JP2008013660A - Thermal decomposition-controlled methacrylic resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition suitable for making films excellent in heat resistance and chemical resistance. <P>SOLUTION: This methacrylate-based polymer (A) is obtained by copolymerizing monomers containing ≥93 pts.wt. of an alkyl methacrylate with 0.01 to 30 wt.% of a specific UV light absorbent. Or, the methacrylate-based polymer (A) is characterized by containing acrylate-based cross-linked elastic particles (B) containing an alkyl acrylate as a main component. The methacrylate-based polymer (A) can be processed to obtain a film having the characteristics. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a methacrylic resin in which thermal decomposition is suppressed and a film formed by molding the methacrylic resin.

  Polymethacrylate resins polymerized only from methacrylic acid ester monomers have excellent transparency, hardness, heat resistance, and chemical resistance, and are used in a wide range of fields. However, there is a drawback that thermal decomposition is likely to occur by heating at 250 to 300 ° C. In order to improve this, for example, a technique such as copolymerization of a methacrylic acid ester and an acrylic acid ester monomer is taken.

However, in the copolymerization with the acrylate monomer, it is necessary to use 10% by weight or more of the acrylate monomer with respect to the methacrylic acid ester monomer in order to suppress depolymerization. (Patent Documents 1 and 2)
JP 2004-137298 A JP 2004-137299 A

  MEANS TO SOLVE THE PROBLEM This invention solves the above-mentioned subject, the methacrylate ester type polymer which suppressed thermal decomposability, without impairing the heat resistance, hardness, transparency, and chemical resistance which methacrylate ester has, and methacryl containing this The present invention relates to a film that can be formed from an acid ester resin composition.

The present invention
A methacrylic acid ester monomer and an acrylic acid ester monomer (hereinafter referred to as a methacrylic acid ester monomer) are in a range of 93/7 to 100/0 by weight. A methacrylate ester-based polymer obtained by copolymerizing a monomer mixture in which the weight ratio of the ultraviolet absorbent represented by (1) is 100 / 0.01 to 100/30.

（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）に関する、
アクリル酸エステル系架橋弾性体（Ｂ）不在化において重合した際に得られるメタクリル酸エステル系重合体（Ｅ）を含有する請求項１記載のメタクリル酸エステル系重合体（請求項２）に関する、
当該グラフト重合の際にグラフトされないで単独重合体として存在するメタクリル酸エステル系重合体（Ｄ）を含有する請求項１又は請求項２記載のメタクリル酸エステル系重合体（請求項３）に関する、
アクリル酸エステル系架橋弾性体（Ｂ）存在下においてグラフト重合したアクリル酸エステル系グラフト重合体（Ｃ）を含有する請求項１〜請求項３のいずれかに記載のメタクリル酸エステル系重合体（請求項４）に関する、
請求項１〜４に記載のメタクリル酸エステル系重合体を成形してなるフィルム（請求項５）に関する、
請求項５に記載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６）に関する、
請求項５に記載のフィルムを共押出しによって熱可塑性樹脂に積層することにより得られる共押出成形品（請求項７）に関する、
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７記載の共押出成形品（請求項８）、に関するものである。

(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 ester polymer (Claim 2) according to claim 1, comprising a methacrylic ester polymer (E) obtained by polymerization in the absence of the acrylic ester cross-linked elastic body (B).
The methacrylic ester polymer (Claim 3) according to claim 1 or 2, comprising a methacrylic ester polymer (D) which is not grafted during the graft polymerization and exists as a homopolymer.
The methacrylic acid ester polymer according to any one of claims 1 to 3 containing the acrylate ester graft polymer (C) graft-polymerized in the presence of the acrylic ester cross-linked elastic body (B). Regarding item 4),
About the film (Claim 5) formed by shape | molding the methacrylate ester-type polymer of Claims 1-4,
Regarding a laminated product (Claim 6) obtained by laminating the film of claim 5 on a laminate.
Regarding a coextrusion molded article (Claim 7) obtained by laminating the film according to Claim 5 on a thermoplastic resin by coextrusion,
The co-extruded product according to claim 7, 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 8). ).

  In the methacrylic resin of the present invention, depolymerization at the time of processing is suppressed, and the resulting film has an effect of being excellent in chemical resistance and thermal decomposition resistance.

  The methacrylic ester polymer (A) of the present invention is a methacrylic ester polymer (E) obtained by polymerization in the absence of an acrylate ester cross-linked elastic body (B), and / or the graft polymerization. In this case, it contains at least a methacrylic ester polymer (D) which is not grafted and exists as a homopolymer. If necessary, it is graft-polymerized in the presence of an acrylate cross-linked elastic body (B). Acrylic ester-based graft polymer (C) (when (C) is used, only the graft portion of (C) is included in the constitution of the present invention) may be contained.

  In the methacrylic acid ester polymer (A) in the present invention, the methacrylic acid ester monomer and the acrylic acid ester monomer (hereinafter referred to as methacrylic acid ester monomer) have a weight ratio of 93/7 to 100/0. It is obtained by copolymerizing a monomer mixture having a weight ratio of 100 / 0.01 to 100/30 of the methacrylic acid ester monomer and the ultraviolet absorber represented by the general formula (1). The weight ratio of the methacrylic acid alkyl ester monomer to the acrylate monomer is more preferably 95/5 to 100/0, further preferably 97/3 to 100/0, and more preferably 100/0. Particularly preferred. A material containing 93% by weight or more of a methacrylic acid alkyl ester is preferable because transparency, hardness, heat resistance and chemical resistance are improved.

  The weight ratio of the methacrylic acid ester monomer to the ultraviolet absorber represented by the general formula (1) is more preferably 100 / 0.01 to 100/25, and 100 / 0.01 to 100/20. More preferably, it is particularly preferably 100 / 0.05 to 100/20. If it is the range of 100 / 0.01-100 / 30, the depolymerization at the time of a process will be suppressed and it 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.

  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 methacrylic ester polymer (A) of the present invention contains at least a methacrylic ester polymer (D) and / or a methacrylic ester polymer (E). The ester-based graft polymer (C) (when (C) is used, only the graft portion of (C) is included in the constitution of the present invention) may be contained.

  The acrylic ester-based crosslinked elastic particle (B) 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 two or more non-conjugated double molecules per molecule. A mixture of polyfunctional monomers having a bond is copolymerized.

  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, tetramethylolmethane tetramethacrylate, tetramethylolmethane tetraacrylate, di Ropirenguriko - dimethacrylate - DOO and dipropylene glyco - diacrylate - DOO, and these two or more kinds may be used in combination.

  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. Moreover, you may copolymerize the ultraviolet absorber shown by General formula (1) as needed.

  The production method of the methacrylic ester polymer (A) 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. However, the emulsion polymerization method is particularly preferable from the viewpoint of easy control of the polymerization behavior.

  In particular, as a method for producing a methacrylate ester-based polymer (A) containing acrylic ester-based crosslinked elastic particles (B) in one pot, in the presence of acrylic ester-based crosslinked elastic particles (B). The method of superposing | polymerizing is mentioned. According to this method, graft-modified acrylate-based crosslinked elastic particles (C) and ungrafted methacrylic ester-based heavy polymers are partially grafted onto the acrylate-based crosslinked elastic particles (B). Coalescence (D) is obtained. The acrylic ester-based crosslinked elastic particles (B) are uniformly dispersed in the methacrylate ester-based polymer (D) by graft modification, which is preferable from the viewpoint of transparency.

  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 it is preferably copolymerized during the production of the methacrylic ester polymer (A).

  The initiator in the polymerization of the methacrylic ester polymer (A) 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 compounds, etc. Initiators 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 graft ratio to the acrylic ester-based crosslinked elastic particles (B) is 30 to 200%, more preferably 50 to 200%, and most preferably 80 to 200%. If the graft ratio is in the range of 30 to 200%, the transparency is good, which is preferable.

  The latex of the methacrylic acid ester polymer (A) obtained by emulsion polymerization is treated by usual coagulation, washing and drying operations, or by spray-drying, freeze-drying, and the like. By introducing a water-soluble organic solvent such as THF, the methacrylic acid ester polymer (A) is separated and recovered from the aqueous phase.

  In the methacrylic acid ester polymer (A) of the present invention, if necessary, a hydrocarbon polymer such as polyglutarimide, glutaric anhydride polymer, lactone-cyclized methacrylic resin, methacrylic resin, polypropylene or polyethylene. , Polyacrylonitrile, polystyrene, polymethyl methacrylate-polystyrene copolymer, poly (meth) acrylamide, polyethylene terephthalate, polybutylene terephthalate, and the like can also be blended. The blending method is not particularly limited as long as the object of the present invention can be achieved.

  In the methacrylic acid ester polymer (A) of the present invention, an inorganic pigment or an organic dye is used for coloring, and an antioxidant, a heat stabilizer, an ultraviolet absorber is used to further improve the stability to heat and light. Agents, ultraviolet stabilizers, etc., or antibacterial agents, deodorizing agents, lubricants, etc. may be added alone or in combination of two or more.

  The methacrylic ester polymer (A) 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 acid ester polymer (A) of the present invention is particularly useful as a film, and is good, for example, by an ordinary melt extrusion method such as an inflation method, a T-die extrusion method, a calendar method, or a solvent casting method. To be processed. 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 equal to or 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 ester polymer (A) 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 ester polymer (A) 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 is carried out by a method of kneading an inorganic filler or crosslinkable polymer particles with a methacrylic ester polymer (A). Is possible. Further, the gloss of the film surface can be reduced by embossing the obtained film.

  The methacrylic ester polymer (A) 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 acid ester polymer (A) of the present invention can be co-extruded includes polyvinyl chloride resin, polycarbonate resin, ABS resin, AS resin, MBS resin, MS resin, and styrene resin. Examples include resins, methacrylic resins, polyglutarimides, glutaric anhydride polymers, lactone cyclized methacrylic resins, polyethylene terephthalate resins, polybutylene terephthalate resins, etc., and two or more of these compositions are used in combination. Also good. 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 ester polymer (A) of the present invention at the time of coextrusion 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 acid ester polymer (A) 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, laminating, laminating, laminating, laminating, hot melt laminating, applying an adhesive to the laminated body, and then drying and laminating the film. 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 the production examples, examples and comparative examples, “parts” represents parts by weight and “%” represents% by weight.
Each abbreviation represents the following substance.

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).

  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 polymer 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 from 100 × solid component amount / charged monomer (%).

(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.
(Measurement of graft ratio)
1 g of the obtained acrylic graft copolymer (A) was dissolved in 40 ml of methyl ethyl ketone, and centrifuged for 1 hour at a rotational speed of 3000 rpm and a temperature of 12 ° C. using a centrifuge (manufactured by Hitachi Koki Co., Ltd., CP60E). Insoluble and soluble components were separated. The obtained insoluble matter was calculated by the following formula as an acrylic ester graft polymer (C).
Graft ratio (%) = {(weight of insoluble matter of methyl ethyl ketone−weight of acrylic ester-based crosslinked elastic particle (B)) / weight of acrylic ester-based crosslinked elastic particle (B)} × 100
(Evaluation of thermal decomposability)
The weight loss rate at 200 ° C., 250 ° C., and 300 ° C. was evaluated using 100 ° C. as a starting point. The analysis was performed under the conditions of a nitrogen flow of 50 ml / min and a heating rate of 10 ° C./min.

(Evaluation of Tg)
The analysis was performed by DSC (manufactured by Seiko Instruments, hot air analyzer TMA-SS), and the measurement was performed under the conditions of a nitrogen flow of 50 ml / min and a heating rate of 10 ° C./min.

(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 chemical resistance)
Copatone (SS Healthcare Japan Co., Ltd.) is thinly applied to the obtained film at a temperature of 23 ° C., allowed to stand at 23 ° C. for 1 hour, and then left at 50 ° C. for 1 hour. The film surface was visually observed and evaluated.
○: Scraped without trace.
Δ: A slight trace is seen.
X: A trace can be clearly confirmed.

(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% 100 parts of the monomer mixture consisting of 30 parts of the monomer mixture consisting of 2 parts of AlMA and 0.2 part of CHP, and 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) 0.3 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、ＭＭＡ１００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、およびＲＵＶＡ（一般式（１）中の、ＸがＨ、Ｒ₁がＨ、Ｒ₂がメチレン基、Ｒ₃がメチル基）０．７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 set to 60 ° C., and the monomer mixture (A) shown in (1) in Table 1 <ie, a single amount consisting of 100% by weight of MMA 70 parts of a monomer mixture consisting of 0.5 parts of tDM and 0.5 parts of CHP with respect to 100 parts of the body mixture, and RUVA (in the general formula (1), X is H, R ₁ is H, R ₂ is a methylene group, R ₃ is a methyl group) 0.7 parts> was continuously added at a rate of 10 parts / hour, and further continued for 1 hour of polymerization, to obtain a methacrylic resin (C). 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２〜７）
最初に仕込むジオクチルスルフォコハク酸ナトリウムおよび単量体組成を表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）〜（７）を得た。
（製造例８）
単量体混合物（Ｂ）および単量体混合物（Ｂ）重合後のジオクチルスルフォコハク酸ナトリウム０．０５部を仕込まない以外は、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（８）を得た。

(Production Examples 2 to 7)
Polymerization is carried out in the same manner as in Production Example 1, except that the sodium dioctylsulfosuccinate and the monomer composition initially charged are changed as shown in Table 1, and then solidified, washed with water and dried to obtain resin powders (2) to ( 7) was obtained.
(Production Example 8)
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 (8) was thus obtained.

(Examples 1-4, Comparative Examples 1-4)
The obtained resin powder was blended as shown in Table 2 and blended for 3 minutes with a mixer (manufactured by Kawata Co., Ltd., Super Floater Model SFC-50). The cylinder temperature was set to 240 ° C., melt kneading was performed, and pelletization was performed. 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.

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

メタクリル酸エステル系重合体（Ａ）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、樹脂の熱分解が抑制できず、または／および、耐薬品性に優れたフィルムを得ることができなかった。

If the monomer composition ratio of the methacrylic ester polymer (A) and the copolymerization conditions of the UV absorber are outside the scope of the present invention, the thermal decomposition of the resin cannot be suppressed and / or the chemical resistance is improved. An excellent film could not be obtained.

Claims (8)

A methacrylic acid ester monomer and an acrylic acid ester monomer (hereinafter referred to as a methacrylic acid ester monomer) are in a range of 93/7 to 100/0 by weight. A methacrylate ester-based polymer obtained by copolymerizing a monomer mixture in which the weight ratio of the ultraviolet absorbent represented by (1) is 100 / 0.01 to 100/30.

(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 methacrylic ester polymer according to claim 1, comprising a methacrylic ester polymer (E) obtained by polymerization in the absence of the acrylic ester cross-linked elastic body (B).   The methacrylic ester polymer according to claim 1 or 2, comprising a methacrylic ester polymer (D) which is not grafted during the graft polymerization and exists as a homopolymer.   The methacrylic ester polymer according to any one of claims 1 to 3, comprising an acrylate graft polymer (C) graft-polymerized in the presence of the acrylate cross-linked elastic body (B).   The film formed by shape | molding the methacrylic ester polymer of Claims 1-4.   A laminate obtained by laminating the film according to claim 5 on a laminate.   A coextrusion molded article obtained by laminating the film according to claim 5 on a thermoplastic resin by coextrusion.   The co-extruded product according to claim 7, wherein the thermoplastic resin is at least one selected from a polyvinyl chloride resin composition, a polycarbonate resin composition, and an ABS resin composition.