JP2008106195A - Methacrylate-based polymer using reactive anthraquinone-based compound, and its resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymer molding superior in colorability, transparency and color durability; and being free from the bleed-out of a coloring agent, by copolymerizing an anthraquinone-based compound having good copolymerizing property with a vinylic monomer, such as an alkyl acrylate, an alkyl methacrylate and styrene. <P>SOLUTION: A methacrylate-based polymer and the like obtained by using a reactive anthraquinone-based compound of a prescribed structure having acryloyl group or methacryloyl group, an ultraviolet absorbent and the vinylic monomer compound, are provided. This polymer is utilized for moldings such as a film, in a wide range. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a methacrylic ester polymer, a methacrylic resin mixture, and a methacrylic resin composition obtained by using a reactive anthraquinone compound.

  Conventionally, acrylic resins have been used in various molded products by blending colorants such as dyes and pigments by utilizing their transparency. For example, various moldings in a wide range of fields such as lamp cases and covers, pachinko parts, retroreflective sheets (used for road signs for road safety, truck tapes, poles, etc.), housings for various electrical products, etc. Used in the body. For example, when a colored methacrylic resin obtained by mixing a colorant such as a dye with a methacrylic resin is used as a film, in order to develop a predetermined degree of coloring, the more the film is colored the thinner It is necessary to add an agent, which is uneconomical.

  When a large amount of colorant is added to a methacrylic resin and a film is formed by a method such as extrusion, problems such as clogging of an extruder vent, adhesion to a so-called eye on a T-die, and coloring of a cooling roll occur. Further, when a large amount of colorant is added, the film surface becomes rough, and problems such as elution (bleed out) of the colorant to the film surface occur.

  Even if a large amount of a colorant is added to the methacrylic resin without causing these problems, a general colorant has poor compatibility with the methacrylic resin and has a low molecular weight. The part volatilizes and the problem that coloring performance is not exhibited arises. In particular, many resin products to which a colorant has been added are affected by ultraviolet rays, heat, etc. due to long-term use, outdoor use, lamp use, and the like, and the color developability deteriorates with time. Or, since the colorant is lost from the methacrylic resin due to long-term use, there arises a problem that the coloring performance deteriorates with time.

  In order to solve these problems, a method using a specific colorant is generally known for the purpose of improving the dispersibility of the colorant in the resin. However, when the film obtained by this method is immersed in warm water or exposed to the outdoors, the added colorant bleeds out. Therefore, problems such as deterioration in coloring performance have not been solved.

  On the other hand, the color derived from the compound exhibiting the colorability by mixing the methacrylic compound and the compound exhibiting the colorability or reacting the methacrylic compound in the presence of the compound exhibiting the colorability. A method for preparing a resin having a pH is disclosed (Patent Documents 1 to 3). Patent Document 1 describes colored polymethyl methacrylate obtained by adding a specific dye during polymerization of methyl (meth) acrylate. This gives a relatively uniform mixture of polymer and dye. However, since the dye is not included as a component of the polymer, the problem of bleeding out of the colorant cannot be solved. Patent Document 2 describes a reaction between a vinyl sulfone type reactive dye or a dichlorotriazine type reactive dye and a reactive non-crosslinked polymer, but since it is difficult to form a copolymer, unreacted dye remains. However, this has the problem of bleeding out.

As a method for improving the color sustainability, Patent Document 3 discloses a method in which an acrylic resin, a polycarbonate resin, an amorphous polyolefin resin, or the like is used in combination with one or more colorants. However, in general, the colorant has a high melting point and is suitable for a resin having a high molding temperature such as a polycarbonate resin, but it is suitable for a resin having a relatively low molding temperature such as an acrylic resin or an amorphous polyolefin resin. Does not sufficiently disperse the colorant in the resin, and as a result, the color persistence cannot be maintained. Furthermore, the problem of bleedout has not been solved.
Japanese Patent Laid-Open No. 8-48899 Japanese Patent Laid-Open No. 9-20873 JP 2004-75709 A

  The object of the present invention is to use a reactive compound having good copolymerizability for vinyl monomers such as acrylic acid alkyl esters, methacrylic acid alkyl esters, and styrene, and having excellent coloring properties. It is to obtain an acrylic polymer which is excellent in the property, transparency, and color persistence and does not cause colorant bleeding out. Still another object of the present invention is to provide a molded article such as a film using the polymer.

  As a result of intensive studies on the above problems, the present inventors have found that a reactive anthraquinone compound having a (meth) acryloyl group in the molecular structure has good copolymerizability with a vinyl monomer and has excellent coloring characteristics. Found to have. Furthermore, a film prepared using a polymer obtained from this reactive anthraquinone compound and a vinyl monomer is excellent in transparency, bending crack resistance, colorability, and color sustainability, and bleed out occurs. Found no. As a result of repeated studies based on these findings, the inventors have completed the present invention.

  That is, the present invention provides a methacrylic acid ester polymer (A) obtained by subjecting a reactive anthraquinone compound represented by the general formula (1) and a methacrylic monomer (i) to a polymerization reaction.

ＸはＨまたはメチル基であり、Ｙは−（ＣＨ₂）_n−であり、そして、ｎは２〜１６の整数である
（請求項１）に関する、
メタクリル系単量体（ｉ）が５０〜９９．９９質量％、反応性アントラキノン系化合物が０．０１〜５０質量％、の割合で用いられることを特徴とする請求項１記載のメタクリル酸エステル系重合体（Ａ）（請求項２）に関する、
重合反応において、メタクリル系単量体（ｉ）が５０〜９９．９９質量％、反応性アントラキノン系化合物が０．０１〜５０質量％、および一般式（２）で表される紫外線吸収剤が０．０１〜３０質量％、の割合で用いられることを特徴とする請求項１記載のメタクリル酸エステル系重合体（Ａ）。

X is H or a methyl group, Y is — (CH ₂ ) _n —, and n is an integer from 2 to 16 (claim 1).
2. The methacrylic acid ester system according to claim 1, wherein the methacrylic monomer (i) is used in a proportion of 50 to 99.99 mass% and the reactive anthraquinone compound is 0.01 to 50 mass%. Regarding the polymer (A) (Claim 2),
In the polymerization reaction, the methacrylic monomer (i) is 50 to 99.99 mass%, the reactive anthraquinone compound is 0.01 to 50 mass%, and the ultraviolet absorber represented by the general formula (2) is 0. The methacrylic ester polymer (A) according to claim 1, wherein the methacrylic acid ester polymer (A) is used in a ratio of 0.01 to 30% by mass.

ＸはＨまたはハロゲン、Ｒ₁はＨ、メチル基または炭素数４〜６のｔ−アルキル基、Ｒ₂は直鎖または枝分かれ鎖状の炭素数２〜１０のアルキレン基、Ｒ₃はＨまたはメチル基である（請求項３）に関する、
メタクリル系単量体（ｉ）に占めるメタクリル酸アルキルエステルの割合が５０質量％以上であることを特徴とする請求項１〜請求項３のいずれかに記載のメタクリル酸エステル系重合体（Ａ）（請求項４）に関する、
メタクリル系単量体（ｉ）が、メタクリル酸アルキルエステルおよびアクリル酸アルキルエステルを含む混合単量体、またはメタクリル酸アルキルエステルである、請求項１〜４のいずれかに記載のメタクリル酸エステル系重合体（Ａ）（請求項５）に関する、
アクリル酸エステル系架橋弾性体粒子をコアとし、メタクリル酸エステル系重合体からなる層を外層とする多層構造重合体粒子（Ｂ）、およびメタクリル酸エステル系重合体を含有するメタクリル系樹脂混合物（Ｃ）であって、
該混合物（Ｃ）が、該アクリル酸エステル系架橋弾性体粒子の存在下で、メタクリル系単量体（ｉ）を重合させることにより得られ、
該アクリル酸エステル系架橋弾性体粒子が、１分子中に２個以上の非共役二重結合を有する多官能性単量体とアクリル系単量体（ｉｉ）とを重合させることにより得られ、
該アクリル系単量体（ｉｉ）が、アクリル酸アルキルエステルを５０質量％以上の割合で含有し、
該メタクリル系単量体（ｉ）が、メタクリル酸アルキルエステルを５０質量％以上の割合で含有し、
該アクリル酸エステル系架橋弾性体粒子を調製するための重合反応工程、および該架橋弾性体粒子の存在下における該メタクリル系単量体（ｉ）の重合反応工程のうちの少なくとも一方の工程において、一般式（１）で表される反応性アントラキノン系化合物が添加され、
該アクリル酸エステル系架橋弾性体粒子の調製のための重合反応、および／又は該アクリル酸エステル系架橋弾性体粒子存在下でのメタクリル系単量体（ｉ）の重合反応に用いられる、アクリル系単量体（ｉｉ）およびメタクリル系単量体（ｉ）が合計量で７０〜９９．９９質量％、および該メタクリル系樹脂混合物（Ｃ）を得るための重合反応に用いられるアントラキノン系化合物の総量が０．０１〜３０質量％の割合で用いられる、メタクリル系樹脂混合物（Ｃ）（請求項６）に関する、
該アクリル酸エステル系架橋弾性体粒子を調製するための重合反応工程、および該架橋弾性体粒子の存在下における該メタクリル系単量体（ｉ）の重合反応工程のうちの少なくとも一方の工程において、更に紫外線吸収剤（２）が添加され、
該アクリル酸エステル系架橋弾性体粒子の調製のための重合反応、および／又は該アクリル酸エステル系架橋弾性体粒子存在下でのメタクリル系単量体（ｉ）の重合反応に用いられる、アクリル系単量体（ｉｉ）およびメタクリル系単量体（ｉ）が合計量で７０〜９９．９９質量％、および該メタクリル系樹脂混合物（Ｃ）を得るための重合反応に用いられるアントラキノン系化合物の総量が０．０１〜３０質量％、紫外線吸収剤が０．０１〜３０質量％の割合で用いられる、請求項６に記載のメタクリル系樹脂混合物（Ｃ）（請求項７）に関する、
前記アクリル系単量体（ｉｉ）が、アクリル酸アルキルエステルおよびメタクリル酸アルキルエステルを含む混合単量体、またはアクリル酸アルキルエステルである、請求項６又は請求項７に記載のメタクリル系樹脂混合物（Ｃ）（請求項８）に関する、
前記メタクリル系単量体（ｉ）が、メタクリル酸アルキルエステルおよびアクリル酸アルキルエステルを含む混合単量体、またはメタクリル酸アルキルエステルである、請求項６〜請求項８のいずれかに記載のメタクリル系樹脂混合物（Ｃ）（請求項９）に関する、
請求項１に記載のメタクリル酸エステル系重合体（Ａ）および請求項６に記載のメタクリル系樹脂混合物（Ｃ）の少なくとも一方と、メタクリル系樹脂混合物（Ｅ）とを含むメタクリル系樹脂組成物（Ｄ）であって、
該メタクリル系樹脂混合物（Ｅ）が、アクリル酸エステル系架橋弾性体粒子をコアとし、メタクリル酸エステル系重合体からなる層を外層とする多層構造重合体粒子（Ｂ₀）、およびメタクリル酸エステル系重合体を含有し、
該メタクリル系樹脂混合物（Ｅ）が、該アクリル酸エステル系架橋弾性体粒子の存在下で、メタクリル系単量体（ｉ）を重合させることにより得られ、
該アクリル酸エステル系架橋弾性体粒子が、１分子中に２個以上の非共役二重結合を有する多官能性単量体とアクリル系単量体（ｉｉ）とを重合させることにより得られ、
該アクリル系単量体（ｉｉ）が、アクリル酸アルキルエステルを５０質量％以上の割合で含有し、
該メタクリル系単量体（ｉ）が、メタクリル酸アルキルエステルを５０質量％以上の割合
で含有し、
該メタクリル系樹脂混合物（Ｅ）１００質量部に対して、該メタクリル酸エステル系重合体（Ａ）およびメタクリル系樹脂混合物（Ｃ）の少なくとも一方が０．１〜２００質量部の割合で含有される、メタクリル系樹脂組成物（Ｄ）（請求項１０）に関する、
前記アクリル系単量体（ｉｉ）が、アクリル酸アルキルエステルおよびメタクリル酸アルキルエステルを含む混合単量体、またはアクリル酸アルキルエステルである、請求項１０に記載の樹脂組成物（Ｄ）（請求項１１）に関する、
前記メタクリル系単量体（ｉ）が、メタクリル酸アルキルエステルおよびアクリル酸アルキルエステルを含む混合単量体、またはメタクリル酸アルキルエステルである、請求項１０または請求項１１に記載の樹脂組成物（Ｄ）（請求項１２）に関する、
請求項１に記載のメタクリル酸エステル系重合体（Ａ）を成形して得られるフィルム（請求項１３）に関する、
請求項６に記載のメタクリル系樹脂混合物（Ｃ）を成形して得られるフィルム（請求項１４）に関する、
請求項１０に記載の樹脂組成物（Ｄ）を成形して得られるフィルム（請求項１５）に関する、
請求項１３〜請求項１５のいずれかに記載のフィルムを少なくとも１つの層として含有する積層体（請求項１６）に関する、ものである。

X is H or halogen, R ₁ is H, a methyl group or a t-alkyl group having 4 to 6 carbon atoms, R ₂ is a linear or branched alkylene group having 2 to 10 carbon atoms, R ₃ is H or methyl Which is a group (Claim 3),
The methacrylic acid ester polymer (A) according to any one of claims 1 to 3, wherein the proportion of the methacrylic acid alkyl ester in the methacrylic monomer (i) is 50% by mass or more. (Claim 4)
The methacrylic acid monomer (i) is a mixed monomer containing a methacrylic acid alkyl ester and an acrylic acid alkyl ester, or a methacrylic acid alkyl ester. Regarding union (A) (Claim 5),
Multilayer structure polymer particles (B) having acrylic ester-based crosslinked elastic particles as a core and a layer made of a methacrylate ester polymer as an outer layer, and a methacrylic resin mixture (C) containing a methacrylate ester-based polymer ) And
The mixture (C) is obtained by polymerizing the methacrylic monomer (i) in the presence of the acrylic ester-based crosslinked elastic particles.
The acrylic ester-based crosslinked elastic particles are obtained by polymerizing a polyfunctional monomer having two or more non-conjugated double bonds in one molecule and an acrylic monomer (ii),
The acrylic monomer (ii) contains an acrylic acid alkyl ester in a proportion of 50% by mass or more,
The methacrylic monomer (i) contains a methacrylic acid alkyl ester in a proportion of 50% by mass or more,
In at least one of a polymerization reaction step for preparing the acrylic ester-based crosslinked elastic particles and a polymerization reaction step of the methacrylic monomer (i) in the presence of the crosslinked elastic particles, A reactive anthraquinone compound represented by the general formula (1) is added,
Acrylic polymer used for the polymerization reaction for the preparation of the acrylic ester-based crosslinked elastic particles and / or the polymerization reaction of the methacrylic monomer (i) in the presence of the acrylic ester-based crosslinked elastic particles The total amount of the anthraquinone compound used in the polymerization reaction for obtaining the monomer (ii) and the methacrylic monomer (i) in a total amount of 70 to 99.99% by mass and the methacrylic resin mixture (C) Methacrylic resin mixture (C) (Claim 6), used at a ratio of 0.01 to 30% by mass,
In at least one of a polymerization reaction step for preparing the acrylic ester-based crosslinked elastic particles and a polymerization reaction step of the methacrylic monomer (i) in the presence of the crosslinked elastic particles, Furthermore, an ultraviolet absorber (2) is added,
Acrylic polymer used for the polymerization reaction for the preparation of the acrylic ester-based crosslinked elastic particles and / or the polymerization reaction of the methacrylic monomer (i) in the presence of the acrylic ester-based crosslinked elastic particles The total amount of the anthraquinone compound used in the polymerization reaction for obtaining the monomer (ii) and the methacrylic monomer (i) in a total amount of 70 to 99.99% by mass and the methacrylic resin mixture (C) Is used in a proportion of 0.01 to 30% by mass and an ultraviolet absorber is used in a proportion of 0.01 to 30% by mass, and relates to the methacrylic resin mixture (C) according to claim 6 (Claim 7).
The methacrylic resin mixture according to claim 6 or 7, wherein the acrylic monomer (ii) is a mixed monomer containing an acrylic acid alkyl ester and a methacrylic acid alkyl ester, or an acrylic acid alkyl ester. C) (Claim 8)
The methacrylic monomer according to any one of claims 6 to 8, wherein the methacrylic monomer (i) is a mixed monomer containing a methacrylic acid alkyl ester and an acrylic acid alkyl ester, or a methacrylic acid alkyl ester. Regarding the resin mixture (C) (Claim 9),
A methacrylic resin composition comprising at least one of the methacrylic acid ester polymer (A) according to claim 1 and the methacrylic resin mixture (C) according to claim 6 and a methacrylic resin mixture (E). D),
The methacrylic resin mixture (E) is a multilayer structure polymer particle (B ₀ ) having an acrylic ester-based crosslinked elastic particle as a core and a layer made of a methacrylate ester-based polymer as an outer layer, and a methacrylate ester-based Containing a polymer,
The methacrylic resin mixture (E) is obtained by polymerizing the methacrylic monomer (i) in the presence of the acrylic ester-based crosslinked elastic particles,
The acrylic ester-based crosslinked elastic particles are obtained by polymerizing a polyfunctional monomer having two or more non-conjugated double bonds in one molecule and an acrylic monomer (ii),
The acrylic monomer (ii) contains an acrylic acid alkyl ester in a proportion of 50% by mass or more,
The methacrylic monomer (i) contains a methacrylic acid alkyl ester in a proportion of 50% by mass or more,
At least one of the methacrylic ester polymer (A) and the methacrylic resin mixture (C) is contained at a ratio of 0.1 to 200 parts by mass with respect to 100 parts by mass of the methacrylic resin mixture (E). The methacrylic resin composition (D) (claim 10),
The resin composition (D) according to claim 10, wherein the acrylic monomer (ii) is a mixed monomer containing an alkyl acrylate ester and an alkyl methacrylate ester, or an alkyl acrylate ester. 11),
The resin composition (D) according to claim 10 or 11, wherein the methacrylic monomer (i) is a mixed monomer containing a methacrylic acid alkyl ester and an acrylic acid alkyl ester, or a methacrylic acid alkyl ester. ) (Claim 12),
Regarding a film (Claim 13) obtained by molding the methacrylate polymer (A) according to Claim 1.
Regarding a film (Claim 14) obtained by molding the methacrylic resin mixture (C) according to Claim 6.
Regarding a film (Claim 15) obtained by molding the resin composition (D) according to Claim 10.
It is related with the laminated body (Claim 16) which contains the film in any one of Claims 13-15 as at least 1 layer.

  The reactive anthraquinone compound, which is one of the main components of the present invention, is a good copolymer for (meth) acrylic monomers such as alkyl acrylates and alkyl methacrylates, and vinyl monomers such as styrene. Combines polymerizability and excellent coloring properties. By reacting the reactive anthraquinone compound with another monomer, the methacrylic acid ester polymer of the present invention, a methacrylic resin mixture, and a methacrylic resin composition containing at least one of these are reactive. It has a color tone derived from an anthraquinone compound. Moreover, the bleeding out of a coloring component is suppressed. Moreover, it is excellent in fading resistance.

  The film and laminate containing the polymer, mixture, and composition have a color tone derived from a reactive compound and are excellent in fading resistance.

  In this specification, “(meth) acryl” refers to at least one of acrylic and methacrylic. For example, “(meth) acrylic acid” refers to at least one of acrylic acid and methacrylic acid.

(I) Reactive Anthraquinone Compound The reactive anthraquinone compound, which is one of the main components of the present invention, is a compound represented by the following general formula (1) (hereinafter referred to as a reactive anthraquinone compound (1). ), Compound (1), etc.). For Y reactive draft Torakinon compound used also _{(1) - (CH 2)} n - and is, preferably from n is 4 to 16, more preferably 6 to 16, particularly preferably 8 to 16.

This reactive anthraquinone compound can be prepared using, for example, the method described in Molecular Crystals and Liquid Crystals (1981), 78 (1-4), 271-277, and the like. The final synthesis step for introducing a reactive functional group can be performed, for example, by a method in which acryloyl chloride or methacryloyl chloride is reacted with a hydroxyl group using a base.

  As will be described later, this reactive anthraquinone compound (1) is copolymerized with various monomers, for example, a (meth) acrylic monomer, so as to have a color derived from the compound (1). Coalescence can be obtained. Furthermore, this compound (1) is used as a colorant for various materials, for example, optical recording materials, synthetic resins, fibers, paints, paper, oil, cream, organic solvents, etc. by mixing or reacting with various materials. Can do.

  The reactive anthraquinone compound (1), which is one of the main components of the present invention, includes various reactive monomers such as (meth) acrylic monomers such as methacrylic acid alkyl esters and acrylic acid alkyl esters. A polymer having a color derived from the compound (1) can be obtained by copolymerizing with another vinyl monomer (ethylenically unsaturated monomer) that can be copolymerized with the compound (1). it can. In such a polymer, the reactive anthraquinone compound (1) is incorporated in the polymer (randomly incorporated in the (meth) acrylic polymer). Therefore, bleeding out of the coloring component is suppressed. Moreover, it is excellent in fading resistance.

A polymer (A ₀ ) derived from the reactive anthraquinone compound (1); a methacrylic acid ester polymer (A) as a representative example thereof; and a polymer derived from the reactive anthraquinone compound (1) are shown below. The methacrylic resin mixture (C) containing the contained multilayer polymer particles and the methacrylic resin composition (D) will be described.
(I) Polymer (A ₀ )
The polymer (A ₀ ) of the present invention is obtained by reacting the reactive anthraquinone compound (1) with a copolymerizable monomer.

  Examples of the monomer include methacrylic acid alkyl esters, acrylic acid alkyl esters, and ethylenically unsaturated monomers.

  The methacrylic acid alkyl ester is preferably an alkyl group having 1 to 12 carbon atoms in view of polymerization reactivity and cost, and may be linear or branched. Specific examples thereof include methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate and the like, and these monomers are one kind or two or more kinds. May be used in combination.

  The alkyl acrylate is preferably one having 1 to 12 carbon atoms in the alkyl group from the viewpoint of polymerization reactivity and cost, and may be linear or branched. Specific examples thereof include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, and n-octyl acrylate. These monomers may be used alone or in combination of two or more.

  Examples of the ethylenically unsaturated monomers include vinyl halides such as vinyl chloride and vinyl bromide; vinyl cyanides such as acrylonitrile and methacrylonitrile; vinyl esters such as vinyl formate, vinyl acetate and vinyl propionate; styrene, Aromatic vinyl derivatives such as vinyltoluene and α-methylstyrene; vinylidene halides such as vinylidene chloride and vinylidene fluoride; acrylic acid and salts thereof such as acrylic acid, sodium acrylate and calcium acrylate; β-hydroxyethyl acrylate Alkyl acrylate derivatives such as dimethylaminoethyl acrylate, glycidyl acrylate, acrylamide and N-methylol acrylamide; methacrylic acid such as methacrylic acid, sodium methacrylate and calcium methacrylate And salts thereof; methacrylic acid alkyl ester derivatives such as methacrylamide, β-hydroxyethyl methacrylate, dimethylaminoethyl methacrylate, glycidyl methacrylate, and the like. Two or more of these monomers may be used in combination.

In the polymer (A ₀ ) of the present invention, an ultraviolet absorber (2) may be copolymerized as necessary.

  The polymerization reaction of the reactive anthraquinone compound (1) and the above monomer is not particularly limited, and emulsion polymerization, emulsion-suspension polymerization, suspension polymerization, bulk polymerization, and solution weight used in this field are used. Any of the legal can be utilized. The reaction conditions are appropriately determined according to the type and amount of the monomer used.

(II) Methacrylate polymer (A)
The methacrylic acid ester polymer (A) of the present invention (hereinafter sometimes referred to as polymer (A)) is a polymerization reaction of reactive anthraquinone compound (1) and methacrylic monomer (i). To be obtained.

  This methacrylic monomer (i) is a methacrylic acid alkyl ester alone or a methacrylic acid alkyl ester as a main component, an acrylic acid alkyl ester, and, if necessary, an ethylene copolymer copolymerizable with these esters. It is a mixed monomer containing an unsaturated monomer.

  The methacrylic acid alkyl ester is preferably an alkyl group having 1 to 12 carbon atoms in view of polymerization reactivity and cost, and may be linear or branched. Specific examples thereof include methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate and the like, and these monomers are one kind or two or more kinds. May be used in combination.

  The alkyl acrylate is preferably one having 1 to 12 carbon atoms in the alkyl group from the viewpoint of polymerization reactivity and cost, and may be linear or branched. Specific examples thereof include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, and n-octyl acrylate. These monomers may be used alone or in combination of two or more.

  Examples of the ethylenically unsaturated monomers include vinyl halides such as vinyl chloride and vinyl bromide; vinyl cyanides such as acrylonitrile and methacrylonitrile; vinyl esters such as vinyl formate, vinyl acetate and vinyl propionate; styrene, Aromatic vinyl derivatives such as vinyltoluene and α-methylstyrene; vinylidene halides such as vinylidene chloride and vinylidene fluoride; acrylic acid and salts thereof such as acrylic acid, sodium acrylate and calcium acrylate; β-hydroxyethyl acrylate Alkyl acrylate derivatives such as dimethylaminoethyl acrylate, glycidyl acrylate, acrylamide and N-methylol acrylamide; methacrylic acid such as methacrylic acid, sodium methacrylate and calcium methacrylate And salts thereof; methacrylic acid alkyl ester derivatives such as methacrylamide, β-hydroxyethyl methacrylate, dimethylaminoethyl methacrylate, glycidyl methacrylate, and the like. Two or more of these monomers may be used in combination.

  The methacrylic monomer (i), which is a raw material of the methacrylic ester polymer (A), preferably contains a methacrylic acid alkyl ester in a proportion of 50% by mass or more, but is not limited thereto. Absent. More preferably, it is a mixed ester composed of 50% by mass or more of methacrylic acid alkyl ester and less than 50% by mass of acrylic acid alkyl ester. More preferably, the methacrylic monomer (i) is a methacrylic acid alkyl ester of 50% by mass or more, an acrylic acid alkyl ester of less than 50% by mass, and the ethylenically unsaturated monomer of 30% by mass or less. It contains in the ratio. Particularly preferably, it contains 60% by mass or more of methacrylic acid alkyl ester, less than 40% by mass of acrylic acid alkyl ester, and 20% by mass or less of the ethylenically unsaturated monomer. When the alkyl acrylate is less than 50% by mass, the resulting methacrylic acid ester polymer (A) is excellent in heat resistance, and sufficient hardness is obtained.

As described above, the methacrylic acid ester polymer (A) is obtained by subjecting the reactive anthraquinone compound (1) and the methacrylic monomer (i) to a polymerization reaction. In the polymerization reaction, the methacrylic monomer (i) is used in a proportion of 50 to 99.99% by mass, and the reactive anthraquinone compound (1) is used in a proportion of 0.01 to 50% by mass. More preferably, the methacrylic monomer (i) is used in a proportion of 60 to 99.99% by mass, and the reactive anthraquinone compound (1) is used in a proportion of 0.01 to 40% by mass. The monomer (i) is used in a proportion of 70 to 99.99% by mass, and the reactive anthraquinone compound (1) is used in a proportion of 0.01 to 30% by mass, particularly preferably a methacrylic monomer (i). Is 70 to 99.9 mass%, and the reactive anthraquinone compound (1) is used at a ratio of 0.1 to 30 mass%. In the reactive anthraquinone compound (1), Y is — (CH ₂ ) _n —, preferably n is 4 to 16, more preferably 6 to 16, and particularly preferably 8 to 16. When the ratio of the reactive anthraquinone compound (1) is 0.01% by mass or more, the resulting polymer (A) has excellent colorability, and when it is 50% by mass or less, the polymer (A) It is excellent in the impact resistance and the bending cracking resistance of a molded product obtained by using, for example, a film.

  Moreover, in the polymer (A) of this invention, you may copolymerize a ultraviolet absorber (2) as needed. When the ultraviolet absorber (2) is copolymerized, the methacrylic acid ester polymer (A) is 50 to 99.99% by mass of the methacrylic monomer (i), and the reactive anthraquinone compound (1). Is used in a proportion of 0.01 to 50% by mass, and the ultraviolet absorber (2) is used in a proportion of 0.01 to 30% by mass. More preferably, the methacrylic monomer (i) is 60 to 99.99% by mass, the reactive anthraquinone compound (1) is 0.01 to 40% by mass, and the ultraviolet absorber (2) is 0.01 to More preferably, the methacrylic monomer (i) is 70 to 99.99% by mass, the reactive anthraquinone compound (1) is 0.01 to 30% by mass, and UV absorption. The agent (2) is used in a proportion of 0.01 to 20% by mass, and particularly preferably, the methacrylic monomer (i) is 70 to 99.9% by mass and the reactive anthraquinone compound (1) is 0.00. 1-30 mass% and a ultraviolet absorber (2) are used in the ratio of 0.05-20 mass%. When the ratio of the reactive anthraquinone compound (1) is 0.01% by mass or more, the resulting polymer (A) has excellent colorability, and when it is 50% by mass or less, the polymer (A) It is excellent in the impact resistance and the bending cracking resistance of a molded product obtained by using, for example, a film. It is particularly preferred that the reactive anthraquinone compound (1) in the methacrylic acid ester polymer (A) is 0.01 to 20% by mass, and further 0.01 to 10% by mass.

  Here, the ultraviolet absorber (2) is a reactive ultraviolet absorber represented by the general formula (2).

  The polymerization reaction between the reactive anthraquinone compound (1) and the methacrylic monomer (i) is not particularly limited, and is an emulsion polymerization method, an emulsion-suspension polymerization method, a suspension polymerization method, a bulk weight used in this field. Both legal methods and solution polymerization methods can be utilized. In the reaction, generally used initiators, dispersants (used in the suspension polymerization method) and the like are used. As the polymerization method, the suspension polymerization method is particularly preferable from an industrial viewpoint. In these polymerization reactions, the reactive anthraquinone compound (1) and the methacrylic monomer (i) are polymerized in one or more steps.

  As the initiator that can be used in the polymerization reaction, organic peroxides, inorganic peroxides, azo compounds and the like that are generally used in the field can be used. Examples of the organic peroxide include t-butyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, succinic acid peroxide, peroxymaleic acid t-butyl ester, cumene hydroperoxide, Benzoyl peroxide, lauroyl peroxide, t-butyl peroxybenzoate, isopropyl t-butyl peroxycarbonate, butyl perbenzoate, 1,1-bis (alkylperoxy) 3,3,5-trimethylcyclohexane, 1, 1-bis (alkylperoxy) cyclohexane or the like is used. As the inorganic peroxide, potassium persulfate, sodium persulfate and the like are used, and as the azo compound, azobisisobutyronitrile and the like are used. These may be used alone or in combination of two or more.

  Of the above initiators, the organic peroxide is added to the polymerization system as it is; raw material monomers (reactive anthraquinone compound (1), methacrylic monomer (i), and ultraviolet ray used if necessary) It can be added by a normal addition method such as a method of mixing with at least one of the absorbents (2) and adding to the polymerization system; a method of dispersing in an aqueous emulsifier solution and adding to the polymerization system. From the viewpoint of the transparency of the polymer (A) to be obtained, a method of mixing and adding to the raw material monomer is preferable.

  Examples of the dispersant used for the suspension polymerization include dispersants generally used for suspension polymerization, polymer dispersants such as polyvinyl alcohol, polyvinyl pyrrolidone, and polyacrylamide; calcium phosphate, hydroxyapatite, magnesium pyrophosphate, and the like. Examples include hardly water-soluble inorganic salts. In the case of using a poorly water-soluble inorganic salt as a dispersant, it is effective to use an anionic surfactant such as α-olefin sulfonic acid soda and dodecylbenzene sulfonic acid soda in order to increase dispersion stability. Further, these dispersants can be added one or more times during the polymerization in order to adjust the particle diameter of the obtained resin particles.

  The resulting slurry of the methacrylic ester polymer (A) is separated and recovered by ordinary dehydration, washing and drying operations.

(III) Methacrylic resin mixture (C)
The methacrylic resin mixture (C) of the present invention has acrylic ester-based crosslinked elastic particles (hereinafter may be referred to as acrylic ester-based crosslinked elastic particles (B-1), core particles (B-1), etc.). The multilayer structure polymer particle (B) which makes the outer layer (B-2) the layer which consists of a methacrylic ester polymer, and the methacrylic ester polymer (C-1). The methacrylic resin mixture (C) is obtained by polymerizing the methacrylic monomer (i) in the presence of the acrylate-based crosslinked elastic particles (B-1), and the particles (B- In at least one of the polymerization reaction step for preparing 1) and the polymerization reaction step of the methacrylic monomer (i) in the presence of the particles (B-1), the reactive anthraquinone system Compound (1) is added. The polymer formed by adding the reactive anthraquinone compound (1) has a color derived from the reactive anthraquinone compound (1).

  Therefore, the methacrylic resin mixture (C) is a multilayer structure polymer particle (B) in which at least one of the acrylate ester-based crosslinked elastic particles (B-1) and the outer layer (B-2) is colored, A colored or uncolored methacrylate polymer (C-1).

  In the methacrylic resin mixture (C) of the present invention, the multilayer polymer particles (B) and the methacrylic acid ester polymer (C-1) are preferably 40:60 to 95: 5, more preferably in mass ratio. Is contained in a ratio of 50:50 to 90:10.

  The acrylic acid ester-based crosslinked elastic particles (B-1), the multilayer structure polymer particles (B), and the multilayer structure polymer particles (B) constituting the multilayer structure polymer particles (B) are contained below. The methacrylic resin mixture (C) will be described sequentially.

(IV-1) Acrylic ester-based crosslinked elastic particles (B-1)
The acrylic ester-based crosslinked elastic particles (B-1) serving as the core of the multilayer structure polymer particle (B) have an acrylic monomer (ii) and two or more non-conjugated double bonds in one molecule. It can be obtained by copolymerizing the polyfunctional monomer (iii) having the above-described reaction and the reactive anthraquinone compound (1) as necessary. Furthermore, in addition to the said monomer, a ultraviolet absorber (2) can also be copolymerized as needed.

  The acrylic monomer (ii) is an acrylic acid alkyl ester alone, or an acrylic acid alkyl ester having a main component of an acrylic acid alkyl ester and, if necessary, an ethylene copolymer copolymerizable with these esters. It is a mixed monomer containing an unsaturated monomer.

  The alkyl acrylate ester preferably has 1 to 12 carbon atoms in the alkyl group from the viewpoint of polymerization reactivity and cost, and may be linear or branched. Specific examples thereof include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, and n-octyl acrylate. . These monomers may be used alone or in combination of two or more.

  As the methacrylic acid alkyl ester and the ethylenically unsaturated monomer, the methacrylic acid alkyl ester that can be contained in the methacrylic monomer (i) used for the preparation of the methacrylic acid ester polymer (A), respectively, and The same compounds as the ethylenically unsaturated monomer can be used.

  The acrylic monomer (ii) contains the alkyl acrylate ester in a proportion of 50% by mass or more. Preferably, the acrylic monomer (ii) comprises an acrylic acid alkyl ester of 50% by mass or more, a methacrylic acid alkyl ester of less than 50% by mass, and the ethylenically unsaturated monomer of 30% by mass or less. Contains in proportions. More preferably, it contains 60% by mass or more of acrylic acid alkyl ester, less than 40% by mass of methacrylic acid alkyl ester, and 20% by mass or less of the ethylenically unsaturated monomer. Usually, the acrylic monomer (ii) is a mixed ester composed of 50% by mass or more of an acrylic acid alkyl ester and less than 50% by mass of a methacrylic acid alkyl ester. When the methacrylic acid alkyl ester is less than 50% by mass, the strength of the molded product obtained using the resulting multilayer structure polymer particles (B), particularly the resistance to bending cracking in the film, is excellent.

  Examples of the polyfunctional monomer (iii) include the following compounds: allyl methacrylate, allyl acrylate, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, diallyl malate, divinyl adipate, divinylbenzene ethylene glycol Dimethacrylate, divinylbenzene ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetramethacrylate, tetramethylol Methane tetraacrylate, dipropylene glycol dimeta Relate, dipropylene glycol diacrylate. These may be used alone or in combination of two or more.

  The polyfunctional monomer (iii) is preferably 0.05 to 20 parts by mass and more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the acrylic monomer (ii). When the amount of the polyfunctional monomer used is 0.05 parts by mass or more, the molded product obtained using the finally obtained multilayer structure polymer particles (B), particularly the impact resistance and resistance of the film. When it is excellent in bending cracking property and is 20 parts by mass or less, impact resistance and bending cracking resistance are excellent.

  As described above, the acrylic ester-based crosslinked elastic particles (B-1) are composed of the acrylic monomer (ii), the polyfunctional monomer (iii), and, if necessary, a reactive anthraquinone compound ( It is obtained by subjecting 1) to a polymerization reaction. The polymerization reaction at this time is not particularly limited, and any of the emulsion polymerization method, emulsion-suspension polymerization method, suspension polymerization method, bulk polymerization method, and solution polymerization method used in this field can be used. Preferably, an emulsion polymerization method is employed. For example, when a suspension polymerization method is employed, a particulate polymer is directly formed. In the emulsion polymerization method, a latex containing fine particles is formed. Usually, the reaction liquid (latex, suspension, etc.) containing the acrylate ester-based crosslinked elastic particles (B-1) obtained by an emulsion polymerization method, a suspension polymerization method, etc. is used as it is as described later in the multilayer structure polymer particles ( Used in the preparation reaction of B). In the case of using another polymerization method, for example, a solution polymerization method, a particulate polymer (acrylic ester-based crosslinked elastic particles (B-1)) is precipitated by an appropriate means after the reaction, and this polymer is contained. The suspension can be used for the preparation reaction of the multilayer structure polymer particles (B) described later.

  The acrylate-based crosslinked elastic particles (B-1) are also suitably used for applications other than the preparation of the multilayer structure polymer particles (B), such as toners and optical recording materials. The acrylic ester-based crosslinked elastic particles (B-1) can be obtained, for example, by subjecting the latex obtained by the emulsion polymerization to a salting-out treatment to form a powder or a lump, and a powder having particles of an appropriate size. In the case of solution polymerization, the bulk / indeterminate polymer obtained by removing the solvent can be pulverized into powder.

  In the reaction for preparing the acrylic ester-based crosslinked elastic particles (B-1), generally used initiators, dispersants (used for suspension polymerization), emulsifiers (used for emulsion polymerization) and the like are used. . The polymerization reaction is particularly preferably an emulsion polymerization method from an industrial viewpoint. In these polymerization reactions, the reactive anthraquinone compound (1) and the acrylic monomer (ii) are polymerized in one or more steps.

  As the initiator that can be used in the polymerization reaction, organic peroxides, inorganic peroxides, azo compounds and the like that are generally used in the field can be used. Examples of the organic peroxide include t-butyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, succinic acid peroxide, peroxymaleic acid t-butyl ester, cumene hydroperoxide, Benzoyl peroxide is used. As the inorganic peroxide, potassium persulfate, sodium persulfate and the like are used, and as the azo compound, azobisisobutyronitrile and the like are used. These may be used alone or in combination of two or more.

  These initiators may be used as a normal redox initiator in combination with a reducing agent (an inorganic reducing agent and / or an organic reducing agent). Examples of reducing agents include the following compounds: sodium sulfite, sodium thiosulfate, sodium formaldehyde sulfoxylate, ascorbic acid, reducing sugar, hydroxyacetone acid, divalent iron salts (such as ferrous sulfate). , Complexes of ferrous sulfate and disodium ethylenediaminetetraacetic acid. In particular, when an organic peroxide is used as an initiator, it is preferable to use a redox initiator from the viewpoint of polymerization stability and particle size control.

  Among the above initiators, the organic peroxide is added as it is to the polymerization system; the raw material monomer (such as acryl monomer (ii)) is mixed and added to the polymerization system; It can be added by a usual addition method such as a method of dispersing and adding to the polymerization system. From the viewpoint of the transparency of the resulting acrylate ester-based crosslinked elastic particles (B-1), a method of adding to the raw material monomer or a method of adding it by dispersing in an aqueous emulsifier solution is preferred.

  The surfactant used for the emulsion polymerization is not particularly limited, and any surfactant for ordinary emulsion polymerization can be used. Specific examples include the following compounds: anionic surfactants such as sodium alkyl sulfonate, sodium alkylbenzene sulfonate, sodium dioctyl sulfosuccinate, sodium lauryl sulfate, and sodium fatty acid; and alkylphenols, fatty alcohols Nonionic surfactants such as reaction products of alcohols such as propylene oxide and ethylene oxide. These surfactants may be used alone or in combination of two or more. Furthermore, you may use cationic surfactants, such as an alkylamine salt, as needed.

  The particle diameter of the acrylic ester-based crosslinked elastic particles (B-1) is not particularly limited, and varies depending on the polymerization method and the treatment after the polymerization (such as pulverization). For example, when the acrylic ester-based crosslinked elastic particles (B-1) are prepared by an emulsion polymerization reaction, the latex particle size obtained is usually 10 to 500 nm, preferably 50 to 300 nm. The acrylic ester-based crosslinked elastic particles (B-1) are colorless or exhibit a color tone derived from the reactive anthraquinone compound (1).

(IV-2) Multilayer structure polymer particles (B) and a methacrylic resin mixture (C) containing the particles (B)
The multilayer structure polymer particle (B) is obtained by polymerizing the methacrylic monomer (i) and, if necessary, the reactive anthraquinone compound (1) in the presence of the core particle (B-1). It is obtained by forming B-2). Furthermore, in addition to the said monomer, a ultraviolet absorber (2) can also be copolymerized as needed.

  A methacrylic ester polymer (C-1) derived from the methacrylic monomer (i) is simultaneously formed during this polymerization reaction. A mixture containing the multilayer structure polymer particles (B) and the methacrylic ester polymer (C-1) can be used as the methacrylic resin mixture (C). Alternatively, a methacrylic acid ester-based polymer (C-1) is prepared in another polymerization system using the methacrylic monomer (i), and these are prepared from the above multilayer structure polymer particles (B) and methacrylic acid. In addition to the mixture containing the ester polymer (C-1), the resulting mixture may be a methacrylic resin mixture (C).

  As said methacrylic monomer (i), the monomer similar to the methacrylic monomer (i) used for preparation of the above-mentioned methacrylic ester polymer (A) is used. As in the case of the methacrylic acid ester polymer (A), the methacrylic acid alkyl ester in the methacrylic monomer (i) is 50% by mass or more and is contained in the methacrylic monomer (i). When the alkyl acrylate ester is less than 50% by mass, the resulting multilayer structure polymer particle (B) or methacrylic resin mixture (C) molded article, for example, a film having excellent heat resistance and sufficient hardness can get.

  The multilayer structure polymer particle (B) is prepared so that at least one of the core particle (B-1) and the outer layer (B-2) is colored. A reactive anthraquinone compound (1) is used in forming the portion that needs to be colored. For example, when the core particle (B-1) is a colored particle, in preparation thereof, as described above, the anthraquinone reactive with the acrylic monomer (ii) and the multifunctional monomer (iii). The system compound (1) is added to carry out copolymerization. When the outer layer (B-2) is a colored layer, the polymerization of the methacrylic monomer (i) and the reactive anthraquinone compound (1) in the presence of the core particles (B-1) Is done. In forming the above (B-1) and / or (B-2), an ultraviolet absorber (2) may be further used as a copolymerization component as necessary.

  In preparing the multilayer polymer particles (B), as described above, in the presence of the core particles (B-1), the methacrylic monomer (i) and, if necessary, the reactive anthraquinone compound (1) Is polymerized to form an outer layer. In the polymerization reaction at this time, as in the case of the preparation of the acrylic ester-based crosslinked elastic particles (B-1), a normal polymerization reaction, for example, an emulsion polymerization method or an emulsion-suspension used in this field. Any of a polymerization method, a suspension polymerization method, a bulk polymerization method, and a solution polymerization method are employed. Preferably, an emulsion polymerization method is employed.

  For example, as described above, the reaction liquid containing the acrylic ester-based crosslinked elastic particles (B-1) obtained by emulsion polymerization or the like is used as it is, and the methacrylic monomer (i) and, if necessary, the same. Then, the reactive anthraquinone compound (1) is added and polymerized. In the reaction, as in the case of the preparation of the acrylic ester-based crosslinked elastic particles (B-1), generally used initiators, dispersants (used for suspension polymerization), emulsifiers (used for emulsion polymerization). Etc. can be used.

  Polymerization reaction for obtaining methacrylic resin mixture (C) of the present invention (namely, polymerization reaction for preparation of core particle (B-1) of multilayer structure polymer particle (B), and methacrylic system using the same In the polymerization reaction for the preparation of the resin mixture (C)), the total amount of the methacrylic monomer (i) and the acrylic monomer (ii) is 70 to 99.99% by mass. The total amount of compound (1) is used in a proportion of 0.01 to 30% by mass. When the ultraviolet absorber (2) is further used as the copolymer component, the total amount of the methacrylic monomer (i) and the acrylic monomer (ii) is 70 to 99.98% by mass. The total amount of the system compound (1) is 0.01 to 30% by mass, and the total amount of the ultraviolet absorber (2) is 0.01 to 30% by mass. When the reactive anthraquinone compound (1) is added to the polymerization reaction system during the preparation of the core particle (B-1) as described above; in the presence of the core particle (B-1), methacryl When added to the polymerization reaction system together with the monomer (i); or may be added to the polymerization reaction system in both of these polymerization reactions. The “total amount” of the reactive anthraquinone compound (1) is the amount of the reactive anthraquinone compound (1) used in each of these cases, and is added to the polymerization reaction system in both of the polymerization reactions. In the case, it refers to the total amount of the reactive anthraquinone compound (1) added to both.

  As for the above amount, the acrylic monomer (ii) is preferably 75 to 99.99% by mass in total amount, and the total amount of the reactive anthraquinone compound (1) is 0.01 to 25% by mass. More preferably, the acrylic monomer (ii) is used in a total amount of 80 to 99.99% by mass, and the total amount of the reactive anthraquinone compound (1) is 0.01 to 20% by mass. It is done. Particularly preferably, the acrylic monomer (ii) is used in a total amount of 80 to 99.95% by mass, and the total amount of the reactive anthraquinone compound (1) is 0.05 to 20% by mass. When the total amount of the reactive anthraquinone compound (1) is 0.01% by mass or more, the molded product formed using the resulting multilayer structure polymer particles (B), for example, the film has good colorability, When the content is 30% by mass or less, the resulting molded article, for example, a film is excellent in impact resistance and bending cracking resistance.

  The multilayer structure polymer particle (B) usually has the acrylic ester-based crosslinked elastic particle (B-1) as a core as described above, but unlike this, the methacrylic ester-based polymer is the innermost layer. It is also possible to form such that particles of a two-layer structure having a layer made of an acrylate-based crosslinked elastic polymer on the surface thereof are used as a core, and a methacrylic acid ester-based polymer as an outer layer.

  The multilayer structure polymer particle (B) is a multilayer structure having two or more layers. For example, the methacrylic monomer (i) and, if necessary, the reactive anthraquinone compound (1) are polymerized in the presence of the core particle (B-1) to form the first layer, It may be a particle having a three-layer structure obtained by polymerizing the methacrylic monomer (i) having a structure and, if necessary, the reactive anthraquinone compound (1) to form a second layer (outer layer). . Further, a layer may be formed in the same manner to form particles of four or more layers.

  As a result of the polymerization reaction, acrylic ester-based crosslinked elastic particles (B-1) are used as a core, and a methacrylic ester-based polymer (methacrylic monomer (i) or methacrylic monomer (i) and reactive anthraquinone. A multilayer structure polymer particle (B) having a layer composed of a polymer derived from the system compound (1) as an outer layer is formed. At the same time, particles comprising a methacrylic monomer (i) or a polymer derived from a methacrylic monomer (i) and a reactive anthraquinone compound (1)), that is, a methacrylic ester polymer (C-1) ) Is also formed. As a result, a methacrylic resin mixture (C) which is a mixture containing the multilayer structure polymer particles (B) and the methacrylic ester polymer (C-1) is obtained. For example, the methacrylic resin mixture (C) is obtained in a latex state by emulsion polymerization. The latex can be salted out to form a powder or agglomerate, which can be obtained as a powder having particles of an appropriate size. Alternatively, the bulk or indefinite shape polymer obtained by removing the solvent can be pulverized into powder. In pulverization, a usual coagulation method such as salting-out, washing and drying methods are used. As a drying method, spray drying, freeze drying, or the like can be used in addition to normal ventilation drying.

  As mentioned above, when the methacrylic resin mixture (C) contains the methacrylic ester polymer (C-1) prepared in another polymerization system, the methacrylic ester polymer (C-1). ) May be a colorless polymer or a polymer containing the reactive anthraquinone compound (1) as a constituent component and having a color tone derived from the compound (1). The methacrylic acid ester polymer (C-1) prepared in another polymerization system contains the multilayer structure polymer particles (B) and the methacrylic acid ester polymer (C-1) with the reaction liquid at the time of preparation. It may be added to the mixture, or may be added to the mixed powder of the multilayer structure polymer particles (B) and the methacrylic ester polymer (C-1) after being powdered.

Since the acrylic ester-based crosslinked elastic particles (B-1) which is the core of the multilayer structure polymer particle (B) is a crosslinked polymer containing a polyfunctional monomer (iii) as a copolymerization component, Has elasticity. In the acrylic ester-based crosslinked elastic particles (B-1), the reactive functional group (double bond) in the molecule of the polyfunctional monomer (iii) remains in the reaction during preparation.
Accordingly, when the polymerization reaction of the methacrylic monomer (i) is carried out in the presence of the acrylic ester-based crosslinked elastic particles (B-1), the remaining reactive functional group is a methacrylic monomer. Graft reaction with body (i). As a result, the acrylic ester-based crosslinked elastic particles (B-1) as the core are firmly bonded to the outer layer formed of the methacrylic monomer (i).

  The particle diameters of the multilayer structure polymer particles (B) and the methacrylic acid ester polymer (C-1) contained in the methacrylic resin mixture (C) vary depending on the polymerization method and are not particularly limited. For example, when obtained as a latex by emulsion polymerization, this latex usually contains particles of 10 to 500 nm, preferably 50 to 500 nm. When this is collected by salting-out or filtration, for example, it can be obtained in the form of a powder in which these particles are aggregated.

(V) Methacrylic resin composition (D)
The methacrylic resin composition (D) of the present invention contains at least one of the methacrylic ester polymer (A) and the methacrylic resin mixture (C), and the methacrylic resin mixture (E), and is further necessary. Depending on the case, it contains other resins, inorganic pigments, organic dyes, additives and the like. This methacrylic resin mixture (E) has a multilayer structure weight in which an acrylic ester-based crosslinked elastic particle (B ₀ -1) is a core and a layer made of a methacrylic ester polymer is an outer layer (B ₀ -2). It contains coalesced particles (B ₀ ) and a methacrylic ester polymer (C-2).

The methacrylic multilayer structure polymer particles (B ₀ ) are basically the same as the multilayer structure polymer particles (B), but the weight of the multilayer structure prepared without using the reactive anthraquinone compound (1). It is a coalesced particle. Since the reactive anthraquinone compound (1) is not used, it is uncolored. The methacrylic multilayer structure polymer particles (B ₀ ) are prepared under the same conditions as the multilayer structure polymer particles (B) except that the reactive compound (1) is not used. When the polymerization reaction of the methacrylic monomer (i) is carried out in the presence of the acrylic ester-based crosslinked elastic particles (B ₀ -1), the methacrylic single-layered polymer particles (B ₀ ) and the methacrylic monomer A methacrylic ester polymer (C-2) derived from the monomer (i) is formed.

  Examples of the other resins include methacrylic resins, polyglutarimides, glutaric anhydride polymers, lactone cyclized methacrylic resins, polyethylene terephthalate resins, polybutylene terephthalate resins, and polyvinylidene fluoride resins.

  Examples of the additive include an antioxidant, a heat stabilizer, and an ultraviolet light stabilizer that are used for the purpose of further improving the stability to heat and light, and further include an antibacterial agent, a deodorizing agent, and a lubricant. These may be contained alone or in combination of two or more.

  In this methacrylic resin composition (D), at least one of the methacrylic ester polymer (A) and the methacrylic resin mixture (C) is 100 parts by mass of the methacrylic resin mixture (E). It is contained at a ratio of 0.1 to 200 parts by mass. The content of at least one of the methacrylic ester polymer (A) and the methacrylic resin mixture (C) is preferably 0.1 to 150 parts by mass, more preferably 0.1 to 100 parts by mass, particularly preferably. Is a ratio of 1 to 100 parts by mass. When the content is 0.1 parts by mass or more, the molded product obtained using the obtained methacrylic resin composition (D), for example, excellent in colorability of the film, and when the content is 200 parts by mass or less, Excellent impact resistance and bending cracking resistance. The other resin is contained in a proportion of 100 parts by mass or less and the additive is contained in a proportion of 10 parts by mass or less with respect to 100 parts by mass of the methacrylic resin mixture (E).

(VI) Molded product, film and laminate using methacrylic resin mixture (C) or methacrylic resin composition (D) The methacrylic resin mixture (C) alone or the mixture (C) and polymer By molding the resin composition (D) which is a composition containing at least one of (A), a molded product having a color tone derived from the reactive anthraquinone compound (1) contained therein can be obtained. . In molding, various plastic processing methods such as injection molding, extrusion molding, blow molding, and compression molding generally used in the field are employed.

  The molded body includes a single-layer film having the predetermined color tone, a laminated film in which the single-layer films are laminated, a laminated film in which another film is laminated on the single-layer film, and a molded body main body. There is a laminate in which a single layer or a laminated film is laminated on the surface.

  The film (single layer or laminated film) having the predetermined color tone can be produced by an ordinary film production method. For example, when a film is prepared using a methacrylic resin mixture (C) or a resin composition (D), an ordinary melt extrusion method such as an inflation method, a T-die extrusion method, a calendar method, or a solvent cast The method is preferably used. This film is subjected to a treatment such as biaxial stretching as required.

  Among the above, in order to obtain a laminated film or a laminated body, for example, a laminated body in which a base material such as a plastic sheet and a film having the predetermined color tone are simultaneously formed to obtain a laminated body in which these are laminated. Alternatively, coextrusion molding is employed. Or the film which has the said predetermined | prescribed color tone is produced previously, and it laminates | stacks on the base material which consists of a metal, a plastics, etc., and can obtain a laminated body. Specific examples of such a method include wet laminating, dry laminating (a method in which an adhesive is applied and dried on a base material such as a steel plate, and then a film is placed on the base material and bonded), extrusion laminating, hot melt Laminate etc. are mentioned.

  As a method of obtaining a laminate by laminating a film having a predetermined color tone on a molded body body of a predetermined shape such as a plastic part, the film is placed in a mold and filled with resin by injection molding. Examples thereof include insert molding or laminate injection press molding, in-mold molding in which a film is preformed, placed in a mold, and filled with resin by injection molding.

  When forming a film by the above-mentioned various methods, if necessary, by simultaneously bringing both sides of the film into contact with a roll or a metal belt, particularly by bringing into contact with a roll or a metal belt heated to a temperature higher than the glass transition temperature. It is also possible to obtain a film having a more excellent surface smoothness.

  The thickness of the film obtained from the methacrylic resin mixture (C) or the resin composition (D) of the present invention is preferably 10 to 300 μm, more preferably 10 to 200 μm. When the thickness of the film is 10 μm or more, the processability of the film is excellent, and when it is 300 μm or less, the resulting film has excellent transparency.

  If necessary, the gloss of the film surface can be reduced by a known method. For example, a method of obtaining a film by adding an inorganic filler or crosslinkable polymer particles to a methacrylic resin mixture (C) and kneading and molding, or an inorganic filler or crosslinkable as a component of the resin composition (D) A method of obtaining a film by adding polymer particles and kneading and molding each component of the composition (D) is used. Alternatively, the gloss of the film surface can be reduced by embossing the obtained film.

The multilayer structure polymer particles (B) contained in the methacrylic resin mixture (C) used in the present invention and the methacrylic multilayer structure polymer particles (B ₀ ) contained in the resin composition (D) are respectively Since it is a multilayer particle having a acrylate-based crosslinked elastic particle (B-1) as a core and a multilayer particle having a methacrylic multilayer structure polymer particle (B ₀ -1) as a core, it has moderate elasticity. As a result, the moldability in the case of preparing a molded body using the methacrylic resin mixture (C) and the resin composition (D) is excellent. For example, as mentioned above, when preparing a film, it is excellent in the moldability at the time of film preparation, and is excellent in the bending cracking resistance of the obtained film.

  The film laminate of the present invention is a colored film for retroreflective materials such as road signs and truck tapes; a colored film used as an alternative to painting of automobile interior materials, automobile exterior materials, etc .; window frames, bathroom equipment, wallpaper, It can be used as a colored film for building materials such as flooring materials; a household sundries, a housing for furniture and electrical equipment, a housing for office equipment such as a facsimile machine, and a colored film used for parts of electrical or electronic devices. Laminates containing this film include lighting lenses, automobile headlights, optical lenses, optical fibers, optical disks, liquid crystal light guide plates, liquid crystal films, medical products that require sterilization, microwave cooking containers, and home appliances. A housing, toy or recreational product.

  The present invention will be described in more detail based on examples, but the present invention is not limited to only these examples.

  The abbreviations used in the following production examples, examples, and comparative examples represent the following substances, respectively.

BA: butyl acrylate MMA: methyl methacrylate LP: lauroyl peroxide CHP: cumene hydroperoxide tDM: tertiary decyl mercaptan AlMA: allyl methacrylate ODB: orthodichlorobenzene (Production Example 1) Reactive anthraquinone compound (1) Production (Production Example 1.1) Synthesis of N- (10-methacryldecanoyl) -1,4-anthraquinone dicarboxylimide (1.1)

８０℃の硫酸（１１．７ｇ）中に１，４−ジアミノ−２，３−ジシアノアントラキノン（２．３０ｇ，８．０ｍｍｏ１）を加えた。この混合物を１４０−１５０℃ で１時間攪拌し、その後４０℃まで冷却した。氷水を徐々に加え、室温まで冷却した。炭酸ナトリウムで中和後、沈殿をろ過し、水とアセトンで洗浄すると、（３）が得られた（２．３７ｇ，収率９６％）。

1,4-Diamino-2,3-dicyanoanthraquinone (2.30 g, 8.0 mmol) was added to sulfuric acid (11.7 g) at 80 ° C. The mixture was stirred at 140-150 ° C for 1 hour and then cooled to 40 ° C. Ice water was gradually added and cooled to room temperature. After neutralizing with sodium carbonate, the precipitate was filtered and washed with water and acetone to obtain (3) (2.37 g, yield 96%).

(Production Example 1.2) Synthesis of t-butyldimethylsilyl bromodecanyl ether (4)
To a solution of 10-bromodecanol (2.03 g, 8.6 mmol) in methylene chloride (17 ml), triethylamine (1.04 g, 10.3 mmol), N, N-dimethylaminopyridine (58 mg, 0.4 mmol), and t-Butyldimethylchlorosilane (1.43 g, 9.5 mmol) was added at room temperature with stirring. The mixture was stirred at this temperature for 3 hours. The extract was washed with a saturated aqueous solution of ammonium chloride, a saturated aqueous solution of sodium hydrogen carbonate, and a saturated saline solution, and then dried over sodium sulfate. After the solvent was distilled off, the target t-butyldimethylsilyl bromodecanyl ether (4) was obtained (2.85 g, crude yield 94%).
(Production Example 1.3) Synthesis of N- (Ot-butyldimethylsilyl) -decanoyl-1,4-diamino-2,3-anthraquinone dicarboxylimide (5) 1,4-diamino-2,3- To a solution of anthraquinone dicarboxylimide (3) (1.54 g, 5.0 mmol) in THF (17 ml), potassium t-butoxide (0.67 g, 6.0 mmol) was gradually added at room temperature with stirring. After adding tetrabutylphosphonium bromide (0.17 g, 0.50 mmol), the mixture was stirred for an additional 30 minutes. Thereafter, a solution of t-butyldimethylsilyl bromodecanyl ether (4) (2.28 g, 6.5 mmol) in THF (3 ml) was added with stirring. The mixture was stirred at 55-60 ° C. for an additional 10 hours. After cooling, it was diluted with methylene chloride and water was added. The insoluble material was filtered through silica gel, and the organic layer was washed with saturated brine and dried over sodium sulfate. After distilling off the solvent, the residue was purified by column chromatography (CH ₂ Cl ₂ ), and N- (Ot-butyldimethylsilyl) -decanoyl-1,4-diamino-2,3-anthraquinone dicarboxylimide (5 ) Was obtained (2.05 g, 71% yield).

(Production Example 1.4) Synthesis of N-decanoyl-1,4-diamino-2,3-anthraquinone dicarboxylimide (6) N- (Ot-butyldimethylsilyl) -decanoyl-1,4-diamino- Acetic acid (0.13 g, 2.16 mmol) was added to a THF (2 ml) solution of 2,3-anthraquinone dicarboxylimide (5) (0.21 g, 0.36 mmol). While stirring, 1M tetrabutylammonium fluoride in THF (1 ml, 1.08 mmol) was added and the mixture was stirred at room temperature for 10 hours. Saturated aqueous sodium hydrogen carbonate solution was added to extract methylene chloride. The organic layer was separated, washed with a saturated aqueous sodium chloride solution, and dried over sodium sulfate. After distilling off the solvent, the residue was purified by column chromatography (CH ₂ Cl ₂ / AcOEt (2/1)) to obtain N-decanoyl-1,4-diamino-2,3-anthraquinone dicarboxylimide (6). (0.11 g, yield = 66%).

(Production Example 1.5) Synthesis of N- (10-methacryldecanoyl) -1,4-anthraquinone dicarboxylimide (1.1) Dicarboxylimide (6) (0.34 g, 0.73 mmol) in methylene chloride To the solution (10 ml) was added triethylamine (0.15 g, 1.46 mmol). To this solution was slowly added methacryloyl chloride (0.11 g, 1.10 mmol) at 10 ° C. or lower and the mixture was stirred at room temperature for 2 hours. Then, triethylamine (0.15 g, 1.46 mmol) and methacryloyl chloride (0.15 g, 1.46 mmol) were added, and the mixture was further stirred for 3 hours. After the reaction, a saturated aqueous sodium hydrogen carbonate solution was added and washed. Then, it dried with sodium sulfate. After removing the solvent, the residue was purified by column chromatography to obtain the target compound (1.1) (0.19 g, yield 49%).
(Production Example 2) Synthesis of N- (12-methacryldecanoyl) -1,4-anthraquinone dicarboximide (1.2) Instead of 10-bromodecanol used in Production Example 1.2, 12-bromo The anthraquinone derivative (1.2) was synthesized by the same method as the method for synthesizing the anthraquinone derivative (1.1) except that dodecanol was used.
The ultraviolet absorber (2.1) used in Example 1 is represented by the following structural formula.

ここでＸはＨであり、Ｒ₁はＨであり、Ｒ₂はn＝２のアルキル鎖であり、Ｒ₃はメチル基である。

Here, X is H, R ₁ is H, R ₂ is an alkyl chain of n = 2, and R ₃ is a methyl group.

(Example 1: Production of methacrylic acid ester polymer (A.1) by suspension polymerization)
In a 1 L polymerization reaction vessel equipped with a stirrer, 100 parts by mass of deionized water, 0.05 part by mass of sodium α-olefin sulfonate, and 0.5 part by mass of tribasic calcium phosphate were charged. Next, the inside of the polymerization reaction vessel was sufficiently replaced with nitrogen gas so that oxygen was not substantially present. Next, tDM 0.2 parts by mass, LP 0.2 parts by mass with respect to 100 parts by mass of the monomer mixture shown in Table 1 (methacrylic monomer (i) composed of 10% by mass BA and 90% by mass MMA) And a monomer mixture comprising 1 part by mass of the anthraquinone derivative (1.1) obtained in Production Example 1 and 1 part by mass of the ultraviolet absorber (2.1) were added at once. Next, the inside of the polymerization reaction vessel was kept at 80 ° C. and reacted for 2.5 hours in a nitrogen atmosphere to obtain a slurry containing a methacrylic ester polymer (A.1). The polymerization conversion rate was 98.4%. The polymerization conversion rate was calculated from the following equation by drying the obtained slurry at 120 ° C. for 1 hour with a hot air dryer, obtaining the mass of the obtained solid content.

Polymerization conversion rate (%) = (mass of solid content / mass of raw material monomer) × 100
The slurry was dehydrated, washed with water, and dried to obtain polymer (A.1) beads (particle size: about 1.3 mm).
It was verified whether or not the anthraquinone derivative was copolymerized in the obtained polymer (A.1).
The polymer (A.1) was dissolved in methyl ethyl ketone, and the solution was concentrated and added to ether or methanol, whereby a fractionation operation for separating the polymer and the unreacted residual anthraquinone derivative (1.1) was performed. Using the resin (A.1-1) obtained after the fractionation operation, spectroscopic analysis (Hitachi U3010) was performed to verify how much the colorant was copolymerized by the absorbance.
As a result, it was found that 90% of the charged amount of anthraquinone derivative was copolymerized. Thus, the obtained polymer (A.1) is an anthraquinone derivative (1.1).
It can be seen that the polymer contains as a copolymerization component.

Anthraquinone derivative introduction rate (%) = (absorbance of visible light absorption maximum of resin A.1-1 after fractionation operation / absorbance of visible light absorption maximum of resin A.1 before fractionation operation) × 100
(Example 2)
A methacrylic ester-based polymer was prepared by the same procedure as in Example 1 except that the anthraquinone derivative (1.2) was used without using the anthraquinone derivative (1.1) used in Example 1. 2) Obtained at a polymerization conversion of 97.2%. The anthraquinone derivative introduction rate was 97.5 (%).

(Example 3)
A methacrylic ester polymer in the same procedure as in Example 1 except that the amount of each of the anthraquinone derivative (1.1) and the ultraviolet absorber (2.1) used in Example 1 was 5 parts by mass. Beads of (A.3) were obtained. The anthraquinone derivative introduction rate was 90.0 (%).

Example 4
A bead of a methacrylic acid ester polymer (A.4) was obtained in the same procedure as in Example 1 except that the ultraviolet absorbent (2.1) used in Example 1 was not used.

(Example 5)
Instead of the methacrylic monomer (i) used in Example 1, the reaction was carried out in the same procedure as in Example 1 except that an ester mixture composed of 30% by mass of BA and 70% by mass of MMA was used. As a result, a methacrylic ester polymer (A.5) was obtained at a polymerization conversion rate of 95.0 (%).

(Example 6)
Instead of the methacrylic monomer (i) used in Example 1, the reaction was carried out in the same procedure as in Example 1 except that an ester mixture composed of 40% by mass of BA and 60% by mass of MMA was used. As a result, a methacrylic ester polymer (A.6) was obtained at a polymerization conversion rate of 92.5 (%).

(Comparative Example 1)
Instead of the anthraquinone derivative (1.1) used in Example 1, a non-polymerizable dye N-methoxypropyl-1,4-anthraquinone dicarboximide (7) (Plast Blue DB-367): Existence Polymer (A′1) beads were obtained in the same procedure as in Example 1 except that 1 part by mass of (manufactured by Hon Chemical Co., Ltd.) was used. When the obtained polymer was subjected to the fractionation operation performed in Example 1, all of the colorant was released from the resin, and a colorless and transparent polymer (A′1-1) was obtained. From this, it was found that the dye was not copolymerized with the resin because a dye having no polymerizability was used.

（比較例２）
実施例１で用いたアントラキノン誘導体（１．１）の量を５５質量部としたこと以外は、実施例１と同様の手順で反応を行った。しかし、反応溶液中に凝集物が生じたために、重合体ビーズは得られなかった。

(Comparative Example 2)
The reaction was performed in the same procedure as in Example 1 except that the amount of the anthraquinone derivative (1.1) used in Example 1 was 55 parts by mass. However, polymer beads were not obtained due to the formation of aggregates in the reaction solution.

(Comparative Example 3)
A bead of a methacrylic ester polymer (A′2) was obtained in the same procedure as in Comparative Example 1 except that the ultraviolet absorbent (2.1) used in Comparative Example 1 was not used. When the obtained polymer was subjected to the fractionation operation performed in Example 1, all of the colorant was released from the resin, and a colorless and transparent polymer (A′2-1) was obtained. From this, it was found that the dye was not copolymerized with the resin because a dye having no polymerizability was used.

実施例１〜６で得られた重合体ビーズ中に、上記アントラキノン誘導体が共重合されているか否かを検証した。また比較例１および３で用いた着色剤が樹脂に共重合されていないことを確認した。
重合体（Ａ．１）をメチルエチルケトンに溶解し、その溶液を濃縮してエーテルまたはメタノールに加えることで、重合体と未反応残存アントラキノン誘導体（１．１）を分離する分別操作を行った。分別操作後に得られた樹脂を用いて分光分析を行い、その吸光度で着色剤がどれだけ共重合されたかを検証した。
その結果、仕込み量の９０％のアントラキノン誘導体が、共重合されていることがわかった。このように、得られた重合体（Ａ．１）は、アントラキノン誘導体（１．１）を共重合成分として含有する重合体であることがわかる。

It was verified whether or not the anthraquinone derivative was copolymerized in the polymer beads obtained in Examples 1 to 6. It was also confirmed that the colorant used in Comparative Examples 1 and 3 was not copolymerized with the resin.
The polymer (A.1) was dissolved in methyl ethyl ketone, and the solution was concentrated and added to ether or methanol, whereby a fractionation operation for separating the polymer and the unreacted residual anthraquinone derivative (1.1) was performed. Spectroscopic analysis was performed using the resin obtained after the fractionation operation, and it was verified how much the colorant was copolymerized by the absorbance.
As a result, it was found that 90% of the charged amount of anthraquinone derivative was copolymerized. Thus, it turns out that the obtained polymer (A.1) is a polymer containing an anthraquinone derivative (1.1) as a copolymerization component.

(Example 7: Production of methacrylic resin mixture (C.1) by emulsion polymerization)
In an 8L polymerization reaction vessel with a stirrer, 200 parts by mass of deionized water, 0.25 parts by mass of sodium dioctylsulfosuccinate, 0.15 parts by mass of sodium formaldehyde sulfoxylate, 0.001 part by mass of ethylenediaminetetraacetate-2-sodium, And 0.00025 parts by mass of ferrous sulfate were charged. Next, the inside of the polymerization reaction vessel was sufficiently replaced with nitrogen gas so that oxygen was not substantially present.

  Separately from this, an acrylic monomer mixture was obtained by adding 0.5 parts by mass of AlMA and 0.2 parts by mass of CHP to 100 parts by mass of an acrylic monomer comprising 90% by mass of BA and 10% by mass of MMA. 30 parts by mass of this monomer mixture, 0.6 part by mass of the anthraquinone derivative (1.1) and 0.3 part by mass of the ultraviolet absorber (2.1) were mixed to obtain a mixture of 30.9 parts by mass.

  The inside of the polymerization reaction vessel is kept at 60 ° C., and a mixture (30.9 parts by mass) containing the anthraquinone derivative (1.1) is continuously added to the reaction vessel at a rate of 10 parts by mass / hour. did. After completion of the addition, the reaction was further carried out for 0.5 hours to obtain a reaction liquid (latex) containing acrylic ester-based crosslinked elastic particles (B-1.1). When this latex was used and the polymerization conversion rate was measured in the same manner as in Example 1, it was 99.0%.

  Further, separately from the above, a methacrylic monomer mixture is obtained by adding 0.5 parts by mass of tBM and 0.5 parts by mass of CHP to 100 parts by mass of methacrylic monomer consisting of 90% by mass of MMA and 10% by mass of BA. It was. 70 parts by mass of this monomer mixture, 1.4 parts by mass of an anthraquinone derivative (1.1) and 0.7 parts by mass of the ultraviolet absorber (2.1) were mixed to obtain a mixture of 72.1 parts by mass.

  Next, 0.05 parts by mass of sodium dioctylsulfosuccinate was charged into the reaction liquid containing the acrylic ester-based crosslinked elastic particles (B-1.1). The polymerization reaction vessel was maintained at 60 ° C., and a mixture (72.1 parts by mass) containing the anthraquinone derivative (1.1) was continuously added at a rate of 10 parts by mass / hour in a nitrogen atmosphere. . After completion of the addition, the reaction was further continued for 1 hour to obtain a reaction solution (latex) containing the multilayer structure polymer particles (B.1) and the methacrylic ester polymer (C-1.1). When this latex was used and the polymerization conversion rate was measured in the same manner as in Example 1, it was 95.0%. The obtained latex was salted out and coagulated with calcium chloride, washed with water and dried to obtain a powdery methacrylic resin mixture (C.1). The introduction rate of the anthraquinone derivative was 90.5%.

(Example 8)
A methacrylic resin mixture (C.2) was obtained in the same procedure as in Example 7 except that no ultraviolet absorber used in Example 7 was used. The polymerization conversion rate was 98.1%. The introduction rate of the anthraquinone derivative was 91.0%.

Example 9
Except that the anthraquinone derivative (1.1) and the ultraviolet absorber (2.1) used in Example 7 were not used, the same procedure as in Example 7 was followed, and methacrylic multilayer structure polymer particles ( to give B ₀ .1) methacrylic ester polymer (C-3.1) and powdery methacrylic resin mixture containing a (E.1). The polymerization conversion rate was 97.0%.
The resulting methacrylic resin mixture (E.1) was used in subsequent experiments to adjust the concentration of the colorant in the resin containing the colorant.

(Comparative Example 4)
Example except that the non-polymerizable dye N-methoxypropyl-1,4-anthraquinone dicarboximide (7) was used instead of the anthraquinone derivative (1.1) used in Example 7. The same procedure as in Example 7 was performed to obtain a powdery methacrylic resin mixture (C.3). The polymerization conversion rate was 95.8%. When the fractionation operation performed in Example 1 was performed on the obtained (C.3), all the colorant was released from the resin, and a colorless and transparent polymer (C.3-1) was obtained. From this, it was found that the dye was not copolymerized with the resin because a dye having no polymerizability was used.

(Comparative Example 5)
As shown in Table 2, a powdery methacrylic resin mixture (C.4) was obtained in the same procedure as in Comparative Example 4 except that no ultraviolet absorber used in Comparative Example 4 was used. The polymerization conversion rate was 97.0%. When the fractionation operation performed in Example 1 was performed on the obtained (C.4), all the colorants were released from the resin, and a colorless and transparent polymer (C4-1) was obtained. From this, it was found that the dye was not copolymerized with the resin because a dye having no polymerizability was used.

（実施例１０：フィルムの製造）
実施例９で得られたメタクリル系樹脂混合物（Ｅ．１）１００質量部と実施例１で得られた重合体（Ａ．１）ビーズ７５質量部とを、１分間ハンドブレンドした。得られた混合物をプレス機（神藤金属工業所製：シントーＦ型）にかけ、１９０℃、５０ｋｇ／ｃｍ²加圧に設定して、厚み１００μｍのフィルムを得た。

(Example 10: Production of film)
100 parts by mass of the methacrylic resin mixture (E.1) obtained in Example 9 and 75 parts by mass of the polymer (A.1) beads obtained in Example 1 were hand-blended for 1 minute. The obtained mixture was applied to a press machine (Shinto Metal Industries, Shinto F type) and set to 190 ° C. and 50 kg / cm ² pressure to obtain a film having a thickness of 100 μm.

  About the obtained film, (a) transparency, (b) bending cracking resistance, (c) bleedability of the colorant, (d) coloring durability and (e) weather resistance were evaluated by the following methods. The results are shown in Table 3.

(A) Evaluation of transparency Haze was measured under the conditions of a temperature of 23 ° C. ± 2 ° C. and a humidity of 50% ± 5% according to JIS K 7361-1.

(B) Evaluation of bending crack resistance The film was bent once by 180 degrees, and the change of the bent portion was visually evaluated at n = 5.

  ○: No cracks are observed in all.

  (Triangle | delta): A crack is recognized or not recognized.

  X: Cracks are observed in all.

(C) Evaluation of bleedability of colorant At the time of film forming, the adhesion of the colorant to the press plate was observed and evaluated according to the following criteria.

  ○: Adhesion of colorant to the press plate is not recognized.

  Δ: Adherence of the colorant to the press plate is observed, but adhering as compared to the case where N-octadodecyl-benzo [k, l] anthraquinone-3,4-dicarboxylimide (7) is used as the colorant. The amount is reduced.

  X: Adhesion of the colorant to the press plate is observed.

(D) Evaluation of coloring durability According to JIS A 1415, an accelerated weather resistance test was performed based on the following conditions.

<Accelerated weathering test method>
Type of testing equipment: Equipment using WS type sunshine carbon arc tester Testing machine: Sunshine weather meter made by Suga Test Equipment
WEL-SUN-DCH-B type Test conditions: Black panel temperature; 63 ° C
There is rain (spray 12 minutes out of 60 minutes)
Irradiance: 30W / m2
The color persistence of the film after exposure for 1000 hours was judged from visual confirmation.

    ○: It has coloring property.

    ×: Fading

(Examples 11 to 17)
A film was obtained in the same procedure as in Example 10 except that each raw material shown in Table 3 was used in the ratio shown in Table 3. About the obtained film, (a) Transparency, (b) Bending cracking resistance, (c) Bleeding property of coloring agent, (d) Coloring durability and (e) Weather resistance were evaluated in the same manner as in Example 10. did. The results are shown in Table 3.
In Examples 10, 12 and 19, since the amount of the crosslinked elastic body contained is small, the bending cracking resistance is evaluated as Δ, but the weather resistance is good because a reactive colorant is used.
In Examples 11 and 13 to 16, since a cross-linked elastic body is contained, the bending cracking resistance is good, and since the reactive colorant is used, the weather resistance is also good.

(Comparative Examples 6-7)
A film was obtained in the same procedure as in Example 10 except that each raw material shown in Table 3 was used in the ratio shown in Table 3. About the obtained film, (a) Transparency, (b) Bending cracking resistance, (c) Bleeding property of coloring agent, (d) Coloring durability and (e) Weather resistance were evaluated in the same manner as in Example 10. did. The results are shown in Table 3.
In Comparative Example 6, since the additive type colorant is used without using the reactive colorant, the bleedability, color persistence and weather resistance of the colorant are poor.
In Comparative Example 7, since no colorant is used, bleeding of the colorant does not occur, but weather resistance is not good because no ultraviolet absorber is added.
In Comparative Example 8, a reactive colorant is not used, but an additive type colorant is used, so that the colorant has poor bleeding properties, color persistence and weather resistance. Further, since the amount of the crosslinked elastic body is small, the bending crack resistance is not good.

表３に示すように、本発明のフィルムは、着色剤がブリードアウトせず、透明性、耐折曲げ割れ性、着色持続性および耐候性に優れていることがわかる。
（e）耐候性
得られたフィルムを耐候性試験機により、以下の条件でフィルムのヘイズ（ΔＥ）の変化をしらべることにより耐候性を評価した。結果を表３に示した。
（耐候性評価条件）
試験機：高照度キセノン（スガ試験機（株）製、SC750-WA型）
ブラックパネル温度：８９℃
照射エネルギー：１６２Ｗ/ｍ²(２８０〜４００ｎｍ)、１，５３０Ｗ/ｍ²（２８０〜８００ｎｍ）
表３に示すように本発明のフィルムは反応性ではない着色剤を用いたものに比べ、耐候性が優れていることがわかる。

As shown in Table 3, it can be seen that in the film of the present invention, the colorant does not bleed out, and is excellent in transparency, bending cracking resistance, coloring durability and weather resistance.
(E) Weather resistance The weather resistance of the obtained film was evaluated by examining changes in the haze (ΔE) of the film under the following conditions using a weather resistance tester. The results are shown in Table 3.
(Weather resistance evaluation conditions)
Testing machine: High illuminance xenon (manufactured by Suga Test Instruments Co., Ltd., SC750-WA type)
Black panel temperature: 89 ° C
Irradiation ^{energy: 162W / m 2 (280~400nm)} , 1,530W / m 2 (280~800nm)
As shown in Table 3, it can be seen that the film of the present invention is superior in weather resistance compared to a film using a non-reactive colorant.

  According to the present invention, there are provided a novel reactive anthraquinone compound and an acrylic copolymer of an ultraviolet absorber having both good copolymerizability for vinyl monomers and excellent coloring properties. The polymer obtained by subjecting this reactive anthraquinone compound and ultraviolet absorber to a vinyl monomer in the polymerization reaction is excellent in transparency, bending cracking resistance, and color persistence, and colorant bleed-out occurs. Absent.

  Films using this polymer are used in various fields. For example, colored films for retroreflective materials such as road signs and truck tapes; colored films used as substitutes for paints such as automotive interior materials and automotive exterior materials; for building materials such as window frames, bathroom equipment, wallpaper, and flooring materials It can be used as a colored film used for daily miscellaneous goods, a housing for furniture or electrical equipment, a housing for office equipment such as a facsimile machine, or a part of an electrical or electronic device. Laminates containing this film are illumination lenses, automotive headlights, optical lenses, optical fibers, optical disks, liquid crystal light guide plates, liquid crystal films, medical supplies that require sterilization, microwave oven cooking containers, and housings for home appliances. Used for toys or recreational products.

Claims (16)

Methacrylic acid ester polymer (A) obtained by subjecting the reactive anthraquinone compound represented by the general formula (1) and the methacrylic monomer (i) to a polymerization reaction

Here, X is H or a methyl group, Y is — (CH ₂ ) _n —, and n is an integer of 2 to 16.   2. The methacrylic acid ester system according to claim 1, wherein the methacrylic monomer (i) is used in a proportion of 50 to 99.99 mass% and the reactive anthraquinone compound is 0.01 to 50 mass%. Polymer (A). In the polymerization reaction, the methacrylic monomer (i) is 50 to 99.99 mass%, the reactive anthraquinone compound is 0.01 to 50 mass%, and the ultraviolet absorber represented by the general formula (2) is 0. The methacrylic ester polymer (A) according to claim 1, wherein the methacrylic acid ester polymer (A) is used in a ratio of 0.01 to 30% by mass.

X is H or halogen, R ₁ is H, a methyl group or a t-alkyl group having 4 to 6 carbon atoms, R ₂ is a linear or branched alkylene group having 2 to 10 carbon atoms, R ₃ is H or methyl It is a group.   The methacrylic acid ester polymer (A) according to any one of claims 1 to 3, wherein the proportion of the methacrylic acid alkyl ester in the entire methacrylic monomer (i) is 50% by mass or more. ).   The methacrylic acid monomer (i) is a mixed monomer containing a methacrylic acid alkyl ester and an acrylic acid alkyl ester, or a methacrylic acid alkyl ester. Combined (A). Multilayer structure polymer particles (B) having acrylic ester-based crosslinked elastic particles as a core and a layer made of a methacrylate ester polymer as an outer layer, and a methacrylic resin mixture (C) containing a methacrylate ester-based polymer ) And
The mixture (C) is obtained by polymerizing the methacrylic monomer (i) in the presence of the acrylic ester-based crosslinked elastic particles.
The acrylic ester-based crosslinked elastic particles are obtained by polymerizing a polyfunctional monomer having two or more non-conjugated double bonds in one molecule and an acrylic monomer (ii),
The acrylic monomer (ii) contains an acrylic acid alkyl ester in a proportion of 50% by mass or more,
The methacrylic monomer (i) contains a methacrylic acid alkyl ester in a proportion of 50% by mass or more,
In at least one of a polymerization reaction step for preparing the acrylic ester-based crosslinked elastic particles and a polymerization reaction step of the methacrylic monomer (i) in the presence of the crosslinked elastic particles, A reactive anthraquinone compound represented by the general formula (1) is added,
Acrylic polymer used for the polymerization reaction for the preparation of the acrylic ester-based crosslinked elastic particles and / or the polymerization reaction of the methacrylic monomer (i) in the presence of the acrylic ester-based crosslinked elastic particles The total amount of the anthraquinone compound used in the polymerization reaction for obtaining the monomer (ii) and the methacrylic monomer (i) in a total amount of 70 to 99.99% by mass and the methacrylic resin mixture (C) Is a methacrylic resin mixture (C) used at a ratio of 0.01 to 30% by mass. In at least one of a polymerization reaction step for preparing the acrylic ester-based crosslinked elastic particles and a polymerization reaction step of the methacrylic monomer (i) in the presence of the crosslinked elastic particles, Furthermore, an ultraviolet absorber (2) is added,
Acrylic polymer used for the polymerization reaction for the preparation of the acrylic ester-based crosslinked elastic particles and / or the polymerization reaction of the methacrylic monomer (i) in the presence of the acrylic ester-based crosslinked elastic particles The total amount of the anthraquinone compound used in the polymerization reaction for obtaining the monomer (ii) and the methacrylic monomer (i) in a total amount of 70 to 99.99% by mass and the methacrylic resin mixture (C) Is a methacrylic resin mixture (C) according to claim 6, wherein 0.01 to 30% by mass and an ultraviolet absorber is used in a proportion of 0.01 to 30% by mass.   The methacrylic resin mixture according to claim 6 or 7, wherein the acrylic monomer (ii) is a mixed monomer containing an acrylic acid alkyl ester and a methacrylic acid alkyl ester, or an acrylic acid alkyl ester. C).   The methacrylic monomer according to any one of claims 6 to 8, wherein the methacrylic monomer (i) is a mixed monomer containing a methacrylic acid alkyl ester and an acrylic acid alkyl ester, or a methacrylic acid alkyl ester. Resin mixture (C). A methacrylic resin composition comprising at least one of the methacrylic acid ester polymer (A) according to claim 1 and the methacrylic resin mixture (C) according to claim 6 and a methacrylic resin mixture (E). D),
The methacrylic resin mixture (E) is a multilayer structure polymer particle (B ₀ ) having an acrylic ester-based crosslinked elastic particle as a core and a layer made of a methacrylate ester-based polymer as an outer layer, and a methacrylate ester-based Containing a polymer,
The methacrylic resin mixture (E) is obtained by polymerizing the methacrylic monomer (i) in the presence of the acrylic ester-based crosslinked elastic particles,
The acrylic ester-based crosslinked elastic particles are obtained by polymerizing a polyfunctional monomer having two or more non-conjugated double bonds in one molecule and an acrylic monomer (ii),
The acrylic monomer (ii) contains an acrylic acid alkyl ester in a proportion of 50% by mass or more,
The methacrylic monomer (i) contains a methacrylic acid alkyl ester in a proportion of 50% by mass or more,
At least one of the methacrylic ester polymer (A) and the methacrylic resin mixture (C) is contained at a ratio of 0.1 to 200 parts by mass with respect to 100 parts by mass of the methacrylic resin mixture (E). A methacrylic resin composition (D).   The resin composition (D) according to claim 10, wherein the acrylic monomer (ii) is a mixed monomer containing an acrylic acid alkyl ester and a methacrylic acid alkyl ester, or an acrylic acid alkyl ester.   The resin composition (D) according to claim 10 or 11, wherein the methacrylic monomer (i) is a mixed monomer containing a methacrylic acid alkyl ester and an acrylic acid alkyl ester, or a methacrylic acid alkyl ester. ).   A film obtained by molding the methacrylic ester polymer (A) according to claim 1.   A film obtained by molding the methacrylic resin mixture (C) according to claim 6.   The film obtained by shape | molding the resin composition (D) of Claim 10.   A laminate comprising the film according to any one of claims 13 to 15 as at least one layer.