.

[Dye (B)]
The amorphous resin composition needs to contain the dye (B) in order to increase the depth of the jet-blackness.
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. More preferably, it is one or more dyes selected from the group consisting of dyes, green dyes, blue dyes, and violet dyes.
From the viewpoint of expressing a deeper jet-blackness, it is preferable to contain three or more dyes, and the dyes are more preferably three or more dyes having different hues, red dyes, yellow dyes. , green dyes, blue dyes and violet dyes. Rather than simply combining only blue dyes and yellow dyes, or combining green dyes and red dyes in a narrow range, a combination that evenly includes the so-called three primary colors of light expresses jet-blackness. This is because it is preferable from the viewpoint of expressing jet-blackness with greater depth. Examples of such combinations include combinations of purple dyes, green dyes, yellow dyes and blue dyes; combinations of purple dyes, yellow dyes, green dyes and red dyes; red dyes, green A combination of appropriate amounts of multiple types of dyes, such as a combination of blue dyes and blue dyes, is mentioned. Among these, there are already many commercial products, and there are many types of weather resistant dyes described later, so it is more desirable. A combination of a red dye, a green dye, a yellow dye and a blue dye is preferred from the viewpoint of easily realizing the jet-blackness.

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

Although the type of dye is not particularly limited, the dye (B) contains one or more dyes selected from the group consisting of anthraquinone dyes, heterocyclic compound dyes, and perinone dyes from the viewpoint of weather resistance. More preferably, it consists of only one or more dyes selected from the group consisting of anthraquinone dyes, heterocyclic compound dyes, and perinone dyes.
Examples of anthraquinone dyes include Solvent Violet 36, Solvent Green 3, 28, Solvent Blue 94, 97, Disperse Red 22, etc., in terms of color index.
Examples of heterocyclic compound dyes include Disperse Yellow 160 and the like when represented by a color index.
Examples of perinone-based dyes include Solvent red 179 and the like when represented by a color index.
These are each used individually by 1 type or in combination of 2 or more types.

The content of the dye (B) is preferably 0.01 mass % or more and 1.5 mass % or less, and more preferably 0.02% by mass or more and 1.0% by mass or less, more preferably 0.03% by mass or more and 0.8% by mass or less, and particularly preferably 0.05% by mass or more and 0.6% by mass or less be. When the content of the dye (B) is 0.01% by mass or more and 1.5% by mass or less, there is a tendency that L ^* , which will be described later, can be adjusted within a predetermined range.

[Carbon black (C)]
From the viewpoint of weather resistance, the amorphous resin composition preferably further contains carbon black (C). The carbon black (C) preferably includes one whose surface is coated with a coating agent, and more preferably one whose surface is coated with a coating agent. By using such carbon black (C), a deeper jet-blackness can be expressed.

Examples of the coating agent include, but are not limited to, zinc stearate, magnesium stearate, calcium stearate, oleic acid amide, stearic acid amide, palmitic acid amide, methylenebisstearylamide and ethylenebisstearylamide (EBS). It preferably contains one or more compounds selected from the group, and more preferably consists of only one or more of the compounds.
Among these, zinc stearate and EBS are more preferred. By using such a coating agent, there is a tendency to achieve a deeper jet-blackness. A coating agent is used individually by 1 type or in combination of 2 or more types.
These compounds are also commonly used as dispersants for pigments such as carbon black. However, when these compounds are used as a dispersant, they are a mixture of just carbon black and powder, so they do not function as a coating agent for coating the surface of carbon black. Carbon black in this state tends to be less jet-black when compounded with an amorphous resin than carbon black whose surface is coated with the coating agent. The present inventors have found that by heating the coating agent to a temperature above its melting point, mixing it with carbon black, applying shear, and sufficiently stirring, the blending ratio of the coating agent and carbon black is exactly the same as when using a dispersant. It was found that the above coating agent functions as a surface coating agent and can significantly improve the jet-blackness even when the composition is the same. The present inventors presume the following as this mechanism. That is, the present inventors have found that there is a gap between the surface of the carbon black and the surface of the resin that is the matrix, and the incident light is scattered here, which makes it difficult to sufficiently express the jet-blackness. I think that it is the cause of a certain "white blur". In this regard, by heating the coating agent to a temperature above its melting point and then mixing it with carbon black and stirring, fine unevenness existing on the surface of the carbon black or voids existing between a plurality of carbon black particles are reduced. It is estimated that it can be easily buried. In addition, by filling the irregularities on the surface of the carbon black or the gaps between the carbon black particles with a coating agent before compounding with the molten resin, the molten resin, which is the matrix at the time of compounding, fills the irregularities and gaps. Regardless of whether or not it is possible to achieve this, it is considered to be an extremely effective means from the viewpoint of sufficiently suppressing "white blur".
Based on the presumed mechanism described above, the coating agent is not particularly limited to the compounds exemplified above, and any substance that is compatible with the methacrylic resin and hardly affects its physical properties can be suitably used. easily analogized.

When the surface of the carbon black is coated with a coating agent, the ratio (Wc/Ws) of the mass Wc of the carbon black and the mass Ws of the coating agent is preferably 20/80 to 60/40, more preferably is between 30/70 and 50/50. When Wc/Ws is within the above range, it tends to be possible to achieve deeper jet-blackness.

The content of carbon black (C) is preferably 0.01% by mass or more and 1.5% by mass or less, more preferably 0.02% by mass or more and 1.5% by mass or less, relative to the total amount of the amorphous resin composition. It is 0% by mass or less, more preferably 0.05% by mass or more and 0.5% by mass or less. When the content of carbon black (C) is 0.01% by mass or more, there is a tendency that even a thin molded article can maintain a high shielding property. In addition, when the content of carbon black (C) is 1.5% by mass or less, it tends to be possible to express deep jet-blackness. In addition, the content of carbon black excluding the coating agent is preferably 0.005% by mass or more and 0.6% by mass or less, more preferably 0.01% by mass, relative to the total amount of the amorphous resin composition. It is 0.5% by mass or more and more preferably 0.03% by mass or more and 0.4% by mass or less.

More specifically, the type of carbon black before coating has an arithmetic mean particle diameter of 10 to 40 nm as determined by microscopic observation, a nitrogen adsorption specific surface area of 50 to 400 m ² /g as defined in JIS K6217:2001, and 950°C. Carbon black that satisfies one or more conditions of 0.5 to 3% by mass of volatile matter when heated for 7 minutes at is preferably used.

[Sliding agent (D)]
From the viewpoint of scratch resistance, the amorphous resin composition preferably further contains a sliding agent (D). The sliding agent (D) is not particularly limited. Fatty acid esters, higher fatty acid mono-, di-, or triglyceride-based release agents, siloxane-based compounds, and the like can be used. Among them, siloxane-based compounds are preferable from the viewpoint of jet-blackness.

The siloxane-based compound is not particularly limited, but includes, for example, a siloxane-based compound containing a poly(meth)acryl group, a siloxane-based compound having an alkyl group having 1 to 11 carbon atoms, and a siloxane-based compound having a polyester group. compounds, siloxane compounds having a hydrocarbon group having 12 to 36 carbon atoms, and the like. Among these, a siloxane-based compound containing a poly(meth)acryl group and a siloxane-based compound having a polyester group are preferred. Moreover, the siloxane-based compound may have any of a linear, cyclic, or branched structure, but among these, a linear siloxane-based compound is preferable.

（式（Ｉ）中、Ｒは、各々独立して、１～１１個の炭素原子を有するアルキル基であり、Ｒ₁は、各々独立して、１～１１個の炭素原子を有するアルキル基又はポリエステル基であり、Ｒ₂は、各々独立して、ポリエステル基又は１２～３６個の炭素原子を有する炭化水素基であり、ｎ、ｍ、及びｐは、各々独立して、０～５８であり、かつ、Ｎ＝ｎ＋ｍ＋ｐ＋２は、１５～７５を満たし、ｍ及びｐが０である場合、全てのＲ₁はポリエステル基である。）
上記摺動剤（Ｄ）は、上記式（Ｉ）で表されるシロキサン系化合物を含むことが好ましく、上記式（Ｉ）で表されるシロキサン系化合物のみであることがより好ましい。 More specifically, the siloxane-based compound is preferably a compound represented by the following formula (I).

(In formula (I), each R is independently an alkyl group having 1 to 11 carbon atoms, and each R ₁ is independently an alkyl group having 1 to 11 carbon atoms, or a polyester group, R ₂ is each independently a polyester group or a hydrocarbon group having from 12 to 36 carbon atoms, and n, m, and p are each independently from 0 to 58; and N=n+m+p+2 satisfies 15 to 75, and all R ₁ are polyester groups when m and p are 0.)
The sliding agent (D) preferably contains the siloxane-based compound represented by the formula (I), and more preferably contains only the siloxane-based compound represented by the formula (I).

The alkyl group having 1 to 11 carbon atoms represented by R or R ₁ is not particularly limited, but examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group and isobutyl group. , sec-butyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, thexyl group, n-heptyl group, n-octyl group, n-ethylhexyl group, n-nonyl group, n- decyl group, and the like.

Hydrocarbon groups having 12 to 36 carbon atoms represented by R ₂ include linear, branched or cyclic aliphatic hydrocarbon groups; aromatic hydrocarbon groups; and the like.

The polyester group represented by R ₁ and/or R ₂ is preferably a group composed of 3 to 30 ester units, more preferably a group composed of 8 to 25 ester units, More preferably, it is a group composed of 15 to 25 ester units. Examples of such polyester groups include, but are not particularly limited to, groups represented by the following formula (V).
Formula (V): -R ^q -(R ^r ) _u H
(In formula (V), R ^q is a group represented by —(CH ₂ ) _s —O—, and each R ^r is independently C(O)—(CH ₂ ) _t —O— is a group represented by, s is 2 to 10, preferably 3 to 7, more preferably 6; t is 2 to 10, preferably 3 to 8, more preferably 4 or 5; is 3 to 30, preferably 8 to 25, more preferably 15 to 25.)
The polyester groups may be composed of the same or different starter molecules. The polyester groups are preferably built up from the same starter molecules. The polyester groups are those obtained by poly(esterification) of lactones, preferably proceeding by ring opening, more preferably caprolactone or valerolactone, especially ε-caprolactone, 3,5,5-trimethylcaprolactone or δ- It is obtained by poly(esterification) of caprolactone, more preferably by poly(esterification) of ε-caprolactone. More preferred compounds of formula (I) wherein R ₁ and/or R ₂ are polyester groups are ε- It is composed of caprolactone units. More preferably, all R ₁ are the same polyester group.
More preferably, in the compound represented by formula (I), one or more R ₂ in addition to R ₁ are polyester groups. Even more preferably, when both R ₁ and one or more R ₂ in the compound of formula (I) are polyester groups, these polyester groups are the same (having the same number of starting molecular units).
When all R ₁ are alkyl groups having 1 to 11 carbon atoms (wherein R ₁ is preferably a methyl group), R ₂ preferably has 12 to 36 carbon atoms and more It is preferably a hydrocarbon group having 20-30 carbon atoms, more preferably 24-30 carbon atoms, and n is preferably 30 or more, more preferably 40-50. When all R ₁ are alkyl groups having 1-11 carbon atoms, p is preferably 0 and m is preferably 30-48.

If one or more of R ₁ and/or R ₂ is a polyester group, n is preferably 10-45, more preferably 20-30 and most preferably 20-30. When R ₂ is a polyester group, p is preferably 0 and m is preferably 1-10, more preferably 2-5.

The siloxane-based compound represented by formula (I) is preferably a compound in which R ₂ is a polyester group or a hydrocarbon group having 12-36 carbon atoms.

Among the siloxane-based compounds represented by formula (I) in which R ₂ is a hydrocarbon group, preferred compounds have R ₁ =R = methyl group, n = 40 to 50, more preferably 40 or 50, and A mixture of compounds in which R ₂ is an alkyl group with 30 carbon atoms or an alkyl group with 24-28 carbon atoms.

Among the siloxane compounds (C) represented by the formula (I) in which R ₁ and/or R ₂ are polyester groups, preferred compounds are R=methyl group, n=20 to 45, and the polyester group is a compound with 15-25 ester units.

Among the siloxane-based compounds represented by formula (I), preferred compounds (p=0, R=methyl group, R ^q when R ₁ and/or R ₂ are polyester groups represented by formula (V) = hexanol group) can be read from Table 1 below. _{One R 1 preferably} has a structure shown in Table 1, and all R _1s more preferably have structures shown in Table 1.

Commercial products of the siloxane-based compound represented by formula (I) are not particularly limited, but examples thereof include TEGOMER (registered trademark) H—Si 6440 P and TEGOPREN (registered trademark) 6846 obtained from Evonik Goldschmidt GmbH. be done.

The siloxane-based compounds of the formula (I) are obtained by reaction of the corresponding hydrogensiloxanes with unsaturated hydrocarbons or saturated alcohols and subsequent (poly)esterification, or by direct reaction of unsaturated polyesters with hydrogensiloxanes. be able to. The reaction can be carried out by hydrosilylation as described in EP-A-1640418 or by dehydrogenative hydrosilylation. For a method for producing a polysiloxane having a polyester group, reference can be made to, for example, EP-A-0208734.

The content of the sliding agent (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, relative to the total amount of the amorphous resin composition. or less, more preferably 0.1% by mass or more and 7% by mass or less, even more preferably 0.1% by mass or more and 6% by mass or less, and particularly preferably 0.5% by mass or more and 5% by mass or less. and most preferably 1% by mass or more and 4% by mass or less. When the content of the sliding agent (D) is 0.01% by mass or more, the scratch resistance of the molded article containing the amorphous resin composition tends to be further improved. Moreover, since the content of the sliding agent (D) is 10% by mass or less, the jet-blackness tends to be further improved.
The content of the siloxane compound 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 or less, relative to the total amount of the amorphous resin composition. is more preferably 0.1% by mass or more and 7% by mass or less, still more preferably 0.1% by mass or more and 6% by mass or less, and particularly preferably 0.5% by mass or more and 5% by mass or less and most preferably 1% by mass or more and 4% by mass or less. When the content of the siloxane-based compound is 0.01% by mass or more, the scratch resistance of the molded article containing the amorphous resin composition tends to be further improved. Moreover, since the content of the siloxane-based compound is 10% by mass or less, the jet-blackness tends to be further improved.

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

Examples of the additives include antistatic agents such as polyether-based, polyetherester-based, polyetheresteramide-based, alkylsulfonate, and alkylbenzenesulfonate; antioxidants, ultraviolet absorbers, heat stabilizers, Stabilizers such as light stabilizers; flame retardants, flame retardant aids, curing agents, curing accelerators, conductivity imparting agents, stress relaxation agents, crystallization accelerators, hydrolysis inhibitors, impact agents, compatibilizers, Nucleating agents, reinforcing agents, reinforcing agents, flow control agents, sensitizers, rubbery polymers, thickeners, anti-settling agents, anti-sagging agents, fillers, anti-foaming agents, coupling agents, rust inhibitors, 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 uses. Also, a rubbery copolymer may be added as a stress relaxation agent or impact imparting agent.

(Heat stabilizer)
Examples of the heat stabilizer include, but are not particularly limited to, antioxidants such as hindered phenol-based antioxidants and phosphorus-based processing stabilizers. Among these, hindered phenol-based antioxidants are preferred. Examples of such heat stabilizers include, but are not limited to, 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-hydroxyphenyl)propionamide, 3,3′,3″,5,5′,5″-hexa-tert-butyl-a,a′,a ''-(Mesitylene-2,4,6-triyl)tri-p-cresol, 4,6-bis(octylthiomethyl)-o-cresol, 4,6-bis(dodecylthiomethyl)-o-cresol, Ethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate, hexamethylenebis[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)-trione, 2 ,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazin-2-ylamine)phenol and the like, pentaerythritol terakis[3-(3,5 -di-tert-butyl-4-hydroxyphenyl)propionate is preferred. These may be used individually by 1 type, and may be used in combination of 2 or more types.

(Ultraviolet absorber)
Examples of the ultraviolet absorber include, but are not limited to, benzotriazole-based compounds, benzotriazine-based compounds, benzoate-based compounds, benzophenone-based compounds, oxybenzophenone-based compounds, phenol-based compounds, oxazole-based compounds, and malonic acid ester-based compounds. , cyanoacrylate-based compounds, lactone-based compounds, salicylic acid ester-based compounds, benzoxazinone-based compounds, and the like. Among these, benzotriazole-based compounds and benzotriazine-based compounds are preferred. These may be used individually by 1 type, and may be used in combination of 2 or more types.

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 moldability. and more preferably 1.0×10 ⁻⁸ Pa or less. Here, "excellent molding processability" means, for example, less adhesion of the ultraviolet absorber to the mold surface during injection molding, less adhesion of the ultraviolet absorber to the roll during film molding, and the like. 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. When it is used, it is particularly important that the moldability is excellent.

From the viewpoint of preventing bleeding out, 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, and even more preferably 160° C. or higher. 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 bleeding out. , more preferably 15% or less, still more preferably 10% or less, and even more preferably 5% or less.

(Flame retardants)
Examples of the flame retardant include, but are not limited to, cyclic nitrogen compounds, phosphorus-based flame retardants, silicon-based flame retardants, cage-like silsesquioxanes or their partially cleaved structures, and silica-based flame retardants.

The kneading method for mixing the amorphous resin composition and various additives includes, but is not particularly limited to, the method described in the "Method for producing an amorphous resin composition" described later. do not have.

[Method for producing amorphous resin composition]
The amorphous resin composition includes, for example, an amorphous resin (A), a dye (B), carbon black (C) blended as necessary, a sliding agent (D), other components, and the like. It can be obtained by melt-kneading (compounding) after sufficiently mixing by stirring. Alternatively, a dye (B) and/or carbon black (C) and a sliding agent (D) are used, and a high-concentration masterbatch based on an amorphous resin (A) is melt-kneaded to prepare the master. The batch may be diluted with another amorphous resin (A) and melt-kneaded.

The melt-kneading method includes, for example, a kneading method using a kneader such as an extruder, a heating roll, a kneader, a roller mixer, or a Banbury mixer. Among these, kneading by 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 the preferred processing temperature of the amorphous resin (A), preferably 140 to 300°C, more preferably 180 to 280°C, still more preferably 160 to 260°C. By setting the kneading temperature to 300°C or less, it is possible to further suppress the generation of residual monomers due to thermal decomposition of the amorphous resin. And there is a tendency that it can be reliably prevented. The kneading rotation speed is preferably 300 rpm or less, more preferably 250 rpm or less, still more preferably 200 rpm or less, from the viewpoint of preventing coloring and thermal decomposition of the amorphous resin composition.
In addition, the discharge amount (kg/hr)/kneading rotation speed (rpm) is the non-crystalline resin (A), the dye (B), the carbon black (C), the sliding agent (D), and other additives such as additives. From the viewpoint of facilitating control of the lightness L ^* within an appropriate range by adjusting the amount of decomposition products of the components, it is preferably performed at 0.2 or more and 1.5 or less, and 0.3 or more and 1.4 or less. is more preferable, and more preferably 0.4 or more and 1.3 or less. By being 0.2 or more and 1.5 or less, it tends to be possible to adjust L ^* to the desired range. When the discharge rate/kneading rotation speed is 0.2 or more, the generation of decomposition products due to shear heat generation is suppressed, and the L ^* value tends to be easily adjusted to 2.5 or less, and the discharge rate/kneading rotation speed is 1. When it is 0.5 or less, the kneading state is not too mild, decomposition occurs appropriately, and the L ^* value tends not to be too low.
As for the mold used for molding, it is preferable that the surface of the mold (the inner surface of the mold cavity) is polished with a polishing number of 1000 to 4000.

[Characteristics of molded body]
(Brightness (L ^* ))
The “brightness (L ^* )” of the molded article of the present embodiment means the lightness value (L ^* ) among the color values in the L ^* a ^* b ^* color system adopted in JIS Z 8729. , "SCE method" means a method of measuring color by using a spectrophotometer conforming to JIS Z 8722 and removing specularly reflected light with a light trap.

The lightness (L ^* ) in the SCE measurement of the molded product of the present embodiment is 0.3 or more and 2.5 or less, preferably 0.35 or more and 2.0 or less, from the viewpoint of having jet blackness and scratch resistance. , more preferably 0.4 or more and 1.8 or less, still more preferably 0.4 or more and 1.6 or less, still more preferably 0.6 or more and 1.6 or less, particularly preferably 0.9 or more and 1.55 It is below. Among them, from the viewpoint of more excellent jet-blackness, it is preferable that L ^* before the scratch resistance test described later is within the above range, and L ^* before the scratch resistance test and L ^* after the scratch resistance test described later are Both are more preferably within the above ranges.
Furthermore, ΔL ^* before and after the scratch resistance test by the test method described later (ΔL ^* = (L ^* after the scratch resistance test) - (L ^* before the scratch resistance test)) is, from the viewpoint of the scratch resistance, It is preferably 1.0 or less, more preferably 0.9 or less, still more preferably 0.8 or less, still more preferably 0.7 or less, and particularly preferably 0.5 or less. Since L ^* before the scratch resistance test is 0.3 or more, ΔL ^* before and after the scratch resistance test tends to be reduced. Also, ΔL
^{When *} is 1.0 or less, it becomes difficult to distinguish visually from the peripheral portion where there is no scratch, and the scratch becomes inconspicuous.

(Relationship between molded body thickness and flow length)
In the molded body of the present embodiment, it is preferable that the thickness t (unit: mm) and the flow length L (unit: mm) satisfy the relationship of the following formula (II).
L/t<150 (II)
When the molded article has the relationship represented by the formula (II), it tends to be possible to satisfactorily fill the resin composition up to the end of the flow inside the mold cavity during injection molding. Moreover, since molding strain can be suppressed by satisfying the relationship represented by the above formula (II), it is also possible to prevent warpage and solvent crack tails. From the same point of view, L/t is more preferably less than 145, even more preferably less than 140. On the other hand, the lower limit of L/t is not particularly limited, but it is preferable that L/t is 100 or more from the viewpoint of further satisfying the demands for lightening and thinning of the compact. The flow length L indicates the length over which the amorphous resin composition flows when obtaining a molded body. Measured by various measuring tools.

The thickness t of the molded body of the present embodiment is preferably 1.5 mm or more and 4.0 mm or less, more preferably 1.8 mm or more and 3.5 mm or less, and 2.0 mm or more and 3.0 mm or less. More preferably, it is particularly preferably 0.5 mm or more and 3.0 mm or less. When the thickness t of the molded body is 1.5 mm or more, there is an effect that the molding distortion can be reduced. On the other hand, when the thickness t is 4 mm or less, the weight of the molded body can be further reduced. For example, when the molded article is used for applications having a design surface such as automobile exterior and interior design materials, the molded article only needs to have a design surface, and the thinner the thickness, the lighter the weight, which is preferable.

The molded product of this embodiment preferably has a gate portion corresponding to the gate of the mold used during molding. The number of gate portions is preferably at least one, more preferably one.

From the viewpoint of productivity, the molded article of the present embodiment is preferably an injection molded article.

The content of the amorphous resin (A) in the molded article of the present embodiment is preferably 50% by mass or more and 99.9% with respect to the total amount of the molded article, from the viewpoint of further improving the jet-blackness of the resulting molded article. % by mass or less, more preferably 60% by mass or more and 98.5% by mass or less, and still more preferably 70% by mass or more and 98% by mass or less.
In addition, the content of the methacrylic resin in the molded article of the present embodiment is preferably 50% with respect to the total amount of the molded article from the viewpoint of further excellent jet-blackness, surface hardness, and scratch resistance of the obtained molded article. % by mass or more and 99.9% by mass or less, more preferably 60% by mass or more and 98.5% by mass or less, and still more preferably 70% by mass or more and 98% by mass or less.

The content of the dye (B) in the molded body of the present embodiment is preferably 0.01% by mass or more and 1.5% by mass or less with respect to the total amount of the molded body from the viewpoint of weather resistance and raw material costs. , More preferably 0.02% by mass or more and 1.0% by mass or less, still more preferably 0.03% by mass or more and 0.8% by mass or less, and particularly preferably 0.05% by mass or more and 0.6% by mass % by mass or less. When the dye (B) is 0.01% by mass or more and 1.5% by mass or less, there is a tendency that L ^* can be adjusted within a predetermined range.

The content of carbon black (C) in the molded article of the present embodiment is preferably 0.01% by mass or more and 1.5% by mass or less, more preferably 0.02% by mass, relative to the total amount of the molded article. % or more and 1.0 mass % or less, more preferably 0.05 mass % or more and 0.5 mass % or less. When the content of carbon black (C) is 0.01% by mass or more, there is a tendency that even a thin molded article can maintain a high shielding property. In addition, when the content of carbon black (C) is 1.5% by mass or less, it tends to be possible to express deep jet-blackness. In addition, the content of carbon black excluding the coating agent is preferably 0.005% by mass or more and 0.6% by mass or less, more preferably 0.01% by mass or more and 0 0.5% by mass or less, more preferably 0.03% by mass or more and 0.4% by mass or less.

The content of the sliding agent (D) in the molded body of the present embodiment is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.1% by mass, relative to the total amount of the molded body. 8% by mass or less, more preferably 0.1% by mass or more and 7% by mass or less, even more preferably 0.1% by mass or more and 6% by mass or less, and particularly preferably 0.5% by mass or more It is 5 mass % or less, and most preferably 1 mass % or more and 4 mass % or less. When the content of the sliding agent (D) is 0.01% by mass or more, the scratch resistance of the molded article tends to be further improved. Moreover, since the content of the sliding agent (D) is 10% by mass or less, the jet-blackness tends to be further improved.
In addition, the content of the siloxane compound 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 or less, relative to the total amount of the molded body. It is preferably 0.1% by mass or more and 7% by mass or less, still more preferably 0.1% by mass or more and 6% by mass or less, particularly preferably 0.5% by mass or more and 5% by mass or less, and most preferably is 1% by mass or more and 4% by mass or less. When the content of the siloxane-based compound is 0.01% by mass or more, the scratch resistance of the molded article tends to be further improved. Moreover, since the content of the siloxane-based compound is 10% by mass or less, the jet-blackness tends to be further improved.

(Manufacturing method of compact)
The molded article of this embodiment can be produced, for example, as follows. First, the above-mentioned amorphous resin composition obtained in the form of pellets, if necessary, is put into a mold cavity of an injection molding machine. In this case, it is preferable to use a mold having a mold cavity having a shape corresponding to the shape of the molded product and having a one-point gate. Also, 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 by another member and cannot be visually confirmed. Then, the amorphous resin composition is injection molded under predetermined conditions by the injection molding machine. Thus, the injection molded article of this embodiment can be obtained.

In addition, the mold temperature during injection molding should be excessive cooling in consideration of the glass transition temperature of the non-crystalline resin and the viewpoint of enhancing the transferability of the polished mold surface when the mold surface is polished. from the viewpoint of suppressing , the temperature is preferably 50° C. or higher and 100° C. or lower, more preferably 60° C. or higher and 95° C. or lower, and even more preferably 65° C. or higher and 90° C. or lower.
However, if the number of the file used for polishing the mold is 5000 or higher, L ^* becomes too low and tends to deviate from the lower limit of L ^* in the present embodiment, so from the viewpoint of controlling the initial L ^* , it is preferable to use a count of less than 5000.

(Application of compact)
The molded article of the present embodiment can be suitably used in applications where jet-blackness and scratch resistance comparable to those of painted articles are required.

Such applications are not particularly limited, but for example, furniture, household goods, storage and stockpile items, building materials such as walls and roofs, toys and playground equipment, hobby applications such as pachinko machines, medical and welfare products, and OA equipment. , AV equipment, battery electrical equipment, lighting equipment, ship, aircraft body parts, vehicle parts, etc. It can be suitably used for Examples of optical applications include various lenses, touch panels, etc., 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 be used as waveguides, optical fibers, coating materials for optical fibers, LED lenses, covers for lens covers EL illumination, and the like.
Electrical and electronic applications include, for example, personal computers, game machines, televisions, car navigation systems, display devices such as electronic paper, printers, copiers, scanners, faxes, electronic notebooks and PDAs, electronic desk calculators, electronic dictionaries, cameras, and videos. Examples include cameras, mobile phones, battery packs, recording medium drives and readers, mice, numeric keypads, CD players, MD players, portable radio/audio players, and the like. In particular, it can be suitably used for designable parts of casings of televisions, personal computers, car navigation systems, electronic paper, and the like.

In particular, it is preferably used as a design material for automobiles. Design materials for automobiles include, for example, automobile exterior design materials and automobile interior design materials, but automobile exterior design materials are preferable from the viewpoint of making more advantageous use of the effects of the present invention. Examples of automotive exterior finishing materials of the present embodiment include tail lamp garnishes, rear lamp garnishes, front lamp garnishes, pillar garnishes, front grilles, rear grilles, and license plate garnishes, and these are suitable. These applications are generally thin-walled elongated parts, and designability is considered important.

EXAMPLES Hereinafter, the present embodiment will be specifically described with reference to examples, but the present embodiment is not limited to the examples described later.
In addition, Examples 1 and 2 are described as reference examples.

[Measurement and evaluation method]
<I. Molecular Weight and Molecular Weight Distribution of Amorphous Resin (A)>
The weight average molecular weight and molecular weight distribution of the amorphous resin were measured using the following equipment and conditions.
Measuring device: Tosoh gel permeation chromatography (HLC-8320GPC)
Columns: 1 TSKgel SuperH2500, 2 TSKgel SuperHM-M, 1 TSKguardcolumn SuperH-H, connected in series With this column, high molecular weights are eluted early, and low molecular weights are eluted slowly.
Detector: RI (differential refraction) detector Detection sensitivity: 3.0 mV/min
Column temperature: 40°C
Sample: 10 mL solution of 0.02 g of thermoplastic resin in tetrahydrofuran Injection volume: 10 μL
Developing solvent: tetrahydrofuran, flow rate: 0.6 mL/min
As standard samples for the calibration curve, the following 10 types of polymethyl methacrylate (Polymethyl methacrylate Calibration Kit PL2020-0101 MM-10) with known monodisperse weight peak molecular weights and different molecular weights were used.
Polymethyl methacrylate used as a standard sample for the calibration curve has the following peak molecular weight of each single peak.
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 was measured with respect to the elution time of the amorphous resin.
Based on the area area in the GPC elution curve and the calibration curve of the cubic approximation formula, the weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), GPC peak top molecular weight (Mp) and GPC of the amorphous resin (A) The ratio (%) of components having a molecular weight of ⅕ or less of the peak top molecular weight (Mp) was determined.

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

<III. Jet blackness>
For the molded articles obtained in Examples and Comparative Examples, the lightness L ^* was measured using a spectrophotometer (manufactured by Konica Minolta Japan Co., Ltd., "CM-700d") by the SCE method (10° field of view/D65 light source). It was measured.
The lower the lightness L ^* , the blacker the color, and the better the jet-blackness.

<IV. Scratch resistance>
The scratch resistance test was carried out by the following method. Using the injection-molded flat evaluation samples obtained in Examples and Comparative Examples, a pure cotton work glove was attached to the tip of a 2 cm square jig of a Gakushin type friction tester (RT-200, manufactured by Daiei Kagaku Seiki Seisakusho). , the surface of the jig that comes into contact with the evaluation sample is covered with No. 6 cotton canvas as shown in Figure 1, and the canvas is fixed so that it does not shift. 40 times in the direction of flow. Lightness L ^* was measured before and after the scratch resistance test, and ΔL ^* was calculated.
ΔL ^* = L ^* after scratch resistance test - L ^* before scratch resistance test
In addition, the surface of the molded article after the scratch resistance test was visually observed, and the scratch resistance was judged according to the following evaluation criteria.
⊚ (Excellent): Abrasion traces are almost invisible.
◯ (Good): Abrasion marks are slightly visible.
x (poor): Abrasion traces are sufficiently visible.
In addition, when ΔL ^* was 0.7 or less, abrasion marks could not be visually recognized and the abrasion resistance was excellent. When ΔL ^* was more than 0.7 and less than or equal to 1.0, the scratch resistance was good, with only slight wear traces visually recognizable. When ΔL ^* was more than 1.0, abrasion marks were sufficiently visible and the scratch resistance was poor.

<V. Heat resistance>
As a heat resistance evaluation, the Vicat softening temperature (VST) of the amorphous resin compositions of Examples and Comparative Examples described later was measured using an HDT tester (heat distortion tester) (manufactured by Toyo Seiki Seisakusho Co., Ltd.) to ISO 306. Measured according to B50.

<VI. Weather resistance>
As weather resistance evaluation, the molded articles obtained in Examples and Comparative Examples were measured using a spectrophotometer ("CM-700d" manufactured by Konica Minolta Japan Co., Ltd.) using the SCE method (10° field of view/D65 light source). After measuring L ^* a ^* b ^* , using a Sunshine Weather Meter S80 manufactured by Suga Test Instruments Co., Ltd., L after exposure conditions 63 ° C. rain (18 minutes rain / 120 minutes irradiation) 2000 hours test ^* a ^* b ^* was also measured and ΔE was calculated. A lower value of ΔE indicates better weather resistance.

[Amorphous resin composition]
The amorphous resin (A), the dye (B), the carbon black (C), and the sliding agent (D) used in the production of the amorphous resin composition in Examples and Comparative Examples to be described later are described below. .

[Raw materials used in Examples and Comparative Examples]
(Amorphous resin (A))
Commercial products used as the amorphous resin (A) and raw materials used to produce the amorphous resin (A) are as follows.
・ Polycarbonate Mitsubishi Engineering grade name: H-3000
Weight average molecular weight: 38,000, molecular weight distribution: 2.3
・Polystyrene PS Japan grade name: G9305
Weight average molecular weight: 250,000, molecular weight distribution: 2.3
The structural unit was St: 100% by mass.
- Methacrylic resin The methacrylic resins (A-1) to (A-4) produced according to Production Examples A1 to A4 below were used.

Raw material of methacrylic resin Methyl methacrylate (MMA): Asahi Kasei Chemicals (2,4-dimethyl-6-t-butylphenol (2,4-di-methyl-6-tert-butylphenol) manufactured by Chugai Boeki as a polymerization inhibitor) 2.5 ppm is added)
- Methyl acrylate (MA): manufactured by Mitsubishi Chemical (with 14 ppm of 4-methoxyphenol manufactured by Kawaguchi Chemical Industry Co., Ltd. added as a polymerization inhibitor)
・n-phenylmaleimide (PMI): manufactured by Nippon Shokubai ・Styrene (St): manufactured by Asahi Kasei ・n-octylmercaptan: manufactured by Arkema ・2-ethylhexyl thioglycolate: manufactured by Arkema ・Lauroyl peroxide: manufactured by NOF ・Calcium phosphate: manufactured by Nippon Kagaku Kogyo Co., Ltd., used as a suspending agent ・Calcium carbonate: manufactured by Shiraishi Industry, used as a suspending agent ・Lauryl sulfate Sodium (sodium lauryl sulfate): manufactured by Wako Pure Chemical Industries, used as a suspension aid

<Production Example A1 (Production of methacrylic resin (A-1))>
Ion-exchanged water: 2 kg, tribasic calcium 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 mixture (a).
Next, ion-exchanged water: 26 kg was put into 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: 62 g were charged.
Thereafter, suspension polymerization was carried out while maintaining the temperature at about 80° C. 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.
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 passed through a 1.68 mm mesh sieve to remove aggregates, and the obtained bead-like polymer was separated. After washing, dehydration and drying, fine polymer particles were obtained.
The resulting fine polymer particles were melt-kneaded in a twin-screw extruder with a diameter of 30 mm set at 240° C., and the strands were cooled and cut to obtain resin pellets [methacrylic resin (A-1)].
The weight average molecular weight of the obtained resin pellet was 102,000, the peak top molecular weight (Mp) was 109,000, and the molecular weight distribution (Mw/Mn) was 1.85. Furthermore, the abundance (%) of the molecular weight component of 1/5 or less of the Mp value was 4.5%. Moreover, the structural unit was MMA/MA=98/2 (% by mass).

<Production Example A2 (Production of methacrylic resin (A-2))>
(First row)
Ion-exchanged water: 2 kg, tribasic calcium 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 mixture (b).
Next, 23 kg of ion-exchanged water was added to a 60 L reactor, the temperature was raised to 80° C., and the mixture (b), methyl methacrylate: 5.5 kg, lauroyl peroxide: 40 g, and 2-ethylhexylthioglycol were mixed. Rate: 90 g was charged. Thereafter, suspension polymerization was carried out while keeping the temperature at about 80°C. An exothermic peak was observed 80 minutes after the raw materials were added.
(Second row)
Then, after the temperature was raised to 92°C at a rate of 1°C/min, the temperature was maintained at 92°C to 94°C for 30 minutes. After that, the temperature was lowered to 80°C at a rate of 1°C/min, and then methyl methacrylate: 16.2 kg, methyl acrylate: 0.75 kg, lauroyl peroxide: 21 g, and n-octyl mercaptan: 17.5 g were added. Then, the temperature was maintained at about 80° C. and suspension polymerization was carried out. An exothermic peak was observed 105 minutes after the raw materials were added. Thereafter, the temperature was raised to 92° C. at a rate of 1° C./min, followed by aging 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 the polymerization reaction solution was passed through a 1.68 mm mesh sieve to remove aggregates, and the obtained bead-like polymer was washed, dehydrated and dried to obtain fine polymer particles. The resulting fine polymer particles were melt-kneaded in a twin-screw extruder of φ30 mm set at 240° C., and the strands were cooled and cut to obtain resin pellets [methacrylic resin (A-2)].
The weight average molecular weight of the obtained resin pellet was 172,000, the peak top molecular weight (Mp) was 197,000, and the molecular weight distribution (Mw/Mn) was 3.65. Furthermore, the abundance (%) of the molecular weight component of 1/5 or less of the Mp value was 24.5%. Moreover, the structural unit was MMA/MA=96.5/3.5 (% by mass).

<Production Example A3 (Production of methacrylic resin (A-3))>
(First row)
Ion-exchanged water: 2 kg, tribasic calcium 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 mixture (c).
Next, ion-exchanged water: 23 kg was added to a 60 L reactor, the temperature was raised to 80 ° C., and the mixture (c) and methyl methacrylate: 7.8 kg, methyl acrylate: 0.16 kg, lauroyl peroxide: 55 g, 2-ethylhexyl thioglycolate: 165 g were charged. Thereafter, suspension polymerization was carried out while maintaining about 80° C., and an exothermic peak was observed.
(Second row)
After that, the temperature was raised to 92° C. at a rate of 1° C./min, and the temperature was maintained at 92° C. to 94° C. for 30 minutes. After that, the temperature was lowered to 80°C at a rate of 1°C/min, and then methyl methacrylate: 15.0 kg, methyl acrylate: 0.3 kg, lauroyl peroxide: 25 g, and n-octyl mercaptan: 18.5 g were added. Then, the temperature was maintained at about 80° C. and suspension polymerization was carried out. After observing an exothermic peak, the temperature was raised to 92° C. at a rate of 1° C./min, followed by aging for 60 minutes to substantially complete the polymerization reaction.
Next, after cooling to 50° C. and adding 20% by mass of sulfuric acid to dissolve the suspending agent, the polymerization reaction solution is passed through a 1.68 mm mesh sieve to remove aggregates, and the obtained bead-like polymer is separated. After washing, dehydration and drying, fine polymer particles were obtained. The fine polymer particles thus obtained were melt-kneaded in a twin-screw extruder of φ30 mm set at 230° C., and the strands were cooled and cut to obtain methacrylic resin pellets (A-3).
The weight average molecular weight of the obtained resin pellet was 127,000, the peak top molecular weight (Mp) was 165,000, and the molecular weight distribution (Mw/Mn) was 4.45. Furthermore, the abundance (%) of the molecular weight component of 1/5 or less of the Mp value was 32.5%. Moreover, the structural unit was MMA/MA=98.1/1.9 (% by mass).

<Production Example A4 (Production of methacrylic resin (A-4))>
Ion-exchanged water: 2 kg, tribasic calcium phosphate: 65 g, calcium carbonate: 39 g, and sodium lauryl sulfate: 0.39 g were put into a container equipped with a stirrer to obtain a mixture (d).
Next, ion-exchanged water: 26 kg was put into a 60 L reactor, the temperature was raised to 80° 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. Thereafter, suspension polymerization was carried out while maintaining the temperature at about 80° C. 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.
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 passed through a 1.68 mm mesh sieve to remove aggregates, and the obtained bead-like polymer was separated. After washing, dehydration and drying, fine polymer particles were obtained.
The fine polymer particles thus obtained were melt-kneaded in a twin-screw extruder of φ30 mm set at 240° C., and the strands were cooled and cut to obtain resin pellets [methacrylic resin (A-4)].
The obtained resin pellets had a weight average molecular weight of 123,000, a peak top molecular weight (Mp) of 109,000, and a molecular weight distribution (Mw/Mn) of 1.83. Furthermore, the abundance (%) of the molecular weight component of 1/5 or less of the Mp value was 4.0%. Moreover, the structural unit was MMA/PMI/St=81/14/5 (% by mass).

(Crystalline resin)
・Polyethylene terephthalate manufactured by Unitika: Grade name: MA-2103

(Dye (B))
As dyes, commercially available products listed in Table 2 were used as compound raw materials. Table 4 shows the amount of each compound.

(Carbon black (C))
For C-A1, carbon black C-A0 shown in Table 3 was subjected to surface coating treatment using a coating agent. Specifically, first, a coating agent of 1.5 times the mass of carbon black C-A0 is weighed and melted by heating it to 160 ° C., which is the melting point or higher, and then a predetermined amount of carbon black is added to it. It was put into the melt and stirred. The melting point of zinc stearate is about 140°C. After sufficiently stirring and dispersing, the mixture was cooled to obtain a surface-coated carbon black.

(Sliding agent (D))
As the siloxane compound, the following commercially available additives were used.
D-1: TEGOMER (registered trademark) H-Si 6440P (manufactured by Evonik)
D-2: Chaline R-170S (manufactured by NOF Corporation)
D-1 is a polysiloxane-based compound having a polyester group D-2 is a polysiloxane-based compound having a poly(meth)acrylic group As other sliding agents, the following commercial products were used.
D-3: zinc stearate (manufactured by Kanto Chemical Co., Ltd.)
D-4: NOFALLOY KA832 (manufactured by NOF Corporation) thermoplastic elastomer

[Examples 1 to 15] [Comparative Examples 1 to 7]
The amorphous resin (A), the dye (B), the carbon black (C), and the sliding agent (D) were each weighed so as to achieve the blending ratio shown in Table 4, and then mixed and dispersed by dry blending. . After sufficiently mixing, the mixed raw material is put into a φ30 mm twin-screw extruder, melt-kneaded (compounded) to form a strand, cooled in a water bath, and cut with a pelletizer to form pellets. Obtained. During compounding, a vacuum line was connected to the vent portion of the extruder to remove volatile components such as moisture and monomer components. Thus, an amorphous resin composition was obtained. The temperature of the resin composition during compounding was 230 to 280°C. In addition, the discharge amount (kg/hr)/kneading rotation speed (rpm) was adjusted to the values shown in Table 4. Table 4 shows the kneading conditions for each example and comparative example.

[Sample for flat evaluation]
(injection molding)
The obtained pellets of the amorphous resin composition were put into an injection molding machine and molded into a flat plate (100 mm×100 mm×3 mmt) to obtain a sample for evaluation. The mold used had a mold surface (inner surface of the mold cavity) that was polished with No. 2000, No. 4000, or No. 8000. Then, the surface of the molded product to which the mold surface on the side polished with the polishing count was transferred was used as the smooth surface of this evaluation sample. That is, the smooth surface area of this evaluation sample was 100 cm ² . The molding conditions for this evaluation sample were set as follows.
Resin temperature: 230°C to 280°C
Mold temperature: 60 to 85°C (30°C only for Comparative Example 7)
The components contained in the molded article obtained and the mass ratio of each component were the same as those of the amorphous resin composition. Table 4 shows the molding conditions for each example and comparative example.

In Example 1, polycarbonate, dye (B), carbon black (C), and sliding agent (D) were blended, and the initial L ^* was appropriate. was at a good level.
In Example 2, polystyrene, dye (B), carbon black (C), and sliding agent (D) were blended, and L ^* was appropriate. was a level.
In Examples 3, 4, and 6, by using the methacrylic resin, the jet-blackness tended to be improved compared to Example 1, and the scratch resistance was at a practically good level.
Also, in Examples 7 to 10, L ^* was appropriate, and addition of the sliding agent (D) made almost no visible scratches after the scratch test, indicating very good scratch resistance.
In Example 5, the abundance of molecular weight components of 1/5 or less of the peak top molecular weight (Mp) obtained from the GPC elution curve was in the range of 6 to 50%. In comparison, the scratch resistance tended to improve.
In Example 11, under the molding conditions described above, a mold that had been polished with a polishing count of No. 2000 was used, so compared to Example 5, L ^* was more appropriate, and the scratch resistance was at a practically favorable level. Met.
In Example 12, under the extrusion conditions, the discharge rate (kg/hr)/ ^kneading rotation speed (rpm) was 1.3, which was out of the most preferable range. Although ΔL ^* increased, it was at a good level for practical use.
In Example 13, the extrusion rate (kg/hr)/ ^kneading rotation speed (rpm) was 0.5, which was the most preferable range. Therefore, the scratch resistance was at a very good level for practical use.
In Example 14, a mold polished with a polish number of 2000 was used, and under the extrusion conditions, the discharge rate (kg/hr)/kneading rotation speed (rpm) was 0.5, which is the most preferable range. Therefore, compared with Example 5, L ^* was more appropriate, and the scratch resistance was at a practically very good level.
In Example 15, a mold polished with a polish number of 2000 was used, and under the extrusion conditions, the discharge rate (kg/hr)/kneading rotation speed (rpm) was 0.5, which is the most preferable range. Therefore, compared to Example 9, L ^* was even more appropriate, and the scratch resistance was at a practically very good level.
On the other hand, in Comparative Example 1, since the dye (B) was not used, the jet-blackness was lowered, and since the polycarbonate alone was used without adding a sliding agent, the scratch resistance was insufficient.
In Comparative Examples 2 and 3, the lower limit of L ^* was not met because the material was polished with a polishing number of No. 8000 under the molding conditions described above. As a result, scratches after the scratch resistance test became more noticeable.
In Comparative Example 4, the addition of the thermoplastic elastomer deviated from the upper limit of L ^* , and scratches after the scratch resistance test became more noticeable.
In Comparative Example 5, compared to Comparative Example 2, the discharge rate (kg/hr)/kneading rotation speed (rpm) was set to 2.0 in the ^extrusion conditions. Scratches after the test became more noticeable.
In Comparative Example 6, a mold polished with a polish number of 4000 was used. Compared to , it was outside the lower limit of L ^* , and scratches after the scratch resistance test became more noticeable.
In Comparative Example 7, since a crystalline resin was used, compared with Examples, L ^* did not decrease unless a large amount of dye was added ^. Easier to stand out.

Regarding the use of the molded article of the present embodiment, it can be industrially used in general for applications requiring jet-blackness and scratch resistance.

Claims (13)

including an amorphous resin (A) and a dye (B),
Lightness (L ^* ) measured by SCE is 0.3 or more and 1.6 or less ,
The amorphous resin (A) is a methacrylic resin,
The content of the amorphous resin (A) in the molded body is 60% by mass or more and 99.9% by mass or less with respect to the total amount of the molded body . molding. The molded article according to claim 1, further comprising carbon black (C). The carbon black (C) is carbon black surface-coated with a coating agent,
The coating agent contains one or more selected from the group consisting of zinc stearate, magnesium stearate, calcium stearate, oleic acid amide, stearic acid amide, palmitic acid amide, methylenebisstearylamide, and ethylenebisstearylamide. The molded article according to claim 2. The molded article according to any one of claims 1 to 3, further comprising a sliding agent (D). The molded article according to claim 4, wherein the sliding agent (D) contains a siloxane compound represented by the following formula (I).

(In formula (I), each R is independently an alkyl group having 1 to 11 carbon atoms, and each R ₁ is independently an alkyl group having 1 to 11 carbon atoms, or a polyester group, R ₂ is each independently a polyester group or a hydrocarbon group having 12 to 36 carbon atoms, and n, m, and p are each independently 0 to 58; and N=n+m+p+2 satisfies 15 to 75, and all R ₁ are polyester groups when m and p are 0.) Any one of claims 1 to 5, wherein the dye (B) contains one or more dyes selected from the group consisting of red dyes, yellow dyes, green dyes, blue dyes, and purple dyes. The molded article according to the item. The molding according to any one of claims 1 to 6, wherein the dye (B) contains one or more dyes selected from the group consisting of anthraquinone dyes, heterocyclic compound dyes, and perinone dyes. body. The weight average molecular weight of the methacrylic resin measured by gel permeation chromatography (GPC) is 50000 to 300000, and
The ratio of components 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 is 6 to 50 with respect to the total area of the GPC elution curve of the methacrylic resin. %, the molded article according to any one of claims 1 to 7 . The molded article according to any one of claims 1 to 8 , which is an injection molded article. 10. The compact according to any one of claims 1 to 9, wherein the thickness t (unit: mm) and the flow length L (unit: mm) satisfy the following formula (II) and have one gate portion. The molded article according to item 1.
L/t<150 (II) The molded article according to any one of claims 1 to 10 , wherein the molded article has a thickness t (unit: mm) of 0.5 or more and 3.0 or less. The molded article according to any one of claims 1 to 11 , which is a tail lamp garnish, a rear lamp garnish, a front lamp garnish, a pillar garnish, a front grille, a rear grille, or a license plate garnish. The methacrylic resin has a weight average molecular weight of 50,000 to 300,000,
The methacrylic resin has a methacrylic acid ester monomer unit content of 80 to 99.9% by mass with respect to the total amount of the methacrylic resin, and the methacrylic acid ester monomer constituting the methacrylic resin The molded article according to any one of claims 1 to 12, wherein the content of other copolymerizable vinyl monomer units is 0.1 to 20% by mass with respect to the total amount of the methacrylic resin.

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