JP4847761B2 - Reactive anthraquinone compound and polymer using the same - Google Patents

Description

  The present invention relates to a reactive anthraquinone compound, an alcohol compound that can be used as a raw material for the reactive anthraquinone compound, a (meth) acrylic acid ester compound obtained from the alcohol compound, and the reactive anthraquinone compound. It relates to a manufacturing method. Furthermore, the present invention relates to a polymer obtained by using the reactive anthraquinone compound, a methacrylic resin mixture, and a methacrylic resin composition.

  Conventionally, acrylic resins have been used in various molded products by blending colorants such as dyes and pigments by utilizing their transparency. For example, used for various molded products in a wide range of fields such as lamp cases and covers, pachinko parts, retroreflective sheets (used for road signs for road safety, poles, etc.), housings for various electrical products, etc. Has been. 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 4). 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 the reaction of a vinylsulfone type reactive dye or a dichlorotriazine type reactive dye with a reactive non-crosslinked polymer, and Patent Documents 3 and 4 describe an anthraquinone dye having a reactive group or Copolymers of colorants and vinyl monomers are described. However, depending on the structure of the vinyl monomer used, copolymerization is low and it is difficult to form a copolymer, so that there is a problem that unreacted dye remains and bleeds out.

As a method for improving the color sustainability, Patent Document 5 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 Japanese Patent Laid-Open No. 9-272814 Japanese translation of PCT publication No. 2004-506064 JP 2004-75709 A

  An object of the present invention is to provide a novel 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 in. Another object of the present invention is to provide an acrylic polymer that is excellent in colorability, transparency, bending cracking resistance, and color sustainability, and that does not cause colorant bleeding out, using the reactive compound. There is to get. 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.

  The reactive anthraquinone compound of the present invention is represented by the following general formula (1):

Wherein X is H, Cl, or Br, Y is — (CH ₂ ) _n — or —CH ₂ CH ₂ (OCH ₂ CH ₂ ) _n —, R is H or a methyl group, and , N is an integer of 1 or more.

In one embodiment, the X is H or Cl, the Y is — (CH ₂ ) _n —, and the n is 4-16.

In one embodiment, the X is Cl, the Y is — (CH ₂ ) _n —, and the n is 12.

In one embodiment, X is H, Y is — (CH ₂ ) _n —, and n is 12.

In one embodiment, the X is H or Cl, the Y is —CH ₂ CH ₂ (OCH ₂ CH ₂ ) _n —, and the n is 1-4.

In one embodiment, X is H, Y is —CH ₂ CH ₂ (OCH ₂ CH ₂ ) _n —, and n is 2.

  The alcohol compound of the present invention is represented by the following general formula (2):

Here, X is H, Cl, or Br, Y is — (CH ₂ ) _n — or —CH ₂ CH ₂ (OCH ₂ CH ₂ ) _n —, and n is an integer of 1 or more. .

  The (meth) acrylic acid ester compound of the present invention is obtained from the above alcohol compound and (meth) acrylic acid or a derivative thereof, and is represented by the following general formula (3):

Wherein X is H, Cl, or Br, Y is — (CH ₂ ) _n — or —CH ₂ CH ₂ (OCH ₂ CH ₂ ) _n —, R is H or a methyl group, and , N is an integer of 1 or more.

  The method for producing a reactive anthraquinone compound of the present invention includes a step of reacting a (meth) acrylic acid ester compound with aminoanthraquinone.

  The methacrylic ester polymer (A) of the present invention is obtained by subjecting the reactive anthraquinone compound and the methacrylic monomer (i) to a polymerization reaction, and the methacrylic monomer (i) is: The methacrylic acid alkyl ester is contained in a proportion of 50% by mass or more, and in the polymerization reaction, the methacrylic monomer (i) is 50 to 99.99% by mass and the reactive anthraquinone compound is 0.01 to 50%. It is used at a rate of mass%.

  In one embodiment, 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.

  The methacrylic resin mixture (C) of the present invention comprises a multilayer structure polymer particle (B) 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 The mixture (C) is obtained by polymerizing the methacrylic monomer (i) in the presence of the acrylate-based crosslinked elastic particles; the acrylate-based crosslinked Elastic particles can be 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 ester-based crosslinked elastic particles and a polymerization reaction step of the methacrylic monomer (i) in the presence of the crosslinked elastic particles, The anthraquinone compound described in 1) is added; a polymerization reaction for the preparation of the acrylic ester-based crosslinked elastic particles and polymerization of the methacrylic monomer (i) in the presence of the acrylic ester-based crosslinked elastic particles Acrylic monomer (ii) and methacrylic monomer (i) used in the reaction are used in a polymerization reaction for obtaining 70 to 99.99% by mass in total amount and the methacrylic resin mixture (C). The total amount of the anthraquinone compound to be used is 0.01 to 30% by mass.

  In one embodiment, 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.

  In one embodiment, 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.

The methacrylic resin composition (D) of the present invention comprises at least one of the methacrylic ester polymer (A) and the methacrylic resin mixture (C), and the methacrylic resin mixture (E); -Based resin mixture (E) having multilayer structure polymer particles (B ₀ ) 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 methacrylate ester-based polymer The methacrylic resin mixture (E) is obtained by polymerizing the methacrylic monomer (i) in the presence of the acrylate-based crosslinked elastic particles; the acrylate-based crosslinked Elastic particles can be 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. ; With respect to 100 parts by mass of the methacrylic resin mixture (E), at least one of the methacrylic ester polymer (A) and the methacrylic resin mixture (C) is contained in a proportion of 0.1 to 200 parts by mass. The

  In one embodiment, 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.

  In one embodiment, 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.

  The film of the present invention is obtained by molding the methacrylic resin mixture (C).

  The film of the present invention is obtained by molding the resin composition (D).

  The laminate of the present invention contains any one of the above films as at least one layer.

  According to the present invention, a novel reactive anthraquinone compound is obtained. This compound has both good copolymerizability with respect to (meth) acrylic monomers such as alkyl acrylates and alkyl methacrylates, and vinyl monomers such as styrene, and excellent coloring properties. The present invention also provides a novel alcohol compound and acrylate ester compound, which are raw materials for the reactive anthraquinone compound, and a method for producing the reactive anthraquinone compound using these compounds. By reacting the reactive anthraquinone compound with another monomer, a polymer having a color tone derived from the anthraquinone compound can be obtained. In this colored polymer, bleeding out of the colored component is suppressed. Moreover, it is excellent in fading resistance.

  The methacrylic ester polymer of the present invention obtained by using the reactive anthraquinone compound, the methacrylic resin mixture, and the methacrylic resin composition containing at least one of them are used for preparing various molded articles. Preferably used. In particular, a film, a laminate including the film, and the like can be advantageously produced. These films and laminates have a color tone derived from a reactive anthraquinone compound, are excellent in fading resistance, and are excellent in impact resistance and folding crack resistance of the film.

  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 of the present invention is a compound represented by the following general formula (1) (hereinafter referred to as reactive anthraquinone compound (1), compound (1), etc.) Sometimes).

Wherein X is H, Cl, or Br, Y is — (CH ₂ ) _n — or —CH ₂ CH ₂ (OCH ₂ CH ₂ ) _n —, R is H or a methyl group, and , N is an integer of 1 or more.

  Of X in the general formula (1), H or Cl is preferable, and H is more preferable from the viewpoint of the cost and handleability of the reactive anthraquinone compound (1).

When Y in the general formula (1) is — (CH ₂ ) _n —, n is preferably 4 to 16. In this formula (1), CH ₂ ═CH (R) —CO— is derived from a (meth) acrylic monomer.

Examples of the group represented by CH ₂ ═CH (R) —CO—OY— when Y in the general formula (1) is — (CH ₂ ) _n — include a methyl methacrylate group and a methyl acrylate group. Group, ethyl methacrylate group, ethyl acrylate group, butyl methacrylate group, butyl acrylate group, hexyl methacrylate group, hexyl acrylate group, octyl methacrylate group, octyl methacrylate group, dodecyl methacrylate group, dodecyl acrylate group Group and the like. Among these, a dodecyl methacrylate group is preferable from the viewpoint of cost and handleability.

When Y in General Formula (1) is —CH ₂ CH ₂ (OCH ₂ CH ₂ ) _n —, n is preferably 1 to 4. In the general formula (1), when Y is —CH ₂ CH ₂ (OCH ₂ CH ₂ ) _n —, examples of the group represented by CH ₂ ═CH (R) —CO—OY— include methacrylic acid (2-ethoxy) ethyl group, acrylic acid (2-ethoxy) ethyl group, methacrylic acid (2- (2-ethoxy) ethoxy) ethyl group, acrylic acid (2- (2-ethoxy) ethoxy) ethyl group, methacrylic acid (2- (2- (2-ethoxy) ethoxy) ethoxy) ethyl group, acrylic acid (2- (2- (2-ethoxy) ethoxy) ethoxy) ethyl group, methacrylic acid (2- (2- (2- (2- ( Examples include 2-ethoxy) ethoxy) ethoxy) ethoxy) ethyl group and acrylic acid (2- (2- (2- (2-ethoxy) ethoxy) ethoxy) ethoxy) ethyl group). Among these, a methacrylic acid (2- (2-ethoxy) ethoxy) ethyl group is preferable from the viewpoint of cost and handleability.

  The reactive anthraquinone compound (1) is obtained by using, for example, an alcohol compound (2) described later to obtain an intermediate (meth) acrylic acid ester compound (3). It can be synthesized from anthraquinone (7).

  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.

(II) Alcohol compound The alcohol compound of the present invention is a compound represented by the following general formula (2). Hereinafter, this compound may be referred to as an alcohol compound (2).

Here, X is H, Cl, or Br, Y is — (CH ₂ ) _n — or —CH ₂ CH ₂ (OCH ₂ CH ₂ ) _n —, and n is an integer of 1 or more. .

  Examples of X, Y, and R in the general formula (2) include the same substituents as X, Y, and R in the structure of the reactive anthraquinone compound (1).

  The alcohol compound (2) of the present invention can be used as a raw material for obtaining a (meth) acrylic ester compound (3) described later, which is an intermediate for obtaining the reactive anthraquinone compound (1). .

  This alcohol compound (2) can be obtained, for example, by a reaction between a bromo-substituted phenol derivative (4) and a bromo-substituted alcohol derivative (5) as described later.

  In addition to the intermediate of the reactive anthraquinone compound (1), the alcohol compound (2) may be used as an intermediate for synthesizing compounds used in, for example, dyes, pigments, pharmaceuticals, cosmetics, and fragrances. Can be used.

(III) (Meth) acrylic acid ester compound The (meth) acrylic acid ester compound of the present invention is a compound represented by the following general formula (3) (hereinafter referred to as (meth) acrylic acid ester compound ( 3), sometimes referred to as compound (3), etc.).

Wherein X is H, Cl, or Br, Y is — (CH ₂ ) _n — or —CH ₂ CH ₂ (OCH ₂ CH ₂ ) _n —, R is H or a methyl group, and , N is an integer of 1 or more.

  Examples of X, Y, and R in the general formula (3) include the same substituents as X, Y, and R in the structure of the reactive anthraquinone compound (1).

  The (meth) acrylic acid ester compound (3) of the present invention is obtained by reacting the alcohol compound (2) with (meth) acrylic acid or a derivative thereof, as will be described later.

  The (meth) acrylic acid ester compound (3) of the present invention is used as an intermediate for synthesizing the reactive anthraquinone compound (1). In addition to the intermediate of the reactive anthraquinone compound (1), this compound can also be used as an intermediate for synthesizing compounds used in, for example, dyes, pigments, pharmaceuticals, cosmetics, and fragrances.

(IV) Production Method of Reactive Anthraquinone Compound (1) As described above, the reactive anthraquinone compound (1) of the present invention comprises the (meth) acrylic acid ester compound (3) and aminoanthraquinone (7). It is obtained by reacting. For example, as shown below, an alcohol compound (2) is synthesized to obtain a (meth) acrylic acid ester compound (3) from the alcohol compound (2). Compound (1) is obtained.

  (IV.1) Synthesis of alcohol compound (2)

  The alcohol compound (2) is obtained by subjecting the bromo-substituted phenol derivative (4) and the bromo-substituted alcohol derivative (5) to the reaction as described above.

  Examples of the bromo-substituted phenol derivative (4) include 4-bromo-2-chlorophenol, and commercially available products can be used.

  The bromo-substituted alcohol derivative (5) is an alcohol having a bromo substituent and having 1 or more carbon atoms. Examples include bromo-substituted alkyl alcohols, and examples thereof include bromomethyl alcohol, 2-bromo-1-ethyl alcohol, 4-bromo-1-butyl alcohol, 6-bromo-1-hexyl alcohol, 8-bromo. There are alcohols such as -1-octyl alcohol and 12-bromo-1-dodecyl alcohol. Among these, 12-bromo-1-dodecyl alcohol is preferable from the viewpoint of cost and handleability.

  This reaction is preferably performed in a solvent. Examples of the solvent include dimethylformamide (DMF), tetrahydrofuran (THF), methylene chloride, chloroform and the like.

  By performing this reaction in the presence of a substance having a dehydrating action such as potassium carbonate, the desired product can be obtained in a high yield.

  The reaction temperature is appropriately set depending on the solvent used, and is preferably 80 to 140 ° C, more preferably 100 to 120 ° C. The reaction time varies depending on the reaction temperature, and is preferably 6 to 12 hours, more preferably 8 to 10 hours.

  After completion of the reaction, the alcohol compound (2) is obtained by adding water to the reaction product, filtering, washing with water, and recrystallizing with methanol.

  (IV.2) Synthesis of (meth) acrylic acid ester compound (3)

  The (meth) acrylic acid ester compound (3) can be obtained by reacting the alcohol compound (2) with (meth) acrylic acid or a derivative thereof. Examples of (meth) acrylic acid or derivatives thereof include acrylic acid, methacrylic acid, acryloyl chloride, and methacryloyl chloride. For example, as in the above scheme, (meth) acryloyl chloride (6) is used. A commercially available product can be used as the (meth) acryloyl chloride (6).

  This reaction is preferably performed in a solvent. As a solvent, the solvent used for the synthesis | combination of the said alcohol type compound (2) is mentioned, for example. Further, a catalyst may be used. Examples of the catalyst include triethylamine, tributylamine, pyridine, paramethylpyridine, N, N-dimethylaminopyridine, 2,6-lutidine and the like.

  The reaction temperature is appropriately set depending on the type of chloride, solvent and catalyst used, and is preferably 0 to 30 ° C, more preferably 10 to 20 ° C. The reaction time varies depending on the reaction temperature, and is preferably 1 to 6 hours, more preferably 3 to 4 hours.

  After completion of the reaction, water is added to the reaction product, and the mixture is extracted with a solvent. Then, the (meth) acrylic acid ester compound (3) can be purified and isolated by an operation such as chromatography.

  (IV.3) Synthesis of reactive anthraquinone compound (1)

  The reactive anthraquinone compound (1) is obtained by subjecting the (meth) acrylic acid ester compound (3) and aminoanthraquinone (7) to a reaction.

  A commercially available product can be used as aminoanthraquinone (7).

  This reaction is preferably performed in a solvent. Examples of the solvent include orthodichlorobenzene (ODB), DMF, dimethyl sulfoxide (DMSO) and the like. Furthermore, a catalyst can also be used, and examples of the catalyst include copper.

  By performing this reaction in the presence of a dehydrating substance such as potassium carbonate, the target product can be obtained in high yield.

  The reaction temperature is appropriately set depending on the type of solvent and catalyst used, and is preferably 150 to 250 ° C, more preferably 180 to 220 ° C. The reaction time varies depending on the reaction temperature, and is preferably 1 to 4 hours, more preferably 2 to 3 hours.

  After completion of the reaction, the reaction product is added with a solvent, filtered and concentrated, and then the reactive anthraquinone compound (1) can be purified and isolated by an operation such as chromatography.

  The reactive anthraquinone compound (1) of the present invention can be used together with various reactive monomers, for example, (meth) acrylic monomers such as methacrylic acid alkyl esters and acrylic acid alkyl esters, and the compound (1). A polymer having a color derived from the compound (1) can be obtained by copolymerization with other polymerizable vinyl monomers (ethylenically unsaturated monomers). 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.

The following is a polymer derived from the reactive anthraquinone compound (1) (A ₀ ); a methacrylic acid ester polymer (A) as a representative example thereof; and a polymer derived from the reactive anthraquinone compound (1). The methacrylic resin mixture (C) containing the contained multilayer polymer particles and the methacrylic resin composition (D) will be described.

(V) Polymer (A ₀ )
The polymer (A ₀ ) of the present invention is obtained by reacting a reactive anthraquinone compound (1) with a monomer copolymerizable with the compound (1).

  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.

  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.

(VI) 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 said methacrylic monomer (i) which is a raw material of a methacrylic ester polymer (A) contains the methacrylic acid alkylester in the ratio of 50 mass% or more. Preferably, the methacrylic monomer (i) comprises 50% by mass or more of methacrylic acid alkyl ester, less than 50% by mass of acrylic acid alkyl ester, and 30% by mass or less of the ethylenically unsaturated monomer. Contains in proportions. More 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. Normally, the methacrylic monomer (i) 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. 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%. 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.

  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.

  Among the initiators, the organic peroxide is added to the polymerization system as it is; the raw material monomer (at least one of the reactive anthraquinone compound (1) and the methacrylic monomer (i)). It can be added by a usual addition method such as a method of mixing and adding to the polymerization system; a method of dispersing in an emulsifier aqueous 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.

(VII) 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 uses as a core and the layer which consists of a methacrylic ester polymer as an outer layer (B-2), and the methacrylic ester polymer (C-1) are contained. 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.

(VII-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 and further the reactive anthraquinone compound (1) if necessary.

  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).

(VII-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). 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 formation of the methacrylic monomer (i) and the reactive anthraquinone compound (1) in the presence of the core particles (B-1) Is done.

  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 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). (Through this process, particles with a three-layer structure are obtained, so four or more layers are listed separately). 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 methacrylic monomer (i) and a polymer derived from the 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.

(VIII) 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 acrylic ester-based crosslinked elastic particles (B ₀ -1) are used as a core and a layer made of a methacrylic ester-based polymer is used as 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 anthraquinone 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 particle (B ₀ -1), the methacrylic single-layered polymer particle (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 other than those described above.

  Examples of the additives include antioxidants, heat stabilizers, UV absorbers, UV stabilizers and the like that are used for the purpose of further improving the stability to heat and light, and antibacterial agents, deodorants, lubricants, and the like. is there. 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).

(IX) 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 equal to or 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 Example 1 of reactive anthraquinone compound (1) Preparation (Example 1.1) Synthesis of 12- (4′-bromo-2′-chloro) -phenoxide decanol

  4-Bromo-2-chlorophenol (37 g, 178 mmol); manufactured by Aldrich) and potassium carbonate (22.4 g) were added to DMF (110 ml), and the mixture was heated to 90 ° C. with stirring. Subsequently, 12-bromo-1-dodecanol (43 g, 152 mmol); manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was heated to 110 ° C. and stirred for 8 hours. After standing overnight, ice water (350 ml) was added to the reaction mixture, followed by filtration. The resulting residue was washed with water and then with methanol. Subsequently, recrystallization is performed with methanol (150 ml), and the precipitated crystals are separated by filtration, washed with cold methanol, and 12- (4′-bromo-2′-chloro) represented by the formula (2.1). -Phenoxide decanol was obtained (48.0 g, 76% yield).

  Example 1.2 Synthesis of 12- (4'-bromo-2'-chloro) -phenoxide decanyl methacrylate

  To THF (100 ml) was added 12- (4′-bromo-2′-chloro) -phenoxide decanol (2.1) (20 g, 51.1 mmol) obtained in Example 1.1 and triethylamine (7.7 g). And cooled to 4 ° C. with stirring. Next, methacryloyl chloride (6.4 g, 61.3 mmol; manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the temperature was raised to 20 ° C. and stirred for 4 hours. After standing overnight, ice water (400 ml) was added to the reaction mixture, and the mixture was extracted and separated with ethyl acetate. The resulting ethyl acetate layer was washed with a saturated aqueous sodium chloride solution, dehydrated and concentrated. After concentration, the residue was purified by silica gel chromatography using toluene to obtain 12- (4′-bromo-2′-chloro) -phenoxide decanyl methacrylate represented by the formula (3.1) (15.2 g). Yield 65%).

  Example 1.3 Synthesis of 1- {12 '-(4 "-N-2" -chloro) -phenoxide decanylmethacryl} -aminoanthraquinone

  To ODB (10 ml), 12- (4′-bromo-2′-chloro) -phenoxide decanyl methacrylate (3.1) (10 g, 21.7 mmol) obtained in Example 1.2, 1-aminoanthraquinone (4 g, 18.1 mmol; manufactured by Wako Pure Chemical Industries, Ltd.), potassium carbonate (3.8 g), and copper (3.8 g) were added, and the mixture was heated to 200 ° C. and stirred for 2 hours. Then, toluene (50 ml) was added to the reaction mixture, filtered, and the filtrate was concentrated. After concentration, the residue was purified by silica gel chromatography using toluene. Subsequently, toluene (40 ml) was added and recrystallization was performed with methanol (160 ml). The precipitated crystals were separated by filtration, washed with methanol, and 1- {12 ′-(4 ″ -N-2 ″ -chloro) -phenoxidedecanylmethacryl} -aminoanthraquinone (hereinafter referred to as the formula (1.1)). In some cases, it was referred to as “aminoanthraquinone derivative (1.1)”) (4.1 g, yield 38%).

(Example 2: Production of methacrylate polymer (A.1))
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 2 parts by mass of the aminoanthraquinone derivative (1.1) obtained in Example 1.3) 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 98.0%. 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 1.5 mm).

(Example 3)
A bead of a methacrylic ester polymer (A.2) was obtained in the same procedure as in Example 2, except that the amount of aminoanthraquinone derivative (1.1) used in Example 2 was 5 parts by mass. .

(Comparative Example 1)
Instead of the aminoanthraquinone derivative (1.1) used in Example 2, a dye represented by the following formula (8) having no polymerizability (1-phenylaminoanthraquinone (Plast Red 8350): Arimoto Polymer (A ′) beads were obtained in the same manner as in Example 2 except that Chemicals) was used.

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

(Comparative Example 3)
Instead of the methacrylic monomer (i) used in Example 2, the reaction was carried out in the same procedure as in Example 2 except that an ester mixture composed of 60% by mass of BA and 40% by mass of MMA was used. went. However, polymer beads were not obtained due to the formation of aggregates in the reaction solution.

  It was verified whether or not the aminoanthraquinone derivative was copolymerized in the polymer (A.1) beads obtained in Example 2.

  First, the polymer (A.1) beads were washed with acetone, and it was confirmed that the aminoanthraquinone derivative (1.1) as the colorant did not elute. Subsequently, the polymer (A.1) beads washed with acetone are subjected to TN analysis with a TN (trace total nitrogen) analyzer (manufactured by Mitsubishi Chemical Corporation, TN-110), and the nitrogen in the polymer (A.1) beads is analyzed. The content was measured. The content of aminoanthraquinone derivative (1.1) was calculated from the obtained measured value. As a result, it was found that 95% of the charged aminoanthraquinone derivative was copolymerized. Thus, it can be seen that the obtained polymer (A.1) is a polymer containing the aminoanthraquinone derivative (1.1) as a copolymerization component.

  On the other hand, when the polymer (A ′) beads obtained in Comparative Example 1 were washed with acetone, the dye was eluted. The nitrogen content of the polymer (A ′) beads after washing with acetone was measured and the content of the dye was calculated to be 0%. That is, it was found that all the dye was washed away with acetone because a dye having no polymerizability was used.

(Example 4: Production of methacrylic resin mixture (C.1))
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 and 0.6 parts by mass of aminoanthraquinone derivative (1.1) were mixed to obtain a mixture of 30.6 parts by mass.

  The polymerization reaction vessel was maintained at 60 ° C., and a mixture (30.6 parts by mass) containing the aminoanthraquinone derivative (1.1) was continuously added to the reaction vessel at a rate of 10 parts by mass / hour. Added. 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 2, 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 and 1.4 parts by mass of aminoanthraquinone derivative (1.1) were mixed to obtain a mixture of 71.4 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 kept at 60 ° C., and a mixture (71.4 parts by mass) containing the aminoanthraquinone derivative (1.1) was continuously added at a rate of 10 parts by mass / hour in a nitrogen atmosphere. did. 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 2, it was 97.5%. 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).

(Comparative Example 4)
The reaction was performed in the same procedure as in Example 4 except that the amount of aminoanthraquinone derivative (1.1) used in Example 4 was changed to the amount shown in Table 2 (total 35 parts by mass). However, a methacrylic resin mixture could not be obtained due to the formation of aggregates in the reaction solution.

(Comparative Example 5)
Except that the dye (1-phenylaminoanthraquinone) represented by the above formula (8) having no polymerizability was used instead of the aminoanthraquinone derivative (1.1) used in Example 4 The same procedure as in Example 4 was followed to obtain a powdery methacrylic resin mixture (C ′). The polymerization conversion rate was 96.0%.

(Production Example 1)
Except for not using the aminoanthraquinone derivative (1.1) used in Example 4, do the same procedure as in Example 2, a methacrylic acid methacrylic multi-layer polymer particles (B 0 _.1) A powdery methacrylic resin mixture (E.1) containing an ester polymer (C-2.1) was obtained. The polymerization conversion rate was 98.5%.

(Example 5: Production of film)
100 parts by mass of the methacrylic resin mixture (E.1) obtained in Production Example 1 and 75 parts by mass of the polymer (A.1) beads obtained in Example 2 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) Bleed property of a coloring agent, and (d) Coloring durability 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.
(Triangle | delta): Although adhesion of the coloring agent to a press board is recognized, compared with the case where 1-phenylamino anthraquinone is used as a coloring agent, the adhesion amount has decreased.
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 6 to 9)
A film was obtained in the same procedure as in Example 5 except that each raw material shown in Table 3 was used in the ratio shown in Table 3. About the obtained film, similarly to Example 5, (a) transparency, (b) resistance to bending cracking, (c) bleeding property of the coloring agent, and (d) coloring durability were evaluated. The results are shown in Table 3.

(Comparative Examples 6-8)
A film was obtained in the same procedure as in Example 5 except that each raw material shown in Table 3 was used in the ratio shown in Table 3. About the obtained film, similarly to Example 5, (a) transparency, (b) resistance to bending cracking, (c) bleeding property of the coloring agent, and (d) coloring durability were evaluated. The results are shown in Table 3.

  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, and color sustainability.

  ADVANTAGE OF THE INVENTION According to this invention, the novel reactive anthraquinone type compound which has the favorable copolymerizability with respect to a vinyl-type monomer and the outstanding coloring characteristic is provided. A polymer obtained by subjecting this reactive anthraquinone compound and a vinyl monomer to a polymerization reaction is excellent in transparency, bending cracking resistance, and coloring durability, and does not cause bleeding out of the colorant.

  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 (18)

Reactive anthraquinone compounds represented by the following general formula (1):

Wherein X is H, Cl, or Br, Y is — (CH ₂ ) _n — or —CH ₂ CH ₂ (OCH ₂ CH ₂ ) _n —, R is H or a methyl group, and , N is an integer of 1 or more. X is H or Cl, Y is - _{(CH 2) n} -, and, and, n is 4 to 16, reactive anthraquinone compound according to claim 1.   The reactive anthraquinone compound according to claim 2, wherein X is Cl, and n is 12.   The reactive anthraquinone compound according to claim 2, wherein X is H, and n is 12. X is H or Cl, Y is _{-CH 2 CH 2 (OCH 2 CH} 2) n - is and, n is 1 to 4, reactive anthraquinone compound according to claim 1.   The reactive anthraquinone compound according to claim 5, wherein X is H, and n is 2. The following general formula (3):

(Wherein X is H, Cl, or Br, Y is — (CH ₂ ) _n — or —CH ₂ CH ₂ (OCH ₂ CH ₂ ) _n —, R is H or a methyl group, N is an integer of 1 or more.)
The manufacturing method of the reactive anthraquinone type compound of any one of Claim 1 to 6 including the process with which the (meth) acrylic acid ester type compound represented by these and aminoanthraquinone are made to react. A methacrylic ester polymer (A) obtained by subjecting the reactive anthraquinone compound according to claim 1 and a methacrylic monomer (i) to a polymerization reaction,
The methacrylic monomer (i) contains a methacrylic acid alkyl ester in a proportion of 50% by mass or more, and in the polymerization reaction, the methacrylic monomer (i) is 50 to 99.99% by mass and the A reactive anthraquinone compound is used in a proportion of 0.01 to 50% by mass,
Polymer (A). The polymer (A) according to claim 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. 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, An anthraquinone compound according to claim 1 is added,
Acrylic monomer used for the polymerization reaction for the preparation of the acrylic ester-based crosslinked elastic particles and the polymerization reaction of the methacrylic monomer (i) in the presence of the acrylic ester-based crosslinked elastic particles ( ii) and methacrylic monomer (i) in a total amount of 70 to 99.99% by mass, and the total amount of anthraquinone compound used in the polymerization reaction for obtaining the methacrylic resin mixture (C) is 0.01 Used at a ratio of ˜30% by mass,
Methacrylic resin mixture (C). The methacrylic resin mixture (C) 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 methacrylic resin mixture (C) 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 methacrylic resin composition comprising at least one of the methacrylic ester polymer (A) according to claim 8 and the methacrylic resin mixture (C) according to claim 10 , 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 methacrylic 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 13 , 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 13 or 14 , 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 resin mixture (C) according to claim 10 . A film obtained by molding the resin composition (D) according to claim 13 . A laminate comprising the film according to claim 16 or 17 as at least one layer.