JP4923501B2 - Molded product comprising methacrylic resin composition - Google Patents

Description

The present invention relates to a molded article such as a film or sheet formed by molding a methacrylic resin having ultraviolet shielding performance.

  A methacrylic resin composition including a crosslinked elastic body excellent in transparency, weather resistance, hardness, and impact resistance is generally used by mixing an ultraviolet absorber. In particular, when used as a film, it is necessary to add a large amount of an ultraviolet absorber as the thickness of the film is reduced.

  However, general UV absorbers are poorly compatible with methacrylic resins and have a low molecular weight, so some of them volatilize during extrusion and cannot exhibit UV shielding performance. Due to the dissipation, there was a problem that the ultraviolet shielding performance deteriorated with time.

  In addition, when a film is formed by a method such as extrusion molding, problems such as clogging of the vent of the extruder, adhesion to the eyes of the T-die, and whitening of the cooling roll occur. Problems such as roughening and elution (bleed out) to the film surface occurred.

  In order to solve these problems, a method of selecting and adding a specific ultraviolet absorber is generally known. However, with the method of simply adding a specific UV absorber, the UV absorber added to the resulting film elutes (bleeds out) when immersed in warm water or when exposed outdoors, resulting in reduced UV shielding performance. Problems such as whitening could not be solved.

On the other hand, the method (patent documents 1-4) of copolymerizing the specific monomer which shows an ultraviolet absorptivity with respect to methacrylic resin is proposed. However, the films obtained by these methods are not satisfactory in bending crack resistance, moldability (thinning of the film), and the like.
JP-A-60-38411 JP-A-5-255447 JP-A-9-194542 JP-A-8-319326

  Therefore, a methacrylic resin composition capable of forming a film excellent in transparency, hardness, impact resistance, bending cracking resistance, moldability and weather resistance has been demanded.

  Therefore, as a result of intensive studies, the present inventors have determined that a specific compound comprising an acrylic ester-based crosslinked elastic particle copolymerized with a methacrylic ester-based polymer and a monomer having a specific chemical structural formula and an ultraviolet-absorbing property. A film obtained from a methacrylic resin composition having a layer structure and a particle size of 1 is excellent in transparency, hardness, impact resistance, bending crack resistance and moldability, and further bend crack resistance after a weather resistance test. And the present invention was found.

（式中、ＸはＨまたはハロゲン、Ｒ₁はＨ、メチルまたは炭素数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またはメチルである。）（請求項１）
アクリル酸エステル系架橋弾性体粒子（Ｂ）における多官能性単量体の添加量が、前記単量体混合物１００重量部に対して、０．０５〜２０重量部である請求項１に記載の共押出成形品（請求項２）、
アクリル酸エステル系架橋弾性体粒子（Ｂ）の平均粒子径が６００Å〜２５００Åである請求項１又は２に記載の共押出成形品（請求項３）、
請求項１〜３のいずれか１項に記載のメタクリル系樹脂（Ｃ）を４０重量％以上含むメタクリル系樹脂組成物を共押出しによって熱可塑性樹脂に積層してなる共押出成形品（請求項４）、
熱可塑性樹脂が、ポリ塩化ビニル系樹脂組成物、ポリカーボネート系樹脂組成物、ＡＢＳ系樹脂組成物から選ばれる少なくとも１種である請求項１〜４のいずれか１項に記載の共押出成形品（請求項５）、
フィルム又はシートである請求項１〜５のいずれかに記載の共押出成形品（請求項６）、
に関する。
That is, the present invention
A methacrylic resin (C) obtained by polymerizing a methacrylic ester polymer (A) in the presence of acrylic ester-based crosslinked elastic particles (B),
The methacrylic acid ester polymer (A) is obtained by copolymerizing a monomer mixture containing 20 to 100% by weight of methacrylic acid alkyl ester and 0 to 80% by weight of acrylic acid alkyl ester,
A monomer mixture containing (a) 50 to 100% by weight of an acrylic acid alkyl ester and 50 to 0% by weight of a methacrylic acid alkyl ester, (b) two acrylate ester-based crosslinked elastic particles (B) per molecule It is obtained by copolymerizing the above-mentioned polyfunctional monomer having a non-conjugated double bond, (c) the ultraviolet absorber represented by the general formula (1), and the copolymerization ratio of the ultraviolet absorber is acrylic acid. 0.01 to 30 parts by weight with respect to 100 parts by weight of the ester-based crosslinked elastic particles (B),
And the methacrylic resin (C) whose content of acrylic ester-based crosslinked elastic particles (B) with respect to the methacrylic resin (C) is 5 to 60% by weight,
A co-extrusion product that is laminated on a thermoplastic resin by co-extrusion.

(Wherein X is H or halogen, R ₁ is H, methyl 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.) (Claim 1)
The addition amount of the polyfunctional monomer in the acrylate-based crosslinked elastic particles (B) is 0.05 to 20 parts by weight with respect to 100 parts by weight of the monomer mixture. Co-extruded product (claim 2),
The average particle diameter of the acrylic ester-based crosslinked elastic particles (B) is from 600 to 2500 共, The co-extruded product according to claim 1 or 2 (claim 3),
A coextrusion molded product obtained by laminating a methacrylic resin composition containing 40% by weight or more of the methacrylic resin (C) according to any one of claims 1 to 3 on a thermoplastic resin by coextrusion (claim 4). ),
The co-extrusion product according to any one of claims 1 to 4, wherein the thermoplastic resin is at least one selected from a polyvinyl chloride resin composition, a polycarbonate resin composition, and an ABS resin composition. Claim 5),
A co-extruded product according to any one of claims 1 to 5 which is a film or sheet (claim 6),
About.

（式中、ＸはＨまたはハロゲン、Ｒ₁はＨ、メチルまたは炭素数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またはメチルである。）（請求項１）、
アクリル酸エステル系架橋弾性体粒子（Ｂ）の平均粒子径が６００Å〜２５００Åである事を特徴とする請求項１に記載のメタクリル系樹脂（請求項２）、
請求項１又は請求項２に記載のメタクリル系樹脂（Ｃ）を４０重量％以上含む事を特徴とするメタクリル系樹脂組成物（請求項３）、
請求項３に記載の樹脂組成物を成形してなるフィルム（請求項４）、
請求項３に記載のメタクリル系樹脂組成物を共押出しによって熱可塑性樹脂に積層することを特徴とする共押出成形品（請求項５）、
熱可塑性樹脂が、ポリ塩化ビニル系樹脂組成物、ポリカーボネート系樹脂組成物、ＡＢＳ系樹脂組成物から選ばれる少なくとも１種であることを特徴とする請求項５記載の共押出成形品（請求項６）、
請求項４のフィルムを被積層体に積層して得られる積層品。（請求項７）、
に関する。

(Wherein X is H or halogen, R ₁ is H, methyl 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.) (Claim 1),
The methacrylic resin (Claim 2) according to claim 1, wherein the average particle diameter of the acrylic ester-based crosslinked elastic particles (B) is 600 to 2500 mm,
A methacrylic resin composition (Claim 3) comprising 40% by weight or more of the methacrylic resin (C) according to Claim 1 or Claim 2,
A film formed by molding the resin composition according to claim 3 (claim 4),
A co-extruded product, wherein the methacrylic resin composition according to claim 3 is laminated on a thermoplastic resin by co-extrusion (claim 5),
The co-extruded product according to claim 5, wherein the thermoplastic resin is at least one selected from a polyvinyl chloride resin composition, a polycarbonate resin composition, and an ABS resin composition (claim 6). ),
A laminate obtained by laminating the film of claim 4 on a laminate. (Claim 7),
About.

  The methacrylic resin of the present invention and the film obtained therefrom are excellent in bending crack resistance after the weather resistance test.

  The methacrylic resin (C) in the present invention is composed of a methacrylic ester polymer (A) and acrylate cross-linked elastic particles (B). It is obtained by polymerizing the methacrylic ester polymer (A) in the presence. Since the acrylic ester-based crosslinked elastic particles (B) are copolymerized with two or more polyfunctional monomers having non-conjugated reactive double bonds per molecule, the resulting polymer is crosslinked. Shows elasticity. In addition, one reactive functional group (double bond) of the polyfunctional monomer remaining unreacted during polymerization of the acrylic ester-based crosslinked elastic particles (B) becomes a graft crossing point, and methacrylic acid During polymerization of the ester polymer (A), a certain proportion of the methacrylic ester polymer (A) is grafted onto the acrylate ester crosslinked elastic particles (B). Thus, when the obtained methacrylic resin (C) is processed and molded, the acrylate-based crosslinked elastic particles (B) are discontinuously and uniformly dispersed in the methacrylic resin (C).

  The methacrylic acid ester polymer (A) in the present invention is obtained by polymerizing a monomer mixture containing 20 to 100% by weight of methacrylic acid alkyl ester and 0 to 80% by weight of acrylic acid alkyl ester in at least one stage. It is. More preferably, it is 60-100 weight% of methacrylic acid alkylesters, and 0-40 weight% of acrylic acid alkylesters. If the alkyl acrylate is in the range of 0 to 80% by weight, the heat resistance of the film that can be formed from the resulting methacrylic resin composition becomes good, which is preferable.

  In the present invention, the methacrylic acid alkyl ester constituting the methacrylic acid ester polymer (A) is preferably one having 1 to 12 carbon atoms in the alkyl group from the viewpoint of polymerization reactivity and cost. But you can. Specific examples thereof include, for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate and the like. More than one species may be used in combination.

  The acrylic acid alkyl ester constituting the methacrylic acid ester polymer (A) in the present invention preferably has 1 to 12 carbon atoms in the alkyl group from the viewpoint of polymerization reactivity and cost, and is linear or branched. But you can. Specific examples thereof include, for example, 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.

  In the methacrylic acid ester polymer (A) of the present invention, an ethylenically unsaturated monomer copolymerizable with methacrylic acid alkyl ester and acrylic acid alkyl ester may be copolymerized as required. It doesn't matter. Examples of these copolymerizable ethylenically unsaturated monomers include vinyl halides such as vinyl chloride and vinyl bromide, vinyl cyanides such as acrylonitrile and methacrylonitrile, vinyl formate, vinyl acetate, and vinyl propionate. Vinyl esters such as styrene, vinyl toluene, aromatic vinyl derivatives such as α-methylstyrene, vinylidene halides such as vinylidene chloride and vinylidene fluoride, acrylic acid such as acrylic acid, sodium acrylate, calcium acrylate, and salts thereof , Alkyl acrylate derivatives such as β-hydroxyethyl acrylate, dimethylaminoethyl acrylate, glycidyl acrylate, acrylamide, N-methylol acrylamide, etc., methacrylic acid, sodium methacrylate, calcium methacrylate, etc. Examples include lauric acid and its salts, methacrylamide, β-hydroxyethyl methacrylate, dimethylaminoethyl methacrylate, methacrylic acid alkyl ester derivatives such as glycidyl methacrylate, etc., and two or more of these monomers are used in combination. Also good.

  The acrylic ester-based crosslinked elastic particle (B) used in the present invention is a monomer mixture containing 50 to 100% by weight of acrylic acid alkyl ester and 50 to 0% by weight of methacrylic acid alkyl ester, and 2 or more per molecule. A mixture composed of a polyfunctional monomer having a non-conjugated double bond and an ultraviolet absorber represented by the general formula (1) are copolymerized in at least one stage.

（式中、ＸはＨまたはハロゲン、Ｒ₁はＨ、メチルまたは炭素数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またはメチルである。）
本発明のアクリル酸エステル系架橋弾性体粒子（Ｂ）において用いられる単量体混合物は、より好ましくは、アクリル酸アルキルエステル６０〜１００重量％およびメタクリル酸アルキルエステル４０〜０重量％である。メタクリル酸アルキルエステルが５０〜０重量％の範囲であれば、得られるメタクリル系樹脂から形成しうるフィルムの耐折曲げ割れ性が良好となり、好ましい。

(Wherein X is H or halogen, R ₁ is H, methyl 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.)
The monomer mixture used in the acrylic ester-based crosslinked elastic particles (B) of the present invention is more preferably 60-100% by weight of alkyl acrylate and 40-0% by weight of methacrylic acid. When the methacrylic acid alkyl ester is in the range of 50 to 0% by weight, the folding resistance of the film that can be formed from the resulting methacrylic resin is improved, which is preferable.

  In the acrylic ester-based crosslinked elastic particles (B) of the present invention, if necessary, an ethylenically unsaturated monomer copolymerizable with a methacrylic acid alkyl ester and an acrylic acid alkyl ester is copolymerized. It doesn't matter.

  Examples of the polyfunctional monomer used in the acrylic ester-based crosslinked elastic particle (B) of the present invention include allyl methacrylate, allyl acrylate, triallyl cyanurate, triallyl isocyanurate, Diallyl phthalate, diallyl maleate, 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, tetramethylol methane tetramethacrylate, tetramethylol methane tetraacrylate, di Ropirenguriko - dimethacrylate - DOO and dipropylene glyco - diacrylate - DOO, and these two or more kinds may be used in combination.

  The addition amount of the polyfunctional monomer in the acrylic ester-based crosslinked elastic particles (B) of the present invention is preferably 0.05 to 20 parts by weight with respect to 100 parts by weight of the monomer mixture. 1-10 weight part is more preferable. When the addition amount of the polyfunctional monomer is in the range of 0.05 to 20 parts by weight, the impact resistance and the bending cracking resistance of the film that can be formed from the methacrylic resin can be compatible, which is preferable.

  Specific examples of the acrylic acid alkyl ester, the methacrylic acid alkyl ester, and the ethylenically unsaturated monomer copolymerizable therewith used in the acrylic acid ester-based crosslinked elastic particle (B) of the present invention are the methacrylic acid esters. In the description of the polymer (A), those listed can be used in the same manner. The average particle diameter of the acrylate ester-based crosslinked elastic particles (B) in the present invention is preferably 600 to 2500 and more preferably 700 to 2000. If the acrylic ester-based crosslinked elastic particles (B) are 600 to 2500 mm, the transparency, impact resistance, and bending crack resistance of the film that can be formed from the resulting methacrylic resin are good, which is preferable.

  In the present invention, the content of the acrylic ester-based crosslinked elastic particles (B) is preferably 5 to 60% by weight, more preferably 10 to 40% by weight when the entire methacrylic resin (C) is 100% by weight. Preferably, 15 to 35% by weight is more preferable. If the content of the acrylic ester-based crosslinked elastic particles (B) is 5 to 60% by weight, the impact resistance of the film that can be formed from the resulting methacrylic resin, the bending resistance, and the hardness of the film, Formability is good, which is preferable.

  The ultraviolet absorber represented by the general formula (1) in the present invention is 2- (2′-hydroxy-5′-methacryloyloxyethylphenyl) -2H-benzotriazole, and 2- (2′-hydroxy-5 ′). -Acryloyloxyethylphenyl) -2H-benzotriazole, 2- (2'-hydroxy-5'-methacryloyloxyethylphenyl) -2H-benzotriazole, 2- (2'-hydroxy-5'-methacryloyloxyethylphenyl) -5-chloro-2H-benzotriazole, 2- (2'-hydroxy-5'-methacryloyloxypropylphenyl) -2H-benzotriazole, 2- (2'-hydroxy-5'-methacryloyloxyethyl-3'- t-butylphenyl) -2H-benzotriazole and the like. 2- (2'-Hydroxy-5'-methacryloyloxyethylphenyl) -2H-benzotriazole is preferred because of cost and handleability.

  The copolymerization ratio of the ultraviolet absorber represented by the general formula (1) in the present invention is preferably 0.01 to 30 parts by weight with respect to 100 parts by weight of the acrylate ester-based crosslinked elastic particles (B). -25 parts by weight is more preferable, 0.01-20 parts by weight is further preferable, and 0.05-20 parts by weight is particularly preferable. The ultraviolet absorber represented by the general formula (1) is at least copolymerized with the acrylate-based crosslinked elastic particles (B), and may be copolymerized with the methacrylic ester-based polymer (A). It doesn't matter. If the copolymerization ratio of the ultraviolet absorber represented by the general formula (1) is in the range of 0.01 to 30 parts by weight, the impact resistance, bending crack resistance, and weather resistance test of the film that can be formed from the resulting methacrylic resin. Later resistance to bending cracking is improved, which is preferable.

  The production method of the methacrylic resin (C) in the present invention is not particularly limited, and any of an emulsion polymerization method, an emulsion-suspension polymerization method, a suspension polymerization method, a bulk polymerization method or a solution polymerization method can be applied. The emulsion polymerization method is particularly preferable from the viewpoint of easy control of the polymerization behavior.

  When the emulsion polymerization method is used, the monomer mixture can be added to the aqueous phase by adding all or part of the monomer mixture to the aqueous phase simultaneously, The continuous addition which adds little by little at a continuous rate is mentioned. In the case of continuous addition, in order to reduce the scale after polymerization (resin polymerized outside the emulsified micelles), add water and an emulsifier to the monomer mixture and stir and add the emulsified beforehand. Is also possible.

  The method for copolymerizing the ultraviolet absorber represented by the general formula (1) in the present invention is not particularly limited, but is copolymerized during the production of the acrylic ester-based crosslinked elastic particles (B) and the methacrylic ester-based polymer (A). It is preferable to do. As the copolymerization method, an emulsion polymerization method, an emulsion-suspension polymerization method, a suspension polymerization method, a bulk polymerization method or a solution polymerization method can be applied, but from the same viewpoint as the production method of the methacrylic resin (C). An emulsion polymerization method is particularly preferred.

  The initiator in the polymerization of the acrylic ester-based crosslinked elastic particles (B) of the present invention is not particularly limited as long as the object of the present invention can be achieved, but organic peroxides, inorganic peroxides, azo Initiators such as compounds can be used. Specifically, for example, t-butyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, succinic acid peroxide, peroxymaleic acid t-butyl ester, cumene hydroper Organic peroxides such as oxide and benzoyl peroxide, inorganic peroxides such as potassium persulfate and sodium persulfate, and oil-soluble initiators such as azobisisobutyronitrile are also used. These may be used alone or in combination of two or more. These initiators are combined with reducing agents such as sodium sulfite, sodium thiosulfate, sodium formaldehyde sulfoxylate, ascorbic acid, hydroxyacetone acid, ferrous sulfate, ferrous sulfate and disodium ethylenediaminetetraacetate It may also be used as a normal redox type initiator.

  The organic peroxide is an inorganic reducing agent such as a divalent iron salt and / or formaldehyde sulfoxylate soda, reducing sugar, ascorbic acid and the like from the viewpoint of polymerization stability and particle size control. It is preferably used as a redox initiator in combination with an organic reducing agent.

  The surfactant used for the emulsion polymerization is not particularly limited, and any surfactant for normal emulsion polymerization can be used. Specifically, for example, anionic surfactants such as sodium alkyl sulfonate, sodium alkyl benzene sulfonate, sodium dioctyl sulfosuccinate, sodium lauryl sulfate, sodium fatty acid, alkylphenols, aliphatic alcohols, etc. And nonionic surfactants such as reaction products of olefins with propylene oxide and ethylene oxide. These surfactants may be used alone or in combination of two or more. Further, a cationic surfactant such as an alkylamine salt may be used.

  The latex of the methacrylic resin (C) obtained by emulsion polymerization is obtained by subjecting the methacrylic resin (C) to an aqueous phase by ordinary coagulation, washing and drying operations, or by treatment such as spray drying and freeze drying. Separated and recovered.

  In the methacrylic resin (C) of the present invention, polyglutarimide, glutaric anhydride polymer, lactone cyclized methacrylic resin, methacrylic resin, polyethylene terephthalate resin, polybutylene terephthalate resin, and the like are blended as necessary. Is also possible. The blending method is not particularly limited as long as the object of the present invention can be achieved.

  The proportion of the methacrylic resin (C) of the present invention in the resin obtained by blending is preferably 40 to 100% by weight, more preferably 50 to 90% by weight, and still more preferably 60 to 80% by weight. If the ratio of the methacrylic resin (C) in the resin obtained by blending is in the range of 40 to 100% by weight, the resulting film has favorable impact resistance and bending cracking resistance, which is preferable.

  In the methacrylic resin (C) of the present invention, an inorganic pigment or an organic dye is used for coloring, and an antioxidant, a heat stabilizer, an ultraviolet absorber, an ultraviolet ray is used to further improve the stability to heat and light. Stabilizers or the like, or antibacterial agents, deodorants, lubricants and the like may be added alone or in combination of two or more.

  The methacrylic resin (C) obtained in the present invention can be processed into various molded products by various plastic processing methods such as injection molding, extrusion molding, blow molding and compression molding.

  The methacrylic resin (C) of the present invention is particularly useful as a film, and is processed satisfactorily by, for example, an ordinary melt extrusion method such as an inflation method, a T-die extrusion method, a calendar method, or a solvent casting method. The In addition, when forming a film, if necessary, both surfaces of the film are brought into contact with a roll or a metal belt at the same time, 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 better film. Further, depending on the purpose, the film can be modified by biaxial stretching or the like.

  10-300 micrometers is preferable and, as for the thickness of the film obtained from the methacrylic resin (C) of this invention, 10-200 micrometers is more preferable. If the thickness of the film is in the range of 10 to 300 μm, the processability of the film and the transparency of the film are good, which is preferable.

  Moreover, the film obtained from the methacrylic resin (C) of the present invention can reduce the gloss of the film surface, if necessary. The method is not particularly limited as long as the object of the present invention can be achieved. For example, the method can be carried out by a method of kneading an inorganic filler or crosslinkable polymer particles with a methacrylic resin (C). is there. Further, the gloss of the film surface can be reduced by embossing the obtained film.

  The methacrylic resin (C) of the present invention can be laminated on a thermoplastic resin by coextrusion. The method of co-extrusion is not particularly limited, and ordinary co-extrusion molding and multilayer extrusion molding are useful. For example, a typical extrusion co-extrusion method such as a profile extrusion method, a T-die extrusion method, an inflation method or a calender method. It is processed well by etc. In addition, when the molded product to be obtained is a film or sheet, if necessary, the same is applied to the roll or metal belt heated to a temperature equal to or higher than the glass transition temperature by bringing both surfaces into contact with the roll or metal belt. By bringing them into contact, it is possible to obtain a film or sheet having better surface properties. Further, depending on the purpose, it is possible to modify the multilayer sheet by biaxial stretching.

  The thermoplastic resin to which the methacrylic resin (C) of the present invention can be coextruded includes polyvinyl chloride resin, polycarbonate resin, ABS resin, AS resin, MBS resin, MS resin, styrene resin, methacrylic resin Examples thereof include compositions such as a series resin, a polyglutarimide, a glutaric anhydride polymer, a lactone cyclized methacrylic resin, a polyethylene terephthalate resin, and a polybutylene terephthalate resin, and two or more of these compositions may be used in combination. From the viewpoint of compatibility and industrial viewpoint, a composition of polyvinyl chloride resin, polycarbonate resin, or ABS resin is preferable.

  The polyvinyl chloride resin in the present invention includes not only vinyl chloride homopolymers, but also copolymers with other monomers such as vinyl chloride and vinyl acetate, and post-chlorinated chlorinated vinyl chloride resins. . Soft vinyl chloride resin is also included.

  The thickness of the methacrylic resin (C) of the present invention at the time of co-extrusion is preferably 10 μm to 5 mm, more preferably 10 μm to 3 mm. If the thickness is less than 10 μm, molding tends to be difficult, and if it exceeds 5 mm, the transparency tends to decrease.

  The film obtained from the methacrylic resin composition of the present invention can be used by being laminated on a laminate. The laminate is not particularly limited as long as the object of the present invention can be achieved, and examples thereof include inorganic articles such as metals and ceramics, and organic articles such as plastic, wood, and leather. As a method of laminating the film, laminating, wet laminating, applying laminating, applying and laminating an adhesive to the laminated body, dry laminating, extrusion laminating, hot melt laminating And so on.

  As a method of laminating a film on a plastic part, the film is placed in a mold and then placed in a mold after insert molding or laminate injection press molding in which resin is filled by injection molding, or after the film is preformed. In-mold molding in which resin is filled by injection molding can be used.

  The film laminate obtained from the methacrylic resin composition of the present invention is used as a substitute for painting such as furniture, automobile interior materials, automobile exterior materials, roofs, rain gutters, outer walls, fences, piles, window frames, bathroom equipment, wallpaper, It can be used for building materials such as flooring materials, household goods, furniture and electrical equipment housings, OA equipment housings such as facsimiles, and parts of electrical or electronic devices. In addition, as molded products, lighting lenses, automobile headlights, optical lenses, optical fibers, optical disks, liquid crystal light guide plates, liquid crystal films, medical supplies that require sterilization, microwave oven cooking containers, household appliance housings, It can be used for toys or recreational items.

  EXAMPLES Next, although this invention is demonstrated further in detail based on an Example, this invention is not limited only to these Examples.

  In addition, each measuring method of the physical property measured in the following Examples and Comparative Examples is as follows.

(Evaluation of polymerization conversion)
The obtained methacrylic resin (C) latex was dried in a hot air dryer at 120 ° C. for 1 hour to determine the amount of solid components, and the polymerization conversion rate (%) was calculated by 100 × solid component amount / charged monomer (%). ) Was calculated.

(Evaluation of average particle diameter of acrylic ester-based crosslinked elastic particles (B))
The obtained film was photographed with a transmission electron microscope (JEM-1200EX, manufactured by JEOL Ltd.) with an acceleration voltage of 80 kV and a RuO ₄ stained ultrathin section method. From the obtained photograph, acrylate-based crosslinked elastic particles ( B) 100 images were selected at random and the average value of their particle sizes was determined.

(Evaluation of average particle diameter of latex)
Using the obtained methacrylic resin (C) latex diluted to a solid content concentration of 0.02% as a sample, from a light transmittance at a wavelength of 546 nm using a spectrophotometer (manufactured by HITACHI, Spectrophotometer U-2000) The average particle size was determined.

(Evaluation of transparency)
For the transparency of the obtained film, haze was measured at a temperature of 23 ° C. ± 2 ° C. and a humidity of 50% ± 5% in accordance with JIS K6714.

(Evaluation of pencil hardness)
The pencil hardness of the obtained film was measured according to JIS S-1005.

(Evaluation of bending crack resistance)
The obtained film was bent 180 degrees once in a 25 ° C. atmosphere, and the change in the bent portion was visually evaluated.
○: No cracking is observed ×: Cracking is observed

(Evaluation of formability)
Film formation was carried out continuously for 3 hours, the operating conditions were observed, and evaluation was performed according to the following criteria.
○: The film has a uniform thickness and can be formed without breakage.
X: The film thickness is uneven or the film is cut.

(Evaluation of bending cracking resistance after weather resistance test)
The obtained film was irradiated with high-illuminance xenon (SC750-WA type, manufactured by Suga Test Instruments Co., Ltd.) under the conditions of 89 ° C. and 162 W / m ² until the energy amount of 430 MJ and 580 MJ was reached. The film was evaluated according to the evaluation method for bending cracking resistance.

(Evaluation of bleeding property of UV absorber)
Film formation was carried out continuously for 3 hours, the state of adhesion of the UV absorber to the cooled first roll was observed, and evaluation was performed according to the following criteria.
○: Adhesion to the cooling roll is not recognized.
X: Adhesion to a cooling roll is recognized.

In the production examples, examples and comparative examples, “parts” represents parts by weight and “%” represents% by weight. Abbreviations represent the following substances.
BA: butyl acrylate MMA: methyl methacrylate CHP: cumene hydroperoxide tDM: tertiary decyl mercaptan AlMA: allyl methacrylate RUVA: 2- (2'-hydroxy-5'-methacryloyloxyethylphenyl) -2-H- Benzotriazole (manufactured by Otsuka Chemical Co., Ltd., RUVA-93).

(Production Example 1) Production of methacrylic resin composition The following substances were charged into an 8 L polymerization apparatus equipped with a stirrer.
Deionized water 200 parts Sodium dioctylsulfosuccinate 0.25 parts Sodium formaldehyde sulfoxylate 0.15 parts Ethylenediaminetetraacetic acid-2-sodium 0.001 parts Ferrous sulfate 0.00025 parts Nitrogen in the polymerization machine After sufficiently substituting with gas and substantially free of oxygen, the internal temperature was set to 60 ° C., and the monomer mixture (B) shown in (1) of Table 1 <that is, BA 90 wt% and MMA 10 wt% 30 parts of a monomer mixture consisting of 1 part of AlMA and 0.2 part of CHP and 100 parts of RUVA (in the general formula (1), X is H, R ₁ is H, R ₂ is methylene group, was added R ₃ is a methyl group) 0.5 parts> continuously at a rate of 10 parts / hour, after completion of the addition, continued for a further 0.5 hour of polymerization, acrylic ester cross-linked elastic body particle The (B) was obtained. The polymerization conversion rate was 99.5%.

その後、ジオクチルスルフォコハク酸ナトリウム０．０５部を仕込んだ後、内温を６０℃にし、表１中（１）に示した単量体混合物（Ａ）＜すなわち、ＢＡ１０重量％およびＭＭＡ９０重量％からなる単量体混合物１００部に対しｔＤＭ０．５部およびＣＨＰ０．５部からなる単量体混合物７０部＞を１０部／時間の割合で連続的に添加し、さらに１時間重合を継続し、メタクリル系樹脂（Ｃ）を得た。重合転化率は９８．５％であった。得られたラテックスを塩化カルシウムで塩析、凝固し、水洗、乾燥して樹脂粉末（１）を得た。

Thereafter, 0.05 part of sodium dioctylsulfosuccinate was charged, the internal temperature was adjusted to 60 ° C., and the monomer mixture (A) shown in (1) in Table 1 <that is, BA 10% by weight and MMA 90% by weight 70 parts of monomer mixture consisting of 0.5 parts of tDM and 0.5 part of CHP> was continuously added at a rate of 10 parts / hour to 100 parts of the monomer mixture consisting of, and polymerization was continued for another hour. A methacrylic resin (C) was obtained. The polymerization conversion rate was 98.5%. The obtained latex was salted out and coagulated with calcium chloride, washed with water and dried to obtain a resin powder (1).

（製造例２〜４、６〜９、１２）
単量体組成を表１のように変更した以外は、製造例１と同様に重合を行い、凝固、水洗、乾燥して樹脂粉末（２）〜（４）、（６）〜（９）および（１２）を得た。但し、製造例（７）では重合中にラテックスが凝集した為、樹脂粉体（７）が得られなかった。

(Production Examples 2-4, 6-9, 12)
Except that the monomer composition was changed as shown in Table 1, polymerization was performed in the same manner as in Production Example 1, coagulated, washed with water, and dried to obtain resin powders (2) to (4), (6) to (9) and (12) was obtained. However, in the production example (7), since the latex aggregated during the polymerization, the resin powder (7) could not be obtained.

(Production Examples 5, 10, 11, 13)
Polymerization was carried out in the same manner as in Production Example 1 except that the sodium dioctylsulfosuccinate initially charged and the monomer composition were changed as shown in Table 1, and the average particle size of the latex was changed by changing the amount of sodium dioctylsulfosuccinate. Was obtained, solidified, washed with water and dried to obtain resin powders (5), (10), (11) and (13).
(Production Example 14)
The monomer mixture (B) and the monomer mixture (B) were polymerized in the same manner as in Production Example 1 except that 0.05 parts of sodium dioctylsulfosuccinate after polymerization was not charged, solidified, washed with water, and dried. Resin powder (15) was obtained.

(Production Example 15)
MMA-EA copolymer produced by suspension polymerization (Sumitomo Chemical Co., Ltd. Sumipex EX: copolymer consisting of about 95% by weight of MMA and about 5% by weight of EA, reduced viscosity 0.30 dl / g) was used. .

(Examples 1, 3-8, Comparative Examples 2-5)
The obtained resin powder was melt-kneaded using a single-screw extruder with a 40 mmφ vent at a cylinder temperature of 240 ° C., and pelletized. In addition, in Production Example (6), 2 parts of Tinuvin P (made by Ciba Special Chemical Co.) represented by the structural formula (2) as an ultraviolet absorber was blended with the obtained resin powder (6) and then melt-kneaded. And pelletized. The obtained pellets were molded at a die temperature of 240 ° C. using a 40 mmφ extruder with a T-die (manufactured by Nakamura Industries Co., Ltd., NEX040395) to obtain a film having a thickness of 100 μm.

（実施例２、比較例１）
得られた樹脂粉末を、表２に示すように配合し、混合機（（株）カワタ製、スーパーフローター型式ＳＦＣ−５０）にて３分間ブレンドした以外は実施例１と同様にペレット化、成形し、厚み１００μｍのフィルムを得た。

(Example 2, Comparative Example 1)
The obtained resin powder was blended as shown in Table 2 and pelletized and molded in the same manner as in Example 1 except that blending was performed for 3 minutes with a mixer (manufactured by Kawata, Super Floater Model SFC-50). Thus, a film having a thickness of 100 μm was obtained.

  Various characteristics using the obtained film were evaluated, and the results are shown in Table 2.

メタクリル系樹脂（Ｃ）の単量体組成比および紫外線吸収剤の共重合条件が、本発明の範囲を外れると、耐候性試験後の耐折り曲げ割れ性に優れたフィルムを得ることができなかった。

When the monomer composition ratio of the methacrylic resin (C) and the copolymerization conditions of the ultraviolet absorber were outside the scope of the present invention, a film excellent in bending crack resistance after the weather resistance test could not be obtained. .

Claims (6)

A methacrylic resin (C) obtained by polymerizing a methacrylic ester polymer (A) in the presence of acrylic ester-based crosslinked elastic particles (B),
The methacrylic acid ester polymer (A) is obtained by copolymerizing a monomer mixture containing 20 to 100% by weight of methacrylic acid alkyl ester and 0 to 80% by weight of acrylic acid alkyl ester,
A monomer mixture containing (a) 50 to 100% by weight of an acrylic acid alkyl ester and 50 to 0% by weight of a methacrylic acid alkyl ester, (b) two acrylate ester-based crosslinked elastic particles (B) per molecule It is obtained by copolymerizing the above-mentioned polyfunctional monomer having a non-conjugated double bond, (c) the ultraviolet absorber represented by the general formula (1), and the copolymerization ratio of the ultraviolet absorber is acrylic acid. 0.01 to 30 parts by weight with respect to 100 parts by weight of the ester-based crosslinked elastic particles (B),
And the methacrylic resin (C) whose content of acrylic ester-based crosslinked elastic particles (B) with respect to the methacrylic resin (C) is 5 to 60% by weight,
A co-extrusion product that is laminated on a thermoplastic resin by co-extrusion.

(Wherein X is H or halogen, R ₁ is H, methyl 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.)   The addition amount of the polyfunctional monomer in the acrylate-based crosslinked elastic particles (B) is 0.05 to 20 parts by weight with respect to 100 parts by weight of the monomer mixture. Co-extrusion molded product   The co-extruded product according to claim 1 or 2, wherein the acrylic ester-based crosslinked elastic particles (B) have an average particle diameter of 600 to 2500 mm.   A coextrusion molded product obtained by laminating a methacrylic resin composition containing 40% by weight or more of the methacrylic resin (C) according to any one of claims 1 to 3 on a thermoplastic resin by coextrusion.   The coextrusion molded product according to any one of claims 1 to 4, wherein the thermoplastic resin is at least one selected from a polyvinyl chloride resin composition, a polycarbonate resin composition, and an ABS resin composition.   It is a film or a sheet, The coextruded product according to any one of claims 1 to 5.